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It would be convenient if we could achieve multi-component (organic and inorganic species) analysis using just one quartz fiber filter (QFF) as an aerosol collection medium. In general, QFF have been used for analyzing carbonaceous materials in aerosols. This study shows a nondestructive, rapid, and simple method using EDXRF (Energy Dispersive X-Ray Fluorescence spectrometry) that has secondary targets and three-dimensional polarization optics for analyzing inorganic multi-elements in aerosols collected on QFFs. Multi-element analysis can be achieved by using EDXRF coupled with fundamental parameter (FP) quantification, as speed of up to 900 s (15 min) per sample. The EDXRF-FP method shows good repeatability, with generally less than 5% variation when measuring each analyzed element. While the elemental concentrations in the blank QFFs in any lots examined in this study could be considered to be lower than the actual samples, the blank level of Ni cannot be ignored. The EDXRF-FP results for each element of the aerosols collected on QFF agreed well with ICP-MS and ICP-AES results. The temporal variations of the selected elements in aerosols obtained by EDXRF-FP showed very good agreement with those obtained by ICP-MS and AES, and thus this method is suitable for elucidating day-to-day variations of multi-elements in aerosols.

Accurate quantification of DNA is highly important in various fields. Determination of phosphorus by ICP-MS is one of the most effective methods for accurate quantification of DNA due to the fixed stoichiometry of phosphate to this molecule. In this paper, a smart and reliable method for accurate quantification of DNA fragments and oligodeoxythymidilic acids by hyphenated HPLC/ICP-MS equipped with a highly efficient interface device is presented. The interface was constructed of a home-made capillary-attached micronebulizer and temperature-controllable cyclonic spray chamber (IsoMist). As a separation column for DNA samples, home-made methacrylate-based weak anion-exchange monolith was employed. Some parameters, which include composition of mobile phase, gradient program, inner and outer diameters of capillary, temperature of spray chamber etc., were optimized to find the best performance for separation and accurate quantification of DNA samples. The proposed system could achieve many advantages, such as total consumption for small amount sample analysis, salt-tolerance for hyphenated analysis, high accuracy and precision for quantitative analysis. Using this proposed system, the samples of 20 bp DNA ladder (20, 40, 60, 80, 100, 120, 140, 160, 180, 200, 300, 400, 500 base pairs) and oligodeoxythymidilic acids (dT12–18) were rapidly separated and accurately quantified.

Adipose tissue-derived stem cells (ASCs) have shown promise in cell therapy because of their ability to self-renew damaged or diseased organs and easy harvest. To ensure the distribution and quantification of the ASCs injected from tail vein, several whole-body imaging techniques including fluorescence optical imaging with quantum dots (QDs) have been employed, but they may suffer from insufficient sensitivity and accuracy. Here, we report quantitative distribution of ASCs in various organs (heart, lung, liver, spleen, and kidney) of mice, which were intravenously injected with QDs-labeled ASCs (QDs-ASCs), through the detection of QDs-derived metallic components by inductively coupled plasma mass spectrometry (ICPMS). For accurate and precise determination, each organ was harvested and completely digested with a mixture of HNO(3) and H(2)O(2) in a microwave oven prior to ICPMS measurement, which was equipped with a microflow injection system and a laboratory-made capillary-attached micronebulizer. After optimization, 16 elements including major components (Cd, Se, and Te) of QDs and essential elements (Na, K, Mg, Ca, P, S, Mn, Fe, Co, Cu, Zn, Se, Sr, and Mo) were successfully determined in the organs. As compared to untreated mice, QDs-ASCs-treated mice showed significantly higher levels of Cd and Te in all organs, and as expected, the molar ratio of Cd to Te in each organ was in good agreement with the molar composition ratio in the QDs. This result indicates that the increment of Cd (or Te) can be used as a tracer for calculating the distribution of ASCs in mice organs. As a result of the calculation, 36.8%, 19.1%, 0.59%, 0.49%, and 0.25% of the total ASCs injected were estimated to be distributed in the liver, lung, heart, spleen, and kidney, respectively.

A new coprecipitation method using iron hydroxide was developed to preconcentrate rare earth elements (REEs) in natural water prior to determination by inductively coupled plasma mass spectrometry (ICP-MS). The precipitate was collected in a syringe filter, which was connected into an ultrasound-assisted on-line elution and ICP-MS measurement system for REEs. Nitrogen (120 mL min−1) was mixed in auxiliary gas of ICP-MS to get rid of the oxide spectral interference with the REEs' measurements. When 10 mL of water sample was used, the blanks of REEs were from 0.001 pg mL−1 of Tm and Lu to 0.22 pg mL−1 of La and Ce. Detection limits calculated from 3-fold standard deviation of blanks were from 0.0006 pg mL−1 of Tm to 0.21 pg mL−1 of Ce. Recoveries of all REEs were from 97.1% to 103.1% with good reproducibility (standard deviation less than 3.3%). The usefulness of the method was confirmed by comparing the analytical results of NMIJ CRM 7201-a obtained with the present method and those obtained with an established solid-phase extraction method.

A syringe-driven chelating column (SDCC) was applied to develop an on-line preconcentration/inductively coupled plasma mass spectrometry (ICP-MS) method for preconcentration and determination of rare earth elements (REEs) in seawater samples. The present on-line preconcentration system consists of only one pump, two valves, an SDCC, an ICP-MS, several connectors, and Teflon tubes. Optimizations of adsorption pH condition, sample loading flow rate, and integration range were carried out to achieve optimum measurement conditions for REEs in seawater sample. Six minutes was enough for a preconcentration and measurement cycle using 10 mL of seawater sample, where the detection limits for different REEs were in the range of 0.005 pg mL−1 to 0.09 pg mL−1. Analytical results of REEs in a seawater certified reference material (CRM), NASS-5, confirmed the usefulness of the present method. Furthermore, concentrations of REEs in Nikkawa Beach coastal seawater were determined and discussed with shale normalized REE distribution pattern.

