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Telomere length is thought to be a biomarker of biological aging. This study examined whether telomere length was associated with urinary concentrations of 8-hydroxy-2'-deoxyguanosine (8-OHdG), a biomarker of oxidative stress, and antioxidative trace elements in 73 female Japanese university students (age: 19.2 ± 0.7 years). We quantified 8-OHdG and selenium in urine by liquid chromatography-mass spectrometry and inductively coupled plasma-mass spectrometry, respectively. Telomere length and urinary concentrations of other essential trace elements (molybdenum, cobalt, and chromium) that were previously measured in the same study participants, were used in this study. We used multiple linear regression analysis to examine the associations of telomere length with urinary 8-OHdG and essential trace element concentrations (covariates: urinary cotinine concentration, age, BMI, and drinking status). The geometric means (geometric standard deviation) of 8-OHdG and selenium were 3.4 (1.5) and 31 (1.3) µg/g creatinine, respectively. Telomere length was not associated with urinary 8-OHdG concentration, but was negatively associated with urinary selenium concentration. In conclusion, telomere length was not associated with urinary 8-OHdG concentration in the young women in this study. Longitudinal studies should be conducted to clarify the association between telomere shortening rate and oxidative stress level.

An automatic pH adjustment instrument was developed for the preparation of analytical samples prior to solid phase extraction, which is widely used as a pretreatment technique for the separation of sample matrixes and preconcentration of elements for analysis. Real-time monitoring of the sample pH condition was performed by observing the light signal intensity of the pH-sensitive wavelength of the pH indicating reagent. A light of pH-insensitive wavelength was selected as the reference light to cancel the signal intensity variation of the pH-sensitive light due to the difference of pH indicating reagent concentration, possible difference in transparency of sample vessels, and minute fluctuation of the light source. The pH condition was elevated by automatic addition of ammonia solution using a nebulizer in the flow line of which an electromagnetic valve was equipped. Open and close operation of the electromagnetic valve was controlled based on the difference between the real-time pH condition and the target pH condition. The effectiveness of the instrument was confirmed by using various pH indicating reagents and by analyzing trace elements in a seawater certified reference material.

A simple and low-cost method of fabricating an optical fiber for a surface plasmon resonance (SPR) sensor was proposed. The method is based on the electroless nickel plating and subsequent displacement gold plating of the core of the optical fiber. The thickness of the nickel and gold thin films deposited on the core of the optical fiber could be controlled by measuring the reflected light intensity from the tip of the optical fiber during the plating processes. The sensitivity and resolution of the SPR sensor with the fabricated optical fiber in the refractive index range from 1.333 to 1.348 were 1324.3 nm/RIU and 7.6 × 10

Cadmium is a toxic metal found ubiquitously throughout the world. Our study evaluated whether cadmium exposure was associated with telomere length in 73 female university students. Determination of telomere length was performed by quantitative polymerase chain reaction using DNA in blood. Urinary cadmium concentration was measured by inductively coupled plasma mass spectrometry. The students' physiological attributes and lifestyle were surveyed by means of a self-administered questionnaire. The geometric mean of urinary cadmium concentration was 0.312 μg/g creatinine, which was lower than the levels previously reported for Japan. Urinary cadmium concentration was not significantly associated with telomere length, though the exposure level of the present subjects was similar to that of previous study subjects which found significantly negative associations. It is possible that other factors affected telomere length in this study population.

A simple purification technique using an anion-exchange monolithic spin tip was described for the elimination of molybdenum oxyanion interfering with precise determination of cadmium in human urine samples by ICP-MS. The tip device named “anion-exchange tip-in monolith (AXTip)” was laboratory-prepared within the confines of a commercially available syringe filter tip by a two-step process: (1) in situ copolymerization of glycidyl methacrylate (GMA) and ethylene dimethacrylate (EDMA) and (2) its subsequent modification with trimethylamine (TMA), as a strong anion-exchange functional group, via ring-opening reaction of epoxide. The adsorption capacity of the AXTip was > 3.2 μmol/tip for molybdenum oxyanion. The performance of the AXTip was evaluated through an adsorption/non-adsorption experiment for molybdenum, cadmium and other metal and metalloid species, using a model solution and human urine samples to optimize the sample solution's pH and dilution factor for the AXTip treatment. In the case of urine sample analysis, 8 times dilution and pH adjustment to 4.0 prior to AXTip treatment were found to allow > 98% elimination of interfering molybdenum oxyanions and quantitative recovery (103 ± 7%) of cadmium. At the optimized conditions, the AXTip treatment reduces Mo/Cd ratio from ~400 in human urines to

