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In recent years, the utilization of high-technology metals such as rare earth elements (REEs), which exist in extremely low quantities in the Earth, has rapidly increased with the development of new types of industrial materials and pharmaceutical products. This review provides an overview of a new type of potential anthropogenic pollution caused by high-technology metals, with a focus on REEs released into environmental waters from waste treatment plants. In this paper, potential anthropogenic pollution was defined as pollution caused by metals gradually enriched in the environment by human activity, although standard and guideline concentrations of these elements are not regulated by environmental quality standards for water pollution. We review the analytical methods of REEs and the potential anthropogenic pollution of REEs with a focus on Gd, from the viewpoints of a comparison of the degree of Gd anomaly, chemical speciation, ecotoxicology, and bioaccessibility. Moreover, we also highlight the comprehensive analysis based on multielement analysis of high-technology metals as well as REEs for the further screening for potential anthropogenic pollution.

In the present study, total suspended particle (TSP) aerosols were simultaneously collected using identical high-volume air samplers at three islands in Okinawa; Cape Hedo Atmosphere and Aerosol Monitoring Station (CHAAMS, Okinawa Island), from 2008 to 2012 Kume Island (KM, ca. 160 km south-west of CHAAMS), and Minami-Daitou Island (MD, ca. 320 km south-east of CHAAMS) from 2008 to 2010. The sample collected were analyzed using energy-dispersive X-ray fluorescence spectrometry (ED-XRF) and synchrotron radiation X-ray fluorescence spectrometry (SR-XRF) to investigation long-range transport of metal elements to Okinawa from the Asian continent. From analytical data on samples collected at CHAAMS for five years, it was found that most elements (Ca, Fe, Ti, Mn, V, Cu, Ni, Pb, As, and Zn) in TSP aerosols showed higher concentrations in the period from October to May, when the continental air mass passed over Okinawa, regardless of Asian dust events. The annual average concentrations of Ni, Cu, Zn, As, Se, and Pb in TSP aerosol samples collected at three islands gradually decreased as the TSP aerosols traveled from west to east in any year. Based on the enrichment factors (EFs) and concentration ratios, it is considered that most of anthropogenic elements such as As, Pb, and Zn in TSP aerosols are derived from coal combustion in the Asian continent. Moreover, it is confirmed from the direction of the air mass reaching the sampling sites that Cu, Zn, As, and Pb in TSP aerosols were transported to the three islands in Okinawa by air mass not only from northwest and north, but also from the west. These TSP aerosols transported from the Asian continent may influences not only the atmospheric environment but also the concentrations of trace metals in coastal seawater in Okinawa, which have to be kept extremely low to preserve the diverse and unique ecosystem in coral reefs.

Pseudo isotope dilution (PID) was suggested as a simple and practical approach for the correction of barium-related spectral interferences on the measurement of europium by inductively coupled plasma mass spectrometry (ICP-MS). The interferents, i.e. oxides and hydroxides of barium, were regarded as pseudo europium isotopes. An equation for calculating the concentration of europium was deduced and the net contribution of europium isotopes can be obtained by measuring the signal intensity ratios of 151I/153I in a sample, a europium standard, and a barium standard, respectively. The validity of the approach was confirmed by the determination of europium in standard solutions with different concentrations of barium. Determination of europium in river water and seawater certified reference materials was carried out, whose results were in coincidence with reference values.

Approximately 20 major-to-ultratrace elements in each organ (mantle, muscle, liver, kidney) of a giant clam, Tridacna crocea, and 16 elements in symbiotic zooxanthellae were determined by ICP-AES, ICP-MS, and CHN coder. The biogeochemical properties of T. crocea were then investigated using multi-element profiling analyses. The values for most elements were the highest in the kidney among all organs. However, the concentrations of Mn, Co, Ni, Zn, Se, Ag, Cd, and Pb in the mantle were higher than those in the muscle and liver. Therefore, these results indicate that most trace elements taken in by T. crocea through zooxanthellae may finally accumulate in the kidney. Moreover, 14 trace elements in zooxanthellae were present in the concentration range from 181 µg g−1 for Zn to 0.58 µg g−1 for U based on dry weight after isolating zooxanthellae from the mantle. The concentrations of some trace metals in zooxanthellae were relatively higher than those in other organs except for the kidney. These results suggest...