A tandem preconcentration method integrating chelating resin adsorption and La coprecipitation was applied to an analysis of Lake Baikal water by high-resolution ICP-MS. As a result, 56 elements were determined in Lake Baikal water: Ca, Na, Mg, K, Si, Sr, B, Li, Ba, P, Fe, Al, Mo, Zn, Mn, Rb, U, As, V, Cu, Pb, W, Y, Cs, Se, Cr, Ni, Ti, Sb, Zr, Sn, Co, Cd, Rh, Te, Hf, Nb, Ru, Ga, Sc, Th, Bi, and all-rare earth elements (all-REEs), except for Pm. The concentrations of these elements covered a range of nine orders of magnitude, from approximately 17 microg mL(-1) of Ca to less than 50 fg mL(-1) of Tm. The elemental concentrations in Lake Baikal water were compared with reference data.

A lanthanum (La) coprecipitation method with low sample consumption was explored for the preconcentration of oxo-anion forming elements prior to a measurement by inductively coupled plasma mass spectrometry (ICP-MS). The preconcentration procedure was composed of two main steps: (1) the formation of a coprecipitate with the lowest possible La and (2) the redissolution of target analytes with minimal use of nitric acid, and the elimination of high concentration La from the analysis sample. Each step was performed in a 25 mL-volume syringe to reduce the sample consumption and to avoid contamination from the experimental environment. Various parameters, such as the concentration and volume of La added into the sample solution, the precipitation pH, the aging time, and the volume of HNO(3) were optimized to obtain good recoveries and high detection sensitivities for V, As, Sb, and W, which could be hardly recovered by solid-phase extraction using a chelating resin. The obtained method was evaluated through the analysis of seawater reference materials (CASS-4 and NASS-5). The recoveries exceeded 80%, and the observed values were in good agreement with the certified values.

PM10 samples were collected at an urban site of Nagoya City during September, 2003, to August, 2004, and annual variations of the concentrations of the elements in PM10 samples were examined by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The annual concentration variations of ca. 30 elements in ambient air were in the range from sub-ng m(-3) to several microg m(-3). From an evaluation by the enrichment factors of the elements, elements such as Al, Ca, Fe, Mg, Ti, Mn, Ba, Sr, Ce, La, Nd, Co, Cs, and Pr, in PM10 samples were found to have originated mostly from natural sources, while the elements such as S, Zn, Pb, Cu, Ni, Sb, Sn, Cd, Bi, W, Tl, and In originated from anthropogenic emission sources. Furthermore, in seasonal variations of the elemental concentrations of PM10 samples in ambient air, the elements originated mostly from natural sources provided significantly high concentrations in spring during the "Kosa" period (the dust season from March to May). On the other hand, the elements mainly from anthropogenic emission sources provided relatively higher concentrations in autumn and winter, which may be explained by the fact that the urban atmospheric structure is stabilized by the temperature-inversion layer formed over the city in those seasons. In addition, all of the elements provided significantly low concentrations in the summer, due to the dilution effect of the oceanic winds as well as due to the convection of air mass up to the high levels.

The determination of 52 impurity elements in niobium materials (niobium metal, niobium oxide (V), and niobium pentaethoxide) was performed by inductively coupled plasma mass spectrometry (ICP-MS) with on-line anion exchange matrix separation as well as direct nebulization. Niobium material samples were decomposed with a mixture of hydrofluoric acid and nitric acid to prepare 10% niobium solutions. In the on-line anion exchange matrix separation/ICP-MS, the niobium and hydrofluoric acid concentrations in sample solution were adjusted to 5% and ca. 8M, respectively. The solution was then injected into the carrier stream from the sample loop of injection valve to pass through an anion exchange resin column. In the anion exchange separation, niobium in the fluoro-complex form was adsorbed on the resin, while impurity elements were eluted. The eluted elements were introduced into ICP-MS for the determination of 25 impurity elements. On the other hand, 27 impurity elements could not be separated well from niobium matrix under the above anion exchange conditions, and then the sample solution with the niobium concentration of max. 0.2% containing internal standard elements was injected from the sample loop of injection valve directly to introduce into ICP-MS. As a result, 52 impurity elements in three kinds of niobium materials could be determined at the ng g(-1) level.

A multiply hyphenated HPLC/UV/ICP-MS system equipped with a fraction collection valve for subsequent MALDI-TOF-MS analysis was constructed, and its applicability to the speciation of metalloprotein...

The multielement determination of PM(10) (airborne particulate matter smaller than 10 microm) samples, which was collected by a high volume air sampler at the urban site of Nagoya City, was carried out by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The present analytical method was validated by analyzing urban particulate matter standard reference material of NIST SRM 1648. The analytical data for ca. 30 elements in PM(10) samples collected during a period from 8 September to 9 October, 2003, were obtained in the concentration range from sub-microg g(-1) to several-10 mg g(-1), but the data for 18 elements among ca. 30 elements were available for the characterization of PM(10) samples in ambient air, because of problems caused by the filter blanks. Then, the trends concerning the distributions of diverse elements in PM(10) samples were analyzed based on the enrichment factors and size distribution factors. The lithophile and siderophile elements were distributed more than 50% in coarse particle fraction (>2.1 microm), which was derived mainly from natural sources, such as soils and crustal minerals. On the other hand, chalcophile elements were distributed more than 50% in fine particle fraction (

An octadecylsilyl silica (ODS) column coated with phosphatidylcholine (PC) was prepared by using a dynamic coating method, and its separation characteristics were evaluated for direct sample inject...

Inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS) are the most powerful analytical methods for trace and ultratrace element analysis with high sensitivity as well as multielement capability, wide liner dynamic range and less interferences. The fundamentals, instrumentation, analytical feasibilities, and applications of these instruments are described.

Rare earth elements (REEs) in seawater were preconcentrated 20-fold (from 50 to 2.5 ml) by a chelating resin-packed minicolumn device and determined by inductively coupled plasma mass spectrometry (ICP-MS). The recoveries for REEs were in the range from 90% for Eu and Dy to 98% for Yb, and their standard deviations were less than 4%. The lower detection limits for REEs ranged from 0.06 ng l−1 for Lu to 0.5 ng l−1 for Sm. The analytical results for REEs in seawater reference materials (NASS-5, CASS-3, and CASS-4), the Take Island coastal seawater, and the Ise Bay coastal seawater were evaluated as the REE distribution patterns with shale-normalization and deep seawater-normalization. Slight relative enrichments of heavy REEs were observed in the Take Island coastal seawater and the Ise Bay coastal seawater, which might be attributed to the input from the river flows containing more dissolved heavy REEs. In addition, positive anomalies of Sm were found in the normalized REE distribution patterns for NASS-5, CASS-3, and CASS-4, which would be attributed to the contamination in the preparation process of reference materials by NRC.