Elemental abundances of prokaryotic and eukaryotic cells as well as organelles were provided as the number of atoms per cell (or organelle). In order to examine the specific uptake of vital elements by cells, E. coli cells were grown in different media and harvested at several time points during the cell growth and proliferation. The major-to-ultratrace elements in the cells were determined by micro-flow injection (μFI)-ICP-MS after microwave-assisted acid digestion of less than 10 mg of dry weight sample. Cyanobacteria and chlorella were also cultivated to compare elemental abundance differences among species. In addition, to further examine the localization and utilization of vital elements in the cells, chloroplasts and mitochondria were isolated from the tissues of spinach leaves, potato tuber, and bovine liver by density-gradient centrifugation using Percoll. The concentration data obtained by ICP-MS measurements were normalized to a per cell (or organelle) basis, taking into account the cell size and water content. Among about 60 elements detectable by ICP-MS, more than 30 elements were quantitatively determined, and it was clearly found that essential elements participating in specific vital functions such as redox reactions were highly accumulated in the microorganisms and organelles.

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.

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 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 (

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.

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...

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.

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...

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.

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.

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...

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.

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 discrete microsampling technique for multielement determination of trace elements by inductively coupled plasma mass spectrometry has been investigated for analyses of samples containing large amounts of matrix elements. In the technique, 100 μl of the sample solution was introduced into the plasma by using a six-way valve, and 10 elements were detected in peak hopping mode during a single mass range scan. As a result, a transient peak profile of the signal for each element was observed at each m/z position. The peak area measurement method was established for the quantitative analysis. The optimization of instrumental conditions and matrix effects in multielement determination were investigated in detail. The discrete microsampling technique was found to reduce some memory effects due to matrices in ICP-MS. The present system was applied to the analyses of standard sediment sample and 30 elements at the μg g−1 level were successfully determined without matrix separation.

An analytical method for multielement determination of trace and ultratrace elements in seawater has been investigated by using ICP-MS. Trace and ultratrace elements were preconcentrated by 10- or 20-times with addition of aluminum into seawater and then the elements were determined by ICP-MS. In this procedure, aluminum was added as the carrier for coprecipitation; it precipitated together with magnesium in seawater. Some trace elements were also measured by ICP-AES after coprecipitation. In addition, major and minor elements in seawater were determined by ICP-AES after dilution with acidified water. As the result, 37 elements in total could be determined in coastal seawater. The present results are compared with the concentrations of the elements in open seawater.

Simultaneous multielement determination of minor and trace elements in the urine reference sample by an ICP-MS/AES combined system is described. The biological reference sample of NIST SRM 2670 Freeze-dried Human Urine (elevated) was used for analysis. The sample preparation was kept to a minimum: the urine sample was diluted 25-fold with 0.1M nitric acid, in which Ge, In and Tl were added as the internal standard elements. Eighteen elements at theμg/ ml-ng/ml levels were simultaneously determined by the present combined system. In addition, the present combined system was also applied to the correction of polyatomic interference in the determination of chromium in SRM 2670, where interference with 52Cr due to 40Ar12C was corrected by estimating the correction factor of 40Ar12C from correlation between the ion count of 40Ar12C and the emission intensity of carbon in the sample.

The effects of the solute properties in aqueous solutions on the separation characteristics in ultrasonic atomization were experimentally examined. For the aqueous solutions of monohydric alcohols (methanol, ethanol and 1-propanol) and ketone (2-butanone), the content in the accompanying liquid was larger than that in the residual solution. For the aqueous solutions of dihydric alcohol (propylene glycol), trihydric alcohol (glycerol) and amides (formamide and acetamide), on the other hand, the content in the accompanied liquid was smaller. From these, it was considered that the hydrophilic and hydrophobic properties of solute molecules govern the separation characteristics in ultrasonic atomization. For the aqueous solutions of carboxylic acids (acetic acid and propioloc acid) and inorganic salts (Li2SO4, Na2SO4, K2SO4, Rb2SO4 and Cs2SO4), the content in the accompanied liquid was the same as that in the residual solution. These results indicate that ionized molecules in water were not separated by ultrasonic atomization.

