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Cold stress is an adverse environmental condition that affects plant growth, development, and crop productivity. Under cold stress conditions, the expression of numerous genes that function in the stress response and tolerance is induced in various plant species, and the dehydration-responsive element (DRE) binding protein 1/C-repeat binding factor (DREB1/CBF) transcription factors function as master switches for cold-inducible gene expression. Cold stress strongly induces these DREB1 genes. Therefore, it is important to elucidate the mechanisms of DREB1 expression in response to cold stress to clarify the perception and response of cold stress in plants. Previous studies indicated that the central oscillator components of the circadian clock, CIRCADIAN CLOCK-ASSOCIATED 1 (CCA1) and LATE ELONGATED HYPOCOTYL (LHY), are involved in cold-inducible DREB1 expression, but the underlying mechanisms are not clear. We revealed that the clock-related MYB proteins REVEILLE4/LHY-CCA1-Like1 (RVE4/LCL1) and RVE8/LCL5 are quickly and reversibly transferred from the cytoplasm to the nucleus under cold stress conditions and function as direct transcriptional activators of DREB1 expression. We found that CCA1 and LHY suppressed the expression of DREB1s under unstressed conditions and were rapidly degraded specifically in response to cold stress, which suggests that they act as transcriptional repressors and indirectly regulate the cold-inducible expression of DREB1s. We concluded that posttranslational regulation of multiple clock-related transcription factors triggers cold-inducible gene expression. Our findings clarify the complex relationship between the plant circadian clock and the regulatory mechanisms of cold-inducible gene expression.

In 2004, the term "metallomics" was coined to describe integrated biometal science (H. Haraguchi, Metallomics as Integrated Biometal Science, J. Anal. At. Spectrom., 2004, 19, 5-14). Around 10 years have passed since then, and the history of metallomics over the last decade is reviewed here, discussing the development of metallomics before and after the proposal. Furthermore, the future outlook of metallomics research will be considered, in terms of topics such as the organization of platforms for metallomics research related to trace metal sciences, a simplified model of the biological system and omics-sciences, research subjects in metallomics, recent trends of metallomics research, and the challenge of single biological cell analysis.

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.

Salmon egg cells were the subject of investigation for all-elements analysis in a single biological cell, where the elements in egg cells were simultaneously determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS) after microwave-assisted acid digestion. As a result, 74 elements among 78 stable isotope elements were determined or detected, although H, C, N, and O were determined separately by conventional CHN elemental analysis. In addition, the survey of protein-binding metallic elements as well as metalloid elements in salmon egg cell cytoplasm was performed by the fractionation analysis with a hyphenated system of high-performance liquid chromatography (HPLC)/ICP-MS using a 3-[(3-cholamidopropyl)-dimethylammonio]-1-propane sulfonate (CHAPS)-coated octadecylsilyl silica (ODS) column and a size exclusion chromatography (SEC) column.

ヒト毛髪のキューティクル層における酸化染毛剤 (ヘアカラー) の染毛機構について研究した。一般に酸化染毛においては, 酸化染料モノマーが毛髪内部のコルテックスへ浸透し, 酸化重合して発色するとされている。精密に作製した染色毛の横断面切片を観察した結果, 酸化染料はコルテックスだけでなくキューティクル層にも染着していることを確認した。キューティクル層には水道水などに由来するさまざまな外因性の金属が蓄積するが, 遷移金属が多いと染色性は増加する一方で, 脱色性は低下した。キューティクル層において過酸化水素による酸化反応が活発になり, 内部浸透が不利になった結果と考えられた。また, 透過型電子顕微鏡によりcuticular CMC (cell membrane complex) のβ-layerに金属が偏在していることが示唆され, キューティクル層においてはcuticular CMCのβ-layer, δ-layer界面が酸化染料の有力な反応の場として考えられた。

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.

Chemical speciation of arsenic species in human blood serum was performed by high-performance liquid chromatography/inductively coupled plasma mass spectrometry (HPLC/ICP-MS) with direct sample inj...

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.

Assay of alkaline phosphatase (ALP) in salmon egg cell cytoplasm was performed by size exclusion chromatography (SEC) with fluorescence detection of enzymatic activity and element-selective detecti...