Low flow-resistant alkyl methacrylate-based monolithic stationary phases of different hydrophobicity were constructed for reversed-phase capillary liquid chromatography by thermally initiated radical polymerization of respective methacrylate ester monomer with different alkyl chain (C2, C4, C6, C12, C18) and ethylene glycol dimethacrylate (EDMA) in a 250 microm i.d. fused silica capillary. The hydrophobicity was basically controlled by changing the length and/or the density of the alkyl-chain, while the composition and the ratio of porogenic solvent were adjusted to obtain highly permeable rigid monoliths with adequate column efficiency. Among the prepared monolithic stationary phases, C18-methacrylate monoliths polymerized from a binary porogenic solvent of isoamyl alcohol and 1,4-buthandiol exhibited the most promising performance in terms of hydraulic resistance and column efficiency. The pressure drops of 20-cm long monolithic columns were below approximately 0.4 MPa at a normal linear velocity of 1mm/s (a flow rate of 3 microL/min), and the numbers of theoretical plates for alkylbenzenes mostly exceeded 3000 plates/20 cm. The produced monolithic columns had good mechanical strength for high pressure and temperature, and could be properly operated even at a temperature of 80 degrees C and at a pressure of at least 33 MPa. At 80 degrees C, the theoretical plate numbers reached 6000 plates/20 cm because of the enhanced mass transfer. Due to the novel hydraulic resistance and mechanical strength, the separation time could be reduced 120-fold simply by raising the flow rate and column temperature.

The determination of 34 trace metals in a river water certified reference material (CRM), i.e. JSAC 0301-1, which was issued by the Japan Society for Analytical Chemistry in January 2004, was performed by ICP-MS with a high efficiency nebulizer after preconcentration with a laboratory-made chelating resin-packed minicolumn, with which trace metals were concentrated 100-fold from 50 mL of a river water sample to 0.5 mL of the final analysis solution. Trace metals in JSAC 0301-1 were observed in the concentration range from 19 microg L(-1) of Al to 0.000053 microg L(-1) of Bi. It was found that most of the concentrations of trace metals, including rare earth elements (REEs), in JSAC 0301-1 were lower than those in JAC 0031, which was also a previously issued CRM prepared with water from the same river as that of JSAC 0301-1. The low concentrations of trace metals in JSAC 0301-1 might be attributed to the fact that there was a heavy rain before collecting the original water sample to prepare the present CRM. Furthermore, the REE distribution patterns of JSAC 0301-1, JAC 0031 and the average values of river water samples in Japan were parallel to each other. These results indicate that the distributions of REEs in JSAC 0301-1 and JAC 0031 were the typical ones of river water samples in Japan.

Recently, the concentration of nitrous oxide (N 2 O) has been studied, because N 2 O is a greenhouse gas whose effect per molecule is more significant than that of carbon dioxide (CO 2 ), and also like chlorofluorocarbons (CFCs) and other ozone-destroying chemical elements it can cause ozone layer depletion. From 1996, the continuous monitoring of N 2 O has been done by gas-chromatography with an electron capture detector at our institute at Nagoya University (RAN) in Japan. Data of N 2 O were analyzed together with monitoring data of CO 2 and methane (CH 4 ) at the same university, by applying power spectral density, auto-correlation and cross-correlation techniques. As a result, weak correlations between N 2 O and CO 2 or CH 4 were found though their origins are thought to be different. This suggests that they are affected by the same phenomena at least partially. Moreover, correlations with the meteorological elements probably associated with the N 2 O data are investigated. We will discuss the origins of N 2 O in a suburb of Nagoya on the basis of temporal variations and correlations with various elements.

In order to elucidate the distributions of the elements among the particulate and dissolved fractions in pond water, major-to-ultratrace elements in different sizes of particles as well as in the filtrate passed through the 0.05 microm filter were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The different sizes of particle samples (ca. 100-300 microg each) were collected on the membrane filters with pore sizes of 10, 3.0, 1.2, 0.4, 0.2 and 0.05 microm, respectively, by sequential fractionation. As a result, about 40 elements in different sizes of particles could be determined by ICP-AES and ICP-MS, after acid digestion using HNO3/HF/HClO4. Then, the fractional distribution factors of major-to-ultratrace elements among the particulate and dissolved fractions were estimated from the analytical results. The total contents of Al, Fe, Ti, REEs (rare earth elements), Bi, Pb and Ag in the particulate fractions (larger than 0.05 microm) were more than 80-90%, while those of Ca, Sr, Cs, W, Ba, Mn and Co in the dissolved fraction, which corresponded to the filtrate passed through the 0.05 microm membrane filter, were more than 80%. It was further found that the fractional distributions of Cu and Zn in the dissolved fraction were ca. 50%. In addition, the enrichment factors (EFs) of the elements in the particulate fractions with particle sizes of 3.0-10 microm and 0.05-0.2 microm were estimated to elucidate their geochemical characteristics in natural water.

The partitionings of major-to-ultratrace elements between industrial waste incineration fly ash (IWIFA) and industrial waste incineration bottom ash (IWIBA) in industrial waste incinerators were investigated by measuring their concentration distributions, where the incineration ash samples were collected from three different types of industrial waste incinerators. The concentrations of the elements in the incineration ash samples were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). As a result, ca. 40 elements in the concentration range from mg g(-1) to sub-microg g(-1) could be determined in both IWIFA and IWIBA samples. The concentration ratios of CF/CB (CF, concentration in fly ash; CB, concentration in bottom ash) for analyte elements were used to evaluate the partitionings of the elements between fly and bottom ashes. Then, the correlations between the CF/CB values of the elements and the dissociation energies of their monoxides were examined to evaluate the kinetic behaviors of the elements during the incineration processes. It was found that lithophile and siderophile elements, which have a large affinity with oxygen, were almost equally distributed between fly and bottom ashes, regardless of the dissociation energies of their monoxides. On the other hand, chalcophile elements with rather large volatility provided different behaviors; the elements with the smaller dissociation energies of monoxides were more partitioned in fly ashes than those with the larger ones.