A hyphenated system of inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS) combined with aid of optical fiber was developed for versatile simultaneous multielement measurement of the elements from the major to ultratrace levels. In the present system, the emission signals from the argon ICP equipped for ICP-MS were led through optical fiber to a sequential-type monochromator for ICP-AES measurement. In consequence, the dynamic range of 9 orders of magnitude from a few pg ml−1 up to ca. 1000 μg ml−1 was obtained, which allowed the simultaneous determination of a variety of elements in the wide concentration range by ICP-MS and/or ICP-AES. The present system was applied to simultaneous multielement analysis of rock and seawater samples.

Multi-element determination of trace elements in seawater by inductively coupled plasma mass spectrometry (ICP-MS) has been investigated. Coprecipitation with gallium hydroxide was used for preconcentration of trace elements and elimination of matrix elements. Most trace elements were quantitatively collected at pH 10 with the concentration factor of 10. In the present experimental method, 17 elements (Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Y, Zr, Sn, La, Pb, Th, U) in a coastal seawater sample could be determined by ICP-MS. In addition, 6 elements (Al, Mn, Fe, Ni, Cu, Zn) among them were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES). The analytical results obtained by ICP-MS and ICP-AES were in fair agreement.

Simultaneous multielement analysis of geological standard rock samples (JG-1 and JB-2) has been successfully performed by inductively coupled plasma mass spectrometry using a discrete microsampling technique. In this technique only 100 μl sample solution was used for simultaneous determination of 5–10 elements in solution.

Vol. 1 No. 1ABSTRACT A lanthanum (La) co-precipitation method was explored for pre-concentration of oxo-anion forming elements followed by measurement with Inductively Coupled Plasma Mass Spectrometry (ICP-MS). The co-precipitation and subsequent washing and elution steps were performed in a 25 mL-volume syringe in order to save the sample consumption and to avoid the contamination from the experimental environment. In the present work, various parameters such as the concentration of La added into the sample solution, the pH, aging time, and so on were optimized to obtain good recoveries and analytical detection limits for V, As, Se, Sb, and W. Generally, in the co-precipitation method, high concentration of precipitant (in this case, La) causes a serious problem of signal memory effect in ICP-MS measurement. To reduce such memory effect, in the present experiment, high level of La was removed by passing the analyte solution (i.e., lanthanum hydroxide dissolved in 1 M HNO3) through a mini column packed with cation-exchange resins. The method thus obtained was evaluated through the measurement of V, As, Se, Sb and W in seawater reference materials (CASS-4 and NASS-5). The recoveries exceeded 80%, and the observed values were in good agreement with the certified values. Thus, the present method was applied to the determination of trace elements in real seawater sample. Keywords: Lanthanum, pre-concentration

The multielement determination of trace metals in seawater was carried out by inductively coupled plasma mass spectrometry (ICP-MS) with aid of a down-sized chelating resin-packed minicolumn for preconcentration. The down-sized chelating resin-packed minicolumn was constructed with two syringe filters (DISMIC 13HP and Millex-LH) and an iminodiacetate chelating resin (Chelex 100, 200-400mesh), with which trace metals in 50mL of original seawater sample were concentrated into 0.50mL of 2M nitric acid, and then 100-fold preconcentration of trace metals was achieved. Then, 0.50mL analysis solution was subjected to the multielement determination by ICP-MS equipped with a MicroMist nebulizer for micro-sampling introduction. The preconcentration and elution parameters such as the sample-loading flow rate, the amount of 1M ammonium acetate for elimination of matrix elements, and the amount of 2M nitric acid for eluting trace metals were optimized to obtain good recoveries and analytical detection limits for trace metals. The analytical results for V, Mn, Co, Ni, Cu, Zn, Mo, Cd, Pb, and U in three kinds of seawater certified reference materials (CRMs; CASS-3, NASS-4, and NASS-5) agreed well with their certified values. The observed values of rare earth elements (REEs) in the above seawater CRMs were also consistent with the reference values. Therefore, the compiled reference values for the concentrations of REEs in CASS-3, NASS-4, and NASS-5 were proposed based on the observed values and reference data for REEs in these CRMs.