Lead isotope ratios in atmospheric suspended particulate matter (SPM) collected in Nagoya City were measured by high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) after microwave-assisted acid digestion. Before analyzing SPM samples, the present method was evaluated by analyzing standard reference material (SRM 981) for common lead isotopic standard from NIST. The analytical results for 207Pb/206Pb and 208Pb/206Pb for SRM 981 were 0.9160±0.0006 and 2.136±0.003, respectively, which were almost coincident with the certified values of 0.91464±0.00033 and 2.1681±0.0008, respectively. The lead isotope ratios in SPM samples collected daily in Nagoya University were analyzed in order to elucidate their origins, and the results were compared with various kinds of ores. It was found that most SPM samples showed some mixed compositions of lead isotope ratios of lead ores from USA and Australia, which suggested utilization of large amount of lead ores imported from these two countries. On the o...

The concentrations of major-to-ultratrace elements in bittern, which was obtained after seawater concentration in the salt preparation process, were investigated by ICP-AES (inductively coupled pla...

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 multielement determination of precious metals (Ru, Rh, Pd, Ir, Pt, and Au) in industrial waste incineration ashes was examined by inductively coupled plasma mass spectrometry (ICP-MS) with exte...

Chemical speciation of arsenic in human urine was performed by HPLC separation with ICP-MS detection in order to investigate the urinary excretion patterns of arsenic metabolites after one-time ingestion of an edible seaweed, hijiki (Hizikia fusiforme). A Japanese male volunteer ingested one serving of ca. 15 g (dry weight) of hijiki (containing ca. 0.9 mg of arsenic), and urine samples were collected at 3-5 h intervals for the following 3 days. As a result, different urinary excretion patterns were observed between inorganic and methylated arsenicals. Toxic inorganic As(V) and As(III) were detected in the urine 3 h after ingestion. The highest concentrations of As(V) and As(III) were observed at 6 and 15 h after ingestion, respectively. In contrast, methylated arsenic species in the urine, such as monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), and arsenobetaine (AB), began to increase 10 h after ingestion and provided the highest concentrations at 21 h after ingestion. These results indicate that a large amount of As(V) from hijiki is excreted rapidly in urine and some part of it is reduced to As(III) in the human body. As(III) may then be converted to non-toxic methylated arsenic species and excreted in urine later than inorganic ones. It can be concluded from these experimental results that detoxification of arsenic occurs in the human body through the rapid urinary excretion of toxic arsenicals or by conversion to organic methylated ones after ingestion of hijiki.

A tandem preconcentration method using a chelating resin was exploited for simultaneous multielement determination of trace metals in seawater by inductively coupled plasma mass spectrometry (ICP-M...

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.

A chelating resin-packed minicolumn was developed to pretreat seawater samples for the determination of trace metals by inductively coupled plasma mass spectrometry (ICP-MS). The preconcentration conditions, such as the flow rate of sample loading, pH for adsorption, amount of ammonium acetate for eliminating matrix elements, and the amount of nitric acid for eluting trace metals from the resin, were investigated and optimized. Firstly, 50 mL of seawater samples was adjusted to pH 6.0 and loaded into the column at the flow rate of 3 mL min - 1 . Secondly, 8 mL of 1 M ammonium acetate and 5 mL of pure water were passed through the column for eliminating matrix elements, such as Mg and Ca. Finally, trace metals were eluted with 2.25 mL of 2 M nitric acid, and then 0.25 mL of internal standard elements (Ge, In, Re, Tl, 100 μg L - 1 each) was added to the eluted solution in order to correct matrix effects in the ICP-MS measurements. The recoveries for 23 elements (Mn, Co, Ni, Cu, Zn, Y, Cd, all-REEs, Pb, and U) were more than 80%. The analytical results for the concentrations of trace metals in seawater reference material (NASS-5) agreed well with certified or reference values. The present method was also applied to the multielement analysis of the coastal seawater samples from the Take Island (Gamagoori, Aichi prefecture, Japan) and the Ise Bay (Nagoya, Aichi prefecture, Japan).

Coastal seawater and river water samples were collected near Nagoya port, located in the coastal area of the Ise Bay, and in six rivers around Nagoya City. The rare earth elements (REEs) in these samples were determined by inductively coupled plasma mass spectrometry (ICP-MS) with chelating resin preconcentration. The concentrations of all REEs except for Pm in coastal seawater and river water samples could be determined at the concentration level from sub-ng L - 1 to 10 ngL - 1 . In order to examine the relative concentration variations, the REE patterns were estimated by normalizing the concentrations of REEs in the water samples to those in Post Archean Average Australian Shale (PAAS). Significantly positive Gd anomalies in the REE patterns were observed for river waters down from the urban areas as well as for coastal seawater. Such Gd anomalies were especially remarkable for river water collected near sewage treatment facilities in the Tenpaku river. It was, thus, concluded that the Gd anomalies in the REE patterns were artificially caused by anthropogenic sources mainly due to recent use of a gadolinium compound as a contrast reagent for magnetic resonance imaging (MRI) in medical diagnosis.