A method for the determination of iron in indium phosphide (InP) wafer is proposed. In the present experiment, an on-line matrix separation system using an ion exchange column was combined with inductively coupled plasma mass spectrometry (ICP-MS) for the determination of ng g−1 level of iron. In the on-line matrix separation, indium and iron in the sample solution was passed through a strongly-basic anion exchange resin column with the 9 M HCl carrier solution, where indium was eluted from the column and iron was adsorbed on it. Then, iron was eluted with the carrier solution of 0.3 M HCl containing 1 ng ml−1 cobalt, and it was directly introduced into the ICP-MS nebulizer. In ICP-MS measurement, cobalt in the carrier solution was used as an internal standard to correct the change in sensitivity due to matrix effect, and the peak area integration was performed to quantify iron and cobalt in the integration time range of 20–60 s from the start of the cobalt solution flow. The detection limit (3σ) for iron was 3 ng g−1, and the recoveries for iron in the 0.8, 2.4, and 8.0% indium solutions were almost 100%. The method was applied to the determination of iron in commercially available iron-doped InP wafers. The obtained results for InP wafer samples with the high iron concentration were in good agreement with those obtained by graphite furnace atomic absorption spectrometry (GFAAS).

The speciation of diverse elements in salmon egg cell cytoplasm was performed by a surfactant-mediated HPLC/ICP-MS hyphenated system. In the present experiment, an ODS column coated with CHAPS (3-[(3cholamidopropyl)dimethylammonio]-1-propanesulfonate), which is a zwitterionic bile acid derivative, was employed as a surfactant-mediated separation column, and ICP-MS was used as an element-selective detector. The present surfactantmediated HPLC allowed us to separate large and small molecules within 10 min; large molecules, such as proteins, were eluted within 2.5 min, while small molecules were eluted after 2.5 min, but within 10 min. In the present experiment, Fe, Cu, and Zn in egg cell cytoplasm were observed mostly in species with large molecular weights, indicating that these elements are contained as metalloproteins or metalloenzymes in egg cell cytoplasm. On the contrary, it was found that P, S, Mo, and halogens in egg cell cytoplasm were contained as small molecules or inorganic ions. The major species of P in egg cell cytoplasm was identified as the phosphate ion (PO 4 3‐ ). Molybdenum, Cl, and Br in egg cell cytoplasm were molybdate (MoO4 2‐ ), chloride (Cl ‐ ), and bromide (Br ‐ ) ions, respectively.

A sensitive ion-exclusion chromatographic method has been developed for determination of oxalate, thiosulfate, and thiocyanate. The method is based on separation of these anions on a polymethacrylate-based, weakly acidic cation-exchange resin (TSKgel OApak-A) and detection by means of a glassy carbon (GC) electrode electrochemically modified with polyvinylpyridine (PVP), palladium, and iridium oxide (PVP/Pd/IrO2). The electrochemical behavior of oxalate, thiosulfate, and thiocyanate at this chemically modified electrode (CME) have been investigated by cyclic voltammetry. The results indicated that electrocatalytic oxidation of these anions by the electrode was efficient and that the sensitivity, stability, and lifetime of the electrode were relatively high. Combined with ion-exclusion chromatography the PVP/Pd/IrO2 electrode was used as the working electrode for amperometric detection of these anions. All linear ranges were over two orders of magnitude and detection limits, defined asS/N=3, were 9.0×10−7 mol L−1 for oxalate, 6.7×10−7 mol L−1 for thiosulfate, and 5.6×10−7 mol L−1 for thiocyanate. Correlation coefficients were all>0.998. Coupled with microdialysis sampling the method has been successfully applied to the determination of oxalate, thiosulfate, and thiocyanate in urine.

The leachabilities of major-to-ultratrace elements in industrial waste incineration fly ash (IWIFA) were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS) in order to characterize IWIFA. The leaching data of about 50 elements in the IWIFA sample could be obtained in the concentration range from mg g-1 to sub-µg g-1, when HNO3 and aqua regia were used as the leachants. In addition, morphological observations of IWIFA particles were performed by a scanning electron microscope with an energy dispersive X-ray spectrometer (SEM-EDS) before and after the leaching treatment of the IWIFA samples. From the data for the leaching and morphological observations, the chemical states of the elements in IWIFA were elucidated as follows: (i) core materials of fly ashes were mostly composed of stable oxides of major elements such as Si, Al, Ti, and Fe; (ii) Cu, Zn, Mo, Cd, and Bi were mainly adsorbed on the surface of fly ash particles...

A multielement determination of major-to-trace elements in black tea leaves and their tea infusions was carried out by ICP-AES (inductively coupled plasma atomic emission spectrometry) and ICP-MS (inductively coupled plasma mass spectrometry). Tea infusions were prepared as usual tea beverage by brewing black tea leaves in boiling water for 5 min. About 40 elements in tea leaves and tea infusions could be determined over the wide concentration range in 8 orders of magnitude. The extraction efficiency of each element was estimated as the ratio of its concentration in tea infusions to that in tea leaves. From the experimental results for the extraction efficiencies, the elements in black tea leaves were classified into three characteristic groups: (i) highly-extractable elements (>55%): Na, K, Co, Ni, Rb, Cs and Tl, (ii) moderately-extractable elements (20 - 55%): Mg, Al, P, Mn and Zn, and (iii) poorly-extractable elements (