A method for direct and precise determination of Cd in seawater by ICP-QMS/QMS was developed, where a high matrix introducing unit permitted the direct introduction of seawater without clogging the cones while the matrix effect of seawater was canceled by standard addition. NH3 gas was selected as the reaction gas for removing the MoO interferences with the measurement of Cd isotopes, effectively improving the signal to background ratio. The lower limit of detection obtained at 114Cd was 0.0002 ng mL-1, which is enough for the determination of Cd in natural seawater. The validity of the present method was confirmed by the analysis of two certified reference materials, i.e. NASS-5 and NASS-6, whose observed values of Cd concentration agreed with the certified values. The analytical figures of merit of the present method were comparable to or better than those reported for direct analysis of seawater.

We synthesized a novel adsorbent to recover inorganic arsenic(III) from groundwater, and we investigated its adsorptivity. The adsorbent, which was made by soaking powder made from crushed fisheries waste (scallop shells) in an iron sulfate solution without heat or pressure, adsorbed 0.2 mg of arsenic(III) per gram of adsorbent. This high adsorptivity and the inexpensive, simple, and environmentally benign synthesis method indicate that this easy-to-handle adsorbent may be useful for preparing safe drinking water from groundwater contaminated with toxic arsenic(III).

The present study applied multi-element profiling analysis to the monitoring of coastal seawater around coral reefs to elucidate the elemental characteristics and the biogeochemical cycles. In temporal concentration variation, the long-term monitoring (monthly over one year) and short-term monitoring (3-hourly over two days) were subjected to multi-element determination by ICP-MS with solid phase extraction using chelating resin. In the long-term monitoring, the nutrient-type elements Fe, Ni, Cu, Zn, and Cd and the scavenging-type elements Mn, Co, and Pb showed wide variations in their total, dissolved, and acid-soluble concentrations. The elevated total concentrations of Mn, Fe, Ni, Cu, Zn, Cd, and Pb in short-term variation of October 2011 were possibly caused by mucus secreted from coral. The increased concentrations of trace metals in the coastal seawater around the reefs might play important role to provide bio-essential trace metals to zooxanthellae living in symbiotic animals, such as corals, anemones, and giant clams.

In the present study, ICP-MS with a new hybrid simultaneous preconcentration combining solid phase extraction using chelating resin and iron hydroxide coprecipitation in one batch at a single pH adjustment (pH 6.0) were developed for multielement determination of trace metal ions in seawater. In multielement determination, the present method makes it possible to determine Cr(III), As(V), Se (IV), and other 14 trace metal elements (Ti, V, Co, Ni, Cu, Zn, Zr, Ge, Cd, Sb, Sn, W, Pb, and U) in seawater. Moreover, for speciation analyses of Cr, As, and Se, the pH dependence on recovery for the different chemical forms of Cr, As, and Se was investigated. In speciation analyses, Cr, As, and Se were determined as the total of Cr (III) and a part of Cr (VI), total of As (III) and As (V), and Se(IV), respectively. Determination of total of Se and Cr(VI) remains as future task to improve. Nevertheless, the present method would have possibility to develop as the analytical method to determine comprehensively most metal elements in all standard and guideline values in quality standard in environmental water in Japan, that is, most toxic metal elements in environmental water.

East Asia’s rapid economic growth has led to concerns about the emission of air pollutants. We collected total suspended particle (TSP) aerosol samples simultaneously at three islands in Okinawa, Japan, which are downwind of East Asia, during the Asian dust season, to examine the spatial and temporal variations and chemical transformations of major chemicals in the aerosols. Weekly samples were collected from July 2008 to June 2010, and the concentrations of water-soluble cations, anions, and organic carbon (WSOC) were determined (n = 303). Spatial distribution analysis showed that monthly mean concentrations of non-sea-salt (nss)- SO 4 2 − in the spring (Asian dust season) decreased with increasing distance from Asia, while the trend for NO 3 − was less evident, suggesting that chemical transformation affected the long-range transport of certain chemicals. Temporal variation analysis showed that concentrations of nss- SO 4 2 − , NO 3 − , and WSOC during the spring were about 2.0, 2.4, and 1.8 times those in the summer (cleaner air mass from the Pacific Ocean), respectively. This study demonstrated that air pollutants were transported from the Asian continent to the Okinawa islands and affected the air quality in the region. There may also be impacts on ecosystems, because increased concentrations of particulate NO 3 − could increase nutrient levels around the Okinawa islands.