The elemental composition of the industrial waste incineration bottom ash (IWIBA) samples collected from three different types of incinerator with different kinds of wastes were compared. The major-to-ultratrace elements in the IWIBA 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 milligrams per gram to submicrograms per gram could be determined with relative standard deviations of less than 5%. The IWIBA sample from petrochemical wastes contained lower concentrations of the elements, because fewer mineral constituents were contained in the input waste materials. On the contrary, the elemental concentrations in the IWIBA sample from industrial solid wastes provided the highest values for most elements, while the elemental compositions of the IWIBA sample from food wastes were similar to those of municipal solid waste incineration bottom ash. In addition, it was found from the analytical results that the levels of various heavy metals such as Cr, Mn, Fe, Ni, Cu, As, Zr, Mo, Sb, Ba, and Pb were higher in the IWIBA samples than in municipal solid waste incineration bottom ash. The enrichment factors of the elements in the IWIBA samples were estimated from the analytical results to compare the elemental distributions in incineration bottom ashes in relation to their mining influence factors, which are the indices for human use of the 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.

Flower color in hydrangea is well known to vary greatly. The blue color might develop with aluminum ion (Al 3+ ) from soil; the blue pigment in sepals is an Al-complex with delphinidin 3-glucoside and 5-caffeoyl quinic acid. To clarify the correlation between blue color development and Al-tolerance, flower color and metal content of the sepals were examined with reference to the reflection spectrum and ICP-AES. Blue sepals were found to contain more than 100 ppm Al, and red ones was less than 50 ppm. Change of several element contents along the flower growing stage was also observed. In blue sepals Al ions increased with maturation, but, in red counterpart s the same level was maintained. The content of Fe in blue and red sepals showed a similar behavior to that of Al. However, reconstruction experiments suggested that Al may be responsible for the blue color. Al accumulation and blue color development might reflect a detoxification mechanism for Al in tolerant plants.

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...

The multielement determination of major-to-ultratrace elements in industrial waste incineration bottom ash was carried out by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS) after alkali fusion using LiBO2. The concentrations of 50 elements in bottom ash could be determined over the concentration range from 192 mg g−1 of Si to 0.072 μg g−1 of In. Silicon, Al, Fe, Ca, Na, and Ti, which except for Fe are lithophile elements, were major elements of industrial waste incineration bottom ash. The distributions of major-to-ultratrace elements in incineration bottom ash were evaluated by the enrichment factors. The enrichment factors of major elements in incineration bottom ash indicated that their relative contents were quite similar to those in the continental crust. It was also found that most minor and trace elements in the lithophile element group provided almost the same enrichment factors as those of major elements. On the other ha...

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.

A tandem preconcentration method, in which chelating resin adsorption and La coprecipitation were cooperatively employed for preconcentration, was developed as a pretreatment method for simultaneous multielement determination of trace elements in seawater by ICP-MS. First, the seawater sample (250 ml) was treated with a chelating resin for preconcentration of trace elements, and then trace elements with good recoveries were determined by ICP-MS. Trace elements with the chemical properties of oxoanion- and hydride-formation, which were poorly recovered in the chelating resin preconcentration, were further subjected to preconcentration by La coprecipitation. As a result, more than 30 elements could be determined in the concentration range from 9.6 μg L-1 for Mo to 0.00018 μg L-1 for Tm, when the present tandem method was applied to the analysis of open seawater standard reference material (NASS-4). Furthermore, the analytical results for open seawater reference materials were compared with those for coastal...

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.

An amperometric detector with two working electrodes both modified with polydiphenylamine-dodecyl sulfate (PDPA-DS) was successfully used for the simultaneous determination of electroinactive anions (SO4 2–, Cl–, NO3 –) and cations (Na+, NH4 + and K+) in single-column ion-exclusion cation-exchange chromatography (IEC-CEC). The PDPA-DS chemical modified electrode (CME) was based on the incorporation of dodecyl sulfate (DS) into PDPA by electropolymerization of diphenylamine in the presence of sodium dodecyl sulfate. The electrochemical responses against the anions and cations at the PDPA-DS CME in differential pulse voltammetry were studied. A set of well-defined peaks of electroinactive anions and cations were obtained. The anions and cations were detected conveniently and reproducibly in a linear concentration range 0.01–5.0 mmol/L and their detection limits were in the range 5–9 μmol/L at a signal-to-noise ratio of 3 (S/N = 3). The proposed method was quick, sensitive and simple and was successfully applied to the analysis of lake water samples. The working electrode was stable over one week period of operation with no evidence of chemical and mechanical deterioration.

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.