産業廃棄物焼却飛灰 (フライアッシュ) 試料中の希土類元素の定量を行った. 試料はメタホウ酸リチウムを融剤として用いるアルカリ融解法により溶液化し, 誘導結合プラズマ質量分析法により, 希土類元素の測定を行った. また, 石炭焼却飛灰標準物質の分析も同時に行い, 分析法の評価及び測定値の比較を行った. 本分析法により, 産業廃棄物焼却飛灰中でμg g-1からサブμg g-1レベルで存在する全希土類元素について, 精度良く定量することができた. 産業廃棄物焼却飛灰中の希土類元素の濃度は, 石炭焼却飛灰中と比較して一けたから二けた低いものであった. また, 試料中の希土類元素の存在度について, 地殻中濃度を基準とする希土類元素存在度パターン (希土パターン) を用いて比較すると, 石炭焼却飛灰では地殻と類似した希土パターンが得られたのに対し, 産業廃棄物焼却飛灰では軽希土類元素, Eu, Tbに明らかな正の異常が見られる特徴的な希土パターンが得られた. 更に, 焼却飛灰中希土類元素の溶出挙動について, 1M硝酸溶液を用いて検討したところ, 希土パターンで正の異常が見られた元素の溶出挙動が異なることが分かった. これらの結果は, 工業活動に伴う希土類元素の人為的な利用を反映するものと思われる.

キレート樹脂濃縮を併用した同位体希釈 (ID)/誘導結合プラズマ質量分析法 (ICP-MS) により河川水中Cu, Cd及びPbの同時定量を行った. Cu, Cd, Pbの濃縮同位体スパイクとして65Cu (63Cu, 0.3%; 65Cu, 99.7%), 111Cd (110Cd, 0.63%; 111Cd, 96.44%; 112Cd, 1.82%; 113Cd, 0.43%; 114Cd, 0.59%; 116Cd, 0.10%), 206Pb (204Pb, 0.0342%; 206Pb, 92.1497%; 207Pb, 6.5611%; 208Pb, 1.2550%) の混合溶液を河川水試料に添加し, 一晩放置することにより同位体平衡を達成させた. 河川水中にCu, Cd, Pbは特に低濃度で存在しているため, pH9の回収条件でキレート樹脂濃縮を行った後, 溶液中の63Cu/65Cu, 114Cd/111Cd, 208Pb/206Pbの同位体比を同時測定した. この条件では濃縮時にCdがほぼ100%回収されるのに対しMoはほとんど回収されないため, ICP-MS測定において95Mo16Oと98Mo16Oによる111Cdと114Cdへの多原子イオン干渉は除去される. この結果, 日本分析化学会より頒布されている河川水標準物質 (JAC0031) 及び木曽川河川水中Cu, Cd, Pbを同位体希釈/ICP-MS法により精度良く同時定量することが可能になった.

地球温暖化ガス削減に向けて世界規模での削減努力が行われている。しかし, 地球温暖化ガスの一つである亜酸化窒素は, 二酸化炭素やメタンほどには知られておらず, その発生源, 削減方法についての研究は多くない. 本研究では, 大気中の亜酸化窒素の環境モニタリングを行い, そのデータを基にほかの地球温暖化ガスとの相関を調べることによりその関連性を見いだし, 亜酸化窒素発生源の特定を試みた. 自己相関及び亜酸化窒素との二酸化窒素, メタン, 気象パラメーターとの相互関係を調べた結果, 亜酸化窒素は二酸化炭素, メタンより濃度変化が緩やかで変化の割合が小さいが, いずれのガスについても1日周期が存在することが分かった. 更に亜酸化窒素は, 夏季に大気濃度が上昇すること, また風向きにより濃度が変化することが分かった.

The multielement determination of major-to-ultratrace elements in plant reference materials (SRM Pine Needles, SRM Tomato Leaves, and NIES Tea Leaves) was carried out by ICP-AES (inductively coupled plasma atomic emission spectrometry) and ICP-MS (inductively coupled plasma mass spectrometry). The plant sample was decomposed with nitric acid and hydrofluoric acid in a Teflon beaker on a hot plate. The digest was dissolved in 1 M HNO3 solution, and then subjected to elemental analyses. As a consequence, the analytical data for about 40 elements including rare earth elements (REEs) were obtained over a wide concentration range, for example, from 49600 µg g-1 of Ca to 6.2 ng g-1 of Lu in Tomato Leaves. The enrichment factors, which were estimated by normalizing the observed concentrations of analyte elements in plant reference materials to their soil abundances, were evaluated in order to discuss the relative abundances of various elements between plants and soil. It was found that most of the elements, except for REEs in Pine Needles and Tea Leaves, were significantly accumulated in the plant reference materials. In particular, the essential elements (K, Mg, Ca, Mn, Cu, Zn, B and P) for plant growth provided large enrichment factors.

A study on surface modification of an octadecylsilica (ODS) column with amphoteric surfactants has been carried out for efficient reversed-phase liquid chromatographic separations of hydrophobic analytes only with water eluent. Two amphoteric surfactants each with different terminal groups (betaine-type and sulfobetaine-type surfactants) were employed as the stationary phase modifier, and the separation characteristics of the modified ODS columns were evaluated by comparing the elution times of nucleosides, their bases, and inorganic ions. In both surfactant-modified ODS column systems, the adsorption of amphoteric surfactant led to a decrease in the retention of nucleosides and their bases, while an increase in the retention of inorganic anions. These results indicate that the amphoteric surfactant adsorbed on the ODS surface suppresses the hydrophobicity of the reversed-phase surface, but it also generates a specific electrostatic field. In other words, the modified ODS columns exhibit hydrophobic/electrostatic mixed-mode separation properties. The degree of the contribution of each property to the separation of analytes can be varied with the amount of the adsorbed surfactant. Consequently, nucleosides and their bases were effectively separated on the ODS column coated with 0.55 mmol of betaine-type surfactant in water elution.

The coastal seawater sample was filtered with a membrane filter (pore size 0.45 μm), and the filtrate was further filtered with an ultrafiltration filter (molecular weight permeation limit of 10000 Da). Then, major-to-ultratrace elements in the particles which remained on the membrane filter, the membrane-filtered seawater, and the ultrafiltered seawater were determined by ICP-AES (inductively coupled plasma atomic emission spectrometry) and ICP-MS (inductively coupled plasma mass spectrometry). From these analytical results, the fractional distributions of each element in the particle, large molecule and small molecule fractions of seawater were estimated, where the distributions of the elements in the large molecule fraction were obtained as the differences between the elemental concentrations in membrane-filtered and ultrafiltered seawaters. Furthermore, laboratory-made salts (Salts I—III) were prepared from original, membrane-filtered, and ultrafiltered seawaters. The concentrations of major-to-ultrat...