沖縄県沿岸域の6地点から採水した表層海水中の溶存微量金属を，キレートディスク濃縮法を併用した誘導結合プラズマ質量分析法（ICP-MS）で定量し，10 μg L－1から0.001 μg L－1の濃度レベルの7～10元素の定量値を得た．各海域の微量金属の特徴を考察するために多元素プロファイリングアナリシスを行った結果，沖縄県の市街域沿岸海水では，Zn，Cu，Mn，Pbの定量値が外洋表層海水文献値に比べて10倍以上高濃度を示し，Cdの定量値も比較的高かった．この傾向は本州沿岸域の文献値とよく類似していた．一方，郊外域沿岸海水については，ほとんどの元素の定量値が外洋表層海水に比べて0.5倍から5倍の範囲内であった．また，海洋化学的分類における栄養塩型元素に着目すると，サンゴ礁海域では，Zn，Cdの外洋表層海水文献値による規格化濃度が，Ni，Cuよりも高い傾向にあることが示唆された．

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.

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.

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...

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.

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.

Objective Cytokines have been implicated in the pathophysiology of pulmonary hypertension. We sought to explore the possibility that prostacyclin is a link. Methodology We tested the effects of the cytokines interleukin-1beta (IL-1beta), tumour necrosis factor-alpha (TNF-alpha), and macrophage migration inhibitory factor (MIF) on arachidonic acid metabolism of pulmonary artery smooth muscle cells (PASMCs) with special regard to prostacyclin (PGI2) that protects against pulmonary hypertension. Cultured rat PASMCs were treated with IL-1beta, TNF-alpha, or MIF. Expression of prostacyclin synthase (PGIS) and cyclooxygenase-2 (COX-2) mRNAs, and PGI2 synthesis, were measured. Results We found that PGIS mRNA expression was suppressed by high concentrations of TNF-alpha and MIF, while COX-2 mRNA was induced by all three cytokines tested. IL-1beta increased PGI2 production in a dose-dependent manner. TNF-alpha and MIF also increased PGI2 production, but to a far lesser degree at high concentrations. TNF-alpha paradoxically decreased PGI2 production at a low concentration. Conclusions These results suggest that TNF-alpha and MIF are potentially antagonistic to the action of PGI2 in rat PASMCs via down-regulation of PGIS mRNA. Simultaneous induction of COX-2 mRNA may further counteract the action of PGI2 by increasing the levels of eicosanoids other than PGI2.

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.

In order to determine the risk factors for hearing loss in the elderly, a total of 496 subjects with bilateral hearing loss and 2807 age-matched persons without hearing disturbance were recruited from the participants in an automated multiphasic health screening examination, and their lifestyle and medical data were analysed. Current smokers showed a significantly increased risk of hearing loss compared with non-smokers (odds ratio after adjustment for sex, age, and potential confounders=2.10 (1.53-2.89)), while heavy drinkers did not show an increased risk compared to non-drinkers. Our findings might provide some clues for the primary prevention of age-related hearing loss.

Objectives: Few genetic markers for the prognosis of sarcoidosis have been found. Tumor necrosis factor (TNF)-a has been implicated in the pathogenesis of sarcoidosis. Induced TNF-a or TNF-b levels have been shown to be associated with the polymorphisms of the TNF genes. We investigated the roles of such polymorphisms in the development and prolongation of sarcoidosis. Subjects and measurements: One hundred ten Japanese patients with sarcoidosis and 161 control subjects were genotyped for three biallelic polymorphisms in the promoter region of TNF-a gene by direct sequencing of polymerase chain reaction (PCR) products. A polymorphism of the TNF-b gene (TNFB * 1/TNFB * 2) was detected by Nco I restriction fragment length polymorphism analysis of PCR products spanning intron 1 and exon 2 of the TNF-b gene. Results: None of the polymorphisms conferred susceptibility to sarcoidosis. However, our study identified the allele TNFB * 1, detected by the presence of a Nco I restriction site, as a marker of prolonged clinical course, with the resolution of sarcoidosis being defined as the disappearance of all clinical symptoms, physical signs of active lesions, abnormal chest radiograph findings, and abnormal results of pulmonary function and biochemical tests. When the probability of remission in patients homozygous for TNFB * 2 was defined as 1.00, it was 0.48 (95% confidence interval, 0.26 to 0.88; p < 0.05) in patients with TNFB * 1 (genotypes TNFB * 1/1 and TNFB * 1/2). Conclusions: The TNFB * 1 allele is a marker for prolonged clinical course in patients with sarcoidosis. Our study is the first to link a cytokine gene polymorphism to the prognosis of sarcoidosis. (CHEST 2001; 119:753‐761)

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 (

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.

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.