The simultaneous multielement determination of trace elements in seawater, especially hydride- and oxoanion-forming elements, has been investigated by inductively coupled plasma mass spectrometry with the aid of lanthanum coprecipitation preconcentration. The optimum pH in lanthanum coprecipitation was pH 9.5; at this value, trace elements were well recovered and major constituents of seawater such as Na, Mg, K, and Ca were significantly reduced in the concentrated solutions. The recovery values obtained for V, Cr(III), Mn, As(III), As(V), Se(IV), Y, Sn, Sb(III), Sb(V), W, Bi, and U were more than 85% after lanthanum coprecipitation, while Cr(VI), Se(VI), and Mo(VI) provided poor recoveries of less than 30%. The reproducibility for coprecipitation was within 5% as relative standard deviation. The present method was applied to the determination of trace elements in coastal seawater reference material CASS-3. The analytical values for Mn, As, V, Y, Sb, W, and U were in fairly good agreement with the certifi...

An amperometric detector with two working electrodes modified with polydiphenylamine (PDPA) and polydiphenylamine dodecyl sulfate (PDPA-DS) was successfully used for the simultaneous determination of electroinactive anions (SO42−, Cl−, NO3−) and cations (Na+, NH4+ and K+) in single-column ion-exclusion chromatography–cation-exchange chromatography (IEC-CEC). The PDPA-DS chemically modified electrode (CME) was based on the incorporation of dodecyl sulfate (DS) into PDPA by electropolymerization of diphenylamine (DPA) in the presence of surfactant. The electrochemical responses against the anions and cations in differential pulse voltammetry were studied. A set of well-defined peaks of electroinactive anions and cations were obtained. The relative standard deviations (RSDs) of chromatographic peak height (nA) for anions were all 0.990. Their detection limits were investigated using 3s (where s represents the standard deviation of a blank solution, n = 11). They were 9.86 × 10−7 mol L−1 for SO42−, 6.92 × 10−7 mol L−1 for Cl−, 7.86 × 10−7 mol L−1 for NO3−, 7.86 × 10−7 mol L−1 for Na+, 9.79 × 10−7 mol L−1 for NH4+ and 8.94 × 10−7 mol L−1 for K+. The recoveries of the anions and cations by this method were in the range 97.8–103%. The proposed method was rapid, sensitive and simple and was successfully applied to the analysis of rainwater samples. Both electrodes were stable during a 1 week period of operation with no evidence of chemical or mechanical deterioration.

An amperometric detector based on the chemical modification of poly-o-phenylenediamine (P-OPD) on a gold electrode was successfully used for the determination of electroinactive anions (SO42−, Cl−, NO3−, F−, CH3COO− and PO43−) by single-column ion-exclusion chromatography. All of the anions were detected conveniently and reproducibly in a linear concentration range of 1.0 × 10−5–5.0 × 10−3 mol L−1. The detection limits of the anions were 2.10 × 10−6 mol L−1 for SO42−, 2.47 × 10−6 mol L−1 for Cl−, 3.53 × 10−6 mol L−1 for NO3−, 3.41 × 10−6 mol L−1 for F−, 5.82 × 10−6 mol L−1 for CH3COO− and 3.86 × 10−6 mol L−1 for PO43− at a signal-to-noise ratio of 3. The proposed method was successfully applied to the analysis of rainwater and river water samples. The electrode was stable during a 2 week period of operation with no evidence of chemical or mechanical deterioration.

Ultratrace metal impurities (Be, Al, Ti, Cr, Ni, Nb, Mo, Sn, W, Th, and U) in high purity tantalum metal, tantalum(V) oxide, and tantalum pentaethoxide were determined by a combined system of flow injection with an anion exchange column and inductively coupled plasma mass spectrometry (ICP-MS). In the present combined system, the on-line matrix separation and multielement determination of impurity elements could be performed. When 2 M HCl/0.1 M HF mixed solution and 1 M HNO3/0.1 M HF mixed solution were used as the carrier solutions, Be, Al, and Ti for the former, and Cr, Ni, Nb, Mo, Sn, W, Th, and U for the latter were eluted from the column without any tantalum matrix. The detection limits (3σ) of analyte elements were in the range over 0.003 - 0.14 ng/ml as the sample solution basis. The present method was applied to the determination of metal impurities in high purity tantalum materials. The concentrations of Be, Ti, Mo, Sn, Th, and U were at the ng/g level, while those of other elements were in the range over the μg/g - ng/g level.

飲料に供される緑茶葉の元素組成と溶出成分を調べるために,誘導結合プラズマ発光分析法(ICP-AES)及び誘導結合プラズマ質量分析法(ICP-MS)を用いて主成分から超微量成分までの多元素定量を行うとともに,サイズ排除クロマトグラフィー(SEC)を併用する化学形態別分析を行うことを目的とした。多元素定量分析の結果,緑茶要試料の酸分解溶液について%レベルの主成分元素からng g-1レベルの超微量元素までの40元素の定量を行うことができた。また,緑茶葉試料中の成分を熱水によって抽出した熱水浸出液では,29元素の定量値が得られた。これらの緑茶葉中の全元素量と熱水浸出液中の元素量の比から,各元素の緑茶葉からの浸出率を求めた。その結果,緑茶葉中の元素は浸出率が55%以上(Na,K,Co,Ni,Rb,Cs),20～55%(Mg.Al,P,Mn,Zn,Tl),20%以下(Ca,Fe,Cu,Sr,Y,Zr,Mo,Sn,Ba,希土類元素,Pb)の三つの元素群に分類された。更に,SEC,UV吸収検出器,ICP-AES又はICP-MSをオンラインで結合した複合分析システムにより,緑茶葉浸出液中元素の化学形態別分析を行った。その結果,SECクロマトグラム中に20元素が検出され,それぞれの元素が結合した化学種の分子量に関する知見が得られた。