An amperometric detector based on the chemical modification of Nafion and indium (III) hexacyanoferrate (II, III) thin film (Nafion/In-CN-Fe) onto a glassy carbon (GC) electrode, was first successfully used for the determination of electroinactive cations (Li+, Na+, K+, Rb+, Cs+, NH4 +) in single column ion chromatography (IC). A set of well-defined peaks of electroinactive cations was obtained. The detection limits of the cations are 8.9 × 10–6 mol/L for Li+, 2.3 × 10–6 mol/L for Na+, 5.2 × 10–6 mol/L for K+, 4.8 × 10–6 mol/L for Rb+, 4.0 ׶10–6 mol/L for Cs+ and 5.3 × 10–6 mol/L for NH4 + at a single-to-noise ratio of 3. The proposed method was quick, sensitive and simple. The cations in rainwater and mineral water were successfully analyzed by this method.

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.

人間ドックで何らかの聴力障害を指摘された60歳以上の男女69名に対して, 問診, 鼓膜検査, 純音聴力検査, 67-S語表による語音明瞭度検査を行った。 いわゆる “聴力の生理的年齢変化” と考えられた52名に対して, 聴力レベルを評価した。 喫煙と聴力障害との関連についての検討では, 低周波数250Hzで有意差が認められ, 喫煙が危険因子の1つであると考えられた。 アルコール習慣と聴力障害では明らかな関連は認められなかった。

厚生省特定疾患急性高度難聴調査研究班は, 平成10年度に突発性難聴の重症度基準を作成した。 今回, 我々は, この重症度基準を用いて今まで行われた3回の突発性難聴の全国疫学調査結果の解析を行った。 この重症度基準を用いた分類は, 突発性難聴の治療経過の解析に有用な指標であると考えられた。

The multielement determination of trace elements in coastal seawater by inductively coupled plasma mass spectrometry has been investigated with the aid of chelating resin preconcentration. First, each coastal seawater sample (250 ml) was treated with a chelating resin (Chelex 100) at pH 6 for preconcentration of trace elements. After filtration with a glass filter, the resin on the filter was carefully rinsed with 8 ml of 1 M ammonium acetate solution. Then, trace elements adsorbed on the resin were eluted with 6 ml of 2 M HNO3. As a result, the preconcentration factor of 41.7 fold was obtained, with the total concentration of matrix elements (Na, K, Mg, and Ca) less than 200 mg dm−3. The recovery values were larger than 80% for 22 elements among 29 elements determined. The present method was applied to the determination of trace elements in the coastal seawater certified reference material CASS-3, issued from National Research Council of Canada (NRC), as well as to the coastal seawater sample collected f...

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.

1972年から1998年までの27年間に突発性難聴発症から2週間以内に名大耳鼻咽喉科を受診し, 固定時まで聴力の経過が追えた一側性突発性難聴1739人を対象として耳鳴, 耳閉感と聴力の経過との関係につき検討した。耳鳴有は1542人 (88.7%), 耳鳴無は197人 (11.3%), 耳閉感有は833人 (47.9%), 耳閉感無は906人 (52.1%) であった。 耳鳴無の124人 (62.9%) に耳閉感があり, 全体の比率より有意に高かった。 耳鳴有の症例は耳鳴無の症例に比し初診時聴力は悪い傾向にあったが, 固定時聴力にはほとんど差は認められなかった。 耳閉感の有無は聴力回復の程度と関連を認めなかった。

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.

Several cytokines are involved in the pathophysiology of sarcoidosis. Granulocyte-macrophage colony-stimulating factor (GM-CSF) may be one of these cytokines because its mRNA is expressed by inflammatory cells obtained from the sarcoid lung. We thus asked two questions. Is GM-CSF secreted by bronchoalveolar lavage (BAL) cells? What type of cells express GM-CSF? GM-CSF secreted by the cultured BAL cells from 19 untreated sarcoid patients was measured by an enzyme-linked immunosorbent assay. The individual cells expressing GM-CSF mRNA were identified by in situ hybridization in seven patients. Spontaneous release of GM-CSF by BAL cells was demonstrated in one patient. When stimulated, BAL cells secreted GM-CSF in all subjects studied. In situ hybridization with digoxigenin-labelled GM-CSF cRNA probe revealed that the positive cells were round in shape and larger than lymphocytes, but smaller than large alveolar macrophages that are often irregular in shape. These results strongly indicated that small alveolar macrophages secrete GM-CSF in the sarcoid lesion. This phenomenon may contribute to the enhanced immunological activities observed in sarcoidosis.