The determination of all rare earth elements (REEs) in human blood serum by inductively coupled plasma mass spectrometry (ICP-MS) was performed with the aid of chelating resin (Chelex 100) preconcentration after acid digestion with HNO3 and HClO4. When chelating resin preconcentration was carried out at room temperature, the recoveries of heavy REEs were lower than those of light REEs because of their stable complex formation with residual organic compounds remaining in the digested serum solution. These problems were overcome by heating the solution at 80 °C during the chelating resin preconcentration process. As a result, the recoveries for all REEs were improved to 92–102% in the case of a concentration factor of 4, where the analytical detection limits for REEs were below 0.2 × 10−12 g ml−1. Consequently, all REEs in individual human blood sera collected from five healthy volunteers could be determined by ICP-MS with good precision. The concentrations of REEs in human blood serum were extremely low, in the range from ca. 1 × 10−12 g ml−1 of Eu to ca. 230 × 10−12 g ml−1 of Ce.

誘導結合プラズマ質量分析法(ICP-MS)及び誘導結合プラズマ発光分析法(ICP-AES)を用いて,野菜試料中の多元素定量を以下のように行った。まず,ホウレンソウ乾燥試料0.5gをテフロンビーカーに入れ,硝酸とフッ化水素酸を加えてホットプレート上で加熱分解した。この溶液化した試料を内標準元素(Ge,In,Re各10ppb)を含む1mol dm-3HNO3溶液に調製後,ICP-AES及びICP-MSで測定し,%レベルで存在する元素からppbレベルで存在する元素まで約40元素の定量値を得た。また,異なる産地で栽培されたホウレンソウ試料について,元素濃度の平均とそのばらつきの大きさを検討した。主成分及び少量元素の中で,B,Mg,P,Kの濃度は試料によるばらつきが小さく,一方Ca,Na,Al,Mnについては変動係数が50%以上となった。微量元素及び超微量元素の変動係数は全般的に高く,100%を超える場合も見られた。更に,本分析法を11科23種類の野菜の多元素定量分析に応用し,野菜の種類による元素濃度の類似性と差異を明らかにした。

The multielement determination of major-to-ultratrace elements in river sediment reference material (NIES No.16) and marine sediment reference material (NIES No.12) was investigated by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The sediment samples were decomposed by alkali fusion with lithium metaborate (LiBO2) in a platinum crucible, and the residues were dissolved in 1 M nitric acid. The digested sample solutions were subjected to the analysis by ICP-AES and ICP-MS after appropriate dilution. In consequence, 42 elements were determined over a wide concentration range, for example, from Si 23.8% to Lu 0.29 µg g-1 in the case of marine sediment reference material.

The progress of modern analytical atomic spectrometry is briefly reviewed with emphasis on ICP-AES and ICP-MS; these provide some excellent analytical features such as high sensitivity, wide linear dynamic range, and multielement detection capability. Thus, the multielement determination of the major-to-ultratrace elements from % to sub-ppt (1 ppt = 10−12 g ml−1) level is possible for the biological, geochemical, and environmental samples. The standard or certified reference materials of plant, human blood serum, and the other biological samples were analyzed to establish the reliable analytical methods for the multielement determination by ICP-AES and ICP-MS. The modern analytical methods were applied to: (i) the correlation analysis of the elements in human blood serum, and (ii) the determination of rare earth elements in human blood serum on a personal basis. The speciation of trace elements in natural water was also carried out by the SEC (size exclusion chromatography)/UV absorption detection/ICP-MS ...

An analytical method for the determination of lanthanide elements in the bovine whole blood reference material (IAEA A-13) has been investigated by inductively coupled plasma mass spectrometry (ICP-MS). The bovine whole blood reference material was digested with HNO3 and HClO4, and then the pH of the digested solution was adjusted to 12 with 3 M sodium hydroxide aqueous solution. In this experimental procedure, lanthanide elements in the blood sample were coprecipitated with iron mainly derived from heme-iron in blood itself. In order to minimize matrix effects due to iron, excess iron in the analysis solution was removed by solvent extraction using methyl isobutyl ketone (MIBK) prior to the determination of lanthanide elements by ICP-MS. The recoveries of all lanthanide elements were almost quantitative in the recovery test. In consequence, it has been found that all lanthanide elements in bovine whole blood reference material are at the wide concentration range of 0.90 pg/g for Tm ∼1880 pg/g for Ce.

A system of liquid chromatography combined with inductively coupled plasma mass spectrometry (ICP-MS) has been applied to the determination of rare earth elements (REEs) in geochemical standard reference samples. In liquid chromatography, a strong ion-exchange resin was employed as a stationary phase and ammonium lactate was used as a mobile phase. Multielement detection by ICP-MS was performed in the peak hopping mode to measure the chromatograms for all REEs at the corresponding mass numbers. REEs in the standard rock sample (GSJ JB-1) and the standard sediment sample (Pond Sediment; NIES No.2) were determined by the present measurement system without any correction of the matrix effect and polyatomic ion interferences.

The peculiar ion pairing elution behavior of anions with cations in electrostatic ion chromatography with water as eluent was investigated by using detectors based on conductivity and inductively coupled plasma-atomic emission spectrometry, where a sulfobetaine-type amphoteric surfactant (C14SB) immobilized on an octadecyl silica surface was employed as the stationary phase. Some preferential combinations of anions with cations were experimentally identified; Mg2+, for example, was preferentially paired with the anions in the order NO−3>Br−>NO−2>Cl−>SO2−4. The preferential combination characteristics could be used for the control of ion pair formation of analyte anions with counter cations. When MgSO4, used here as a “decoy electrolyte”, in which Mg2+ and SO2−4 were the “decoy cation” and “decoy anion”, respectively, was added to the original sample solution (Cl−, NO−2, Br− and NO−3 as analyte anions; Na+ K+, Mg2+ and Ca2+ as counter cations) at a relatively high concentration compared to the concentrations of analyte anions, all the analyte anions in the sample solution were eluted with the introduced decoy cation (Mg2+), following the preferential combination. Consequently, all the analyte anions were practically separated as a “decoy cation” form, and they could easily be determined from the calibration graphs of the anions in the decoy cation salts by conductivity detection. The present ion chromatographic method involving the characteristic anion–cation recombination technique was applied to the determination of anions (Cl−, Br−, and NO−3) in a vegetable (radish).

誘導結合プラズマ発光分析法(ICP-AES)及び誘導結合プラズマ質量分析法(ICP-MS)を用いて,天日塩中不溶粒子成分の多元素分析を行った.天日塩試料30gを純水1lに溶解し,この溶液を孔径0.45μmのメンブランフィルター(セルロースアセテート製)で濾過し,濾液を可溶成分,フィルター上に残った成分を不溶粒子成分として分離した.不溶粒子成分は,メンブランフィルターごと混酸(硝酸/フッ化水素酸/過塩素酸)による酸分解を行って溶液化し,ICP-AES及びICP-MSにより測定したところ,%～サブμgg-1の濃度範囲で存在する36元素を定量することができた.既報で報告した天日塩の可溶成分中の元素濃度と合わせて考えると,アルカリ元素,アルカリ土類元素,Mo, Cd等は主に可溶成分に,またAl, Ti, V, Fe, Co, Ga, Y, Sn,希土類元素(REEs)等は主に不溶粒子成分に存在することが明らかになった.これらの不溶粒子成分中元素のうち,Fe, Co, Y, Sn, REEs等は酸添加によってその一部が溶出することから,海水中でコロイド態粒子としても存在していることが示唆された.これに対し,Mn, Cu, Zn, Pbは可溶成分及び不溶粒子成分の両成分に存在し,天日塩中で複数の化学形態で存在することも明らかになった.また,天日塩中不溶粒子成分及び海洋底質標準試料中の元素濃度を比較したところ,両者の間には極めて高い相関があることが明らかになり,天日塩中に取り込まれた不溶粒子成分は堆積物の重要な起源の一つであることを示す結果が得られた.

A rapid and sensitive method for the determination of impurity elements in high purity tantalum metals is proposed. Tantalum metals were digested with nitric acid (HNO3) and hydrofluoric acid (HF). The digested sample solutions were injected into a flow injection system with a cation exchange column. Impurity elements adsorbed were eluted with the mixture of HNO3 and HF, and then the effluent was introduced into an ICP plasma with conventional pneumatic nebulization. In the present flow injection/ICP-MS system, the detection limits, based on 3 times the standard deviation of the blank, were in the range 0.03 - 6 ng/g for the 16 impurity elements (Li, Na, Mg, Mn, Co, Cu, Zn, Ga, Rb, Sr, Cd, In, Ba, Tl, Pb, and Bi).

A unique high performance liquid chromatographic system for the separation of polar organic compounds is described. Strong anion-exchanger was used as the stationary phase and pure water was used as the mobile phase. When the strong anion-exchanger was conditioned with pure water as the mobile phase, the fixed ionic site with its counterion functioned as a zwitterionic stationary phase. This facilitated the separation of the polar organic compounds without need for ionization of the analytes. A strong commercial anion-exchanger (polyacrylate-based type) and a laboratory-made one (ODS-based type; obtained by dynamically coating hexadecyltrimethylammonium salts on the reversed-phase ODS surfaces) were chosen to represent the stationary phases. Five purine and pyrimidine bases and eight nucleosides were chosen to represent the polar organic analytes. All of these polar organic analytes were successfully separated and rapidly eluted with pure water as the mobile phase. Separation mechanisms involved ...

The analytical methods for the determination of inorganic anions by water elution ion chromatography using a zwitterionic column (C14SB-coated column) have been explored, where pure water was used as the mobile phase. In the present ion chromatography, the complicated peaks derived from various "ion pairs" appeared on the chromatogram when the sample solution contained several kinds of cations and anions. The chromatograms with the complicated peaks were simplified by using a preconditioning cation-exchange column. In the preconditioning column, various kinds of countercations of the analyte anions were converted to a particular kind of common cation, and thus all the analyte anions were separated as the common cation form. The more effective separation was achieved by converting to a divalent cation (Mg(2+)) form than a monovalent cation (Na(+)) form, because the anions paired with the divalent cation provided longer elution times than those paired with the monovalent cation. All the analyte anions separated as the common cation form were simply determined from their calibration curves drawn from conductivity detection. In addition, the counterionic determination of the anions was also attempted by using ICP-AES. The analyte anions were determined by measuring their countercations with ICP-AES, where the calibration curve of the countercation measured by ICP-AES could be used.

誘導結合プラズマ質量分析法(ICP-MS)及びICP発光分析法(ICP-AES)を用いて,サクラ(桜)試料中の多元素定量を行った.本研究ではまず茶葉標準試料(NIES No.7)を用いて,試料の酸分解法,多原子イオン干渉の補正に関する基礎検討を行い,その上で茶葉標準試料の多元素分析を行った.その結果,植物試料の溶液化には硝酸とフッ化水素酸による酸分解法がケイ酸質による影響を除去するのに有効であった.本法をサクラ試料の分析に適用し,名古屋大学構内を含む名古屋市内9か所で採取されたサクラ葉,花弁,がく中の主成分から超微量成分元素まで41元素の定量値が得られた.更に,サクラ試料における元素分布及びその地域分布についても考察した.

誘導結合プラズマ質量分析法(ICP-MS)及び誘導結合プラズマ発光分析法(ICP-AES)を,日本分析化学会より頒布されている河川水標準物質(JAC 0031,JAC 0032)中の微量元素の多元素定量に適用した.ICP-MS及びICP-AESによる多元素分析においては,河川水試料の直接導入法とともに微量元素に対してキレート樹脂濃縮法を併用することにより,河川水標準物質中の37元素の定量を行うことができた.Caの12300からTmの0.00012μg l-1まで9けたに及ぶ広い濃度範囲の定量値が得られた.認証値が求められている元素については,おおむね認証値と一致した結果であった.又,希土類元素についても,すべて定量することができ,頁岩中濃度で規格化した希土パターンでは重希土類元素の相対存在度が高く,Ceの負の異常がある天然水特有のパターンが得られた.