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.

A combined system of size exclusion chromatography, UV absorption detection and ICP-MS was used for elucidation of the dissolved states of yttrium and lanthanide elements in lake water collected from Lake Biwa, Japan. The lake water samples were filtered with a membrane filter (pore size 0.45 µm) just after filtration with a glass filter (pore size 1.0 µm). The total concentrations of the dissolved lanthanide elements in the filtrate were determined by ICP-MS after chelating resin preconcentration. For speciation analysis, the above filtered water samples were further preconcentrated 30–500-fold with an ultrafiltration filter, which allowed preconcentration of molecules with molecular masses >10000. The preconcentrated sample solution was then subjected to speciation analysis using the above combined system, where a size exclusion column with the molecular permeation range between 1000 and 300000 was used for molecular separation. In the size exclusion chromatograms obtained with UV absorption detection at 254 nm, two peaks of some large organic molecules were obtained at retention times corresponding to molecular masses of >300000 (peak 1) and about 50000–10000 (peak 2). In the chromatograms, which were measured on-line by ICP-MS, yttrium and lanthanide elements (Y, La, Ce and Pr) were found at the two peak positions corresponding to above large organic molecules.

Ion Chromatographic separation of inorganic ions (anions and cations) was investigated by using three kinds of sulfobetaine-type surfactants (CHAPS, C12SB, and C14SB) as the stationary phases, which were coated by hydrophobic adsorption on the ODS column. In the present separation system, pure water was used as a mobile phase. Since the amount of surfactant adsorbed on the ODS surface significantly influenced the retention behaviors of inorganic ions, the amounts of the sulfobetaine-type surfactants adsorbed were estimated by the breakthrough procedure. The maximum amounts of CHAPS, C12SB and C14SB adsorbed were 0.40, 0.87 and 1.08 mmol, respectively. It was elucidated from the chromatograms of inorganic ions that the retention behavior of inorganic anions was directly related to the surface charges arising from the adsorbed surfactants. The large surface charge was effective for the efficient separation of inorganic ions in water elution. In addition, their retention behavior was strongly affected by the hydrophobicity of the adsorbed surfactants as well as the ionic functional groups of the surfactants which produced the charged surface. The elution order of inorganic anions was correlated with the Hofmeister series. This suggests that the hydration energies of the ions play important roles in separation in the water elution system.

Isotope dilution-inductively coupled plasma mass spectrometry (ID-ICP-MS) was applied to the determination of lead in natural water, and its precision was compared to that of the conventional calibration method. Trace amount of lead in natural water was preconcentrated using a chelating resin of Chelex 100 before ID-ICP-MS, where the preconcentration factor of 50 was obtained. The concentrations of lead were 26.1 pg/g and 266 pg/g for the certified river reference materials (JAC 0031) and the pond water sample, respectively, with the RSD less than 1%.

The dissolved states of trace metal ions in natural water have been investigated by using the ultrafiltration technique and the combined system of size exclusion chromatography /ICP-MS. The Lake Biwa was chosen as the experimented field. The lake water samples were first filtered with the membrane filter (pore size 0.45μm), and then the filtrate solutions were concentrated by 500-fold with the ultrafiltration filter, which concentrated the large organic molecules with the molecular weight larger than 10, 000. The concentrated solutions thus prepared by ultrafiltration were analysed by size exclusion chromatography with the molecular weight permeation range from 10, 000 to 300, 000, where the chromatograms were detected by the UV absorption detector and ICP-MS. The analytical methods were applied to the vertical profile measurements of the SEC chromatograms in Lake Biwa. In consequence, it has been elucidated that most of metal ions in natural water are in the large organic molecule-metal complex forms.

An on-line separation-detection system, liquid chromatography coupled with inductively coupled plasma mass spectrometry (ICP-MS), has been developed and applied to the study on speciation of trace metals in pond water. First, the total concentrations of dissolved metal ions in pond water were determined by ICP-MS after chelating resin preconcentration. Then, pond water was preconcentrated by ultrafiltration using a filter with a molecular weight permeation limit of 10000, providing size exclusion chromatography. Large organic molecules which had combined with trace metals in the preconcentrated samples were separated with a gel filtration column and detected by UV absorption and ICP-MS, sequentially. In consequence, large organic molecules with the molecular weight of ≥300000 and 10000—50000 could be observed. A large number of trace metals (41 elements) were found in those organic molecules. Furthermore, the percentages of metal ions in the forms of large organic molecule–metal complexes were estimated f...