Simultaneous multielement analysis of geochemical and environmental samples such as rock, sediment, seawater, and lake water have been carried out by inductively coupled plasma atomic emission spectroscopy (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). In these experiments, some instrumental improvement and sample pretreatment techniques were required to fulfil accurate multielement determination of 30-50 elements for each sample described above. Consequently, it becomes possible to characterize the samples by comparing the profiles of their multielement concentration distributions. Such multielement profiling analysis of various samples may be useful in the research fields such as geochemistry, environmental chemistry, material science and so forth. >

Rare earth elements (REEs) in a blood serum reference sample, which is a freeze-dried sample issued from the National Institute for Environmental Studies, Japan, have been determined by inductively coupled plasma mass spectrometry (ICP-MS) after sample digestion and concentration pretreatment. The freeze-dried serum sample (ca. 0.8 g), which corresponded to 10 ml of original blood serum, was digested with HNO3 with heating on a hot plate. The digested sample was then diluted with 100 ml of 0.1 M HNO3, and REEs in the diluted solution were adsorbed on chelating resin (Chelex 100). The resin was then filtered with a glass filter. Finally, REEs on the resin were dissolved with 10 ml of 2 M HNO3 aqueous solution, and the sample solution was analyzed by ICP-MS. The concentrations of all the REEs were successfully determined by the present method. The recovery values of REEs were in the range of 70-80%, and the relative standard deviation of the recovery values in repeated experiments (n = 3) was less than 5% for all REEs. In addition, 20 other elements were also determined by ICP-MS and ICP-AES.

The real-time multielement monitoring of airborne particulate matter (APM) was carried out using an inductively coupled plasma mass spectrometry (ICP-MS) instrument equipped with a newly developed gas converter apparatus. By using the gas converter apparatus, gas molecules in the air sample and Ar molecules were almost completely exchanged and the gas-converted air sample could be directly introduced into ICP-MS instruments. Fe in clean room and outdoor air samples was directly measured using the ICP-MS instrument equipped with the converter apparatus. The signal intensities of Be, Ag, Cd, Sn, Sb, Tl, Pb, Bi, Th, and U in the outdoor air sample were successfully measured at every 8 min for 77 h.

Aldol condensation products of two lysyl-derived aldehyde (allysine) residues are involved in cross-linking of collagen. However, the distribution of these cross-links and their age-related changes remain largely unanswered. We have found that the unsaturated aldehydes of aldol condensation cross-links can be fluorescent labeled. When labeled with pyrenesulfonylhydrazine, pyrene dimers and excimers fluoresce at 383 and 485, nm, respectively. (The pyrene dimer is stable in benzene, whereas in polar solvents it exhibits an exponential decay to monomer fluorescing at 378 nm.) Dimers bound to collagen also decay to monomers, but at a more complicated, nonexponential rate. This dissociation in collagen is also associated with gradual decrease in the excimer fluorescence. While dissociated monomers appear to be reassociated by redialysis, the excimer is not regenerated. During fibril formation in vitro of the labeled collagen, two fluorescence changes take place: a very rapid decrease of the excimer fluorescence and a gradual increase of the monomer fluorescence. These changes indicate very early and early conformational changes at the nonhelical terminal telopeptides. The excimer fluorescence also decreases upon thermal and guanidine denaturation. Two different environments for excimer formation are suggested by the latter. It is concluded that pyrenesulfonylhydrazine offers a unique and sensitive probe for the proximity of aldehyde groups as well as for the mobility and conformation changes of the telopeptides in collagen.

Iodoacetamide and its spin-labeled derivative in high concentration ranges (10−2−10−1M) react with unexposed SH-groups of rhodopsin in the dark. The spin-labels bound to these SH-groups are moderately immobilized. While rhodopsin is not spin-labeled with the iodoacetamide at a lower concentration (5 × 10−4 m) in the dark, photobleached rhodopsin is readily spin-labeled with this concentration. The photo-bound spin-labels are highly immobilized and do not change their mobility after the regeneration of rhodopsin. Urea enhances the dark-bleaching of rhodopsin by iodoacetamide and increases the mobility of the bound spin-labels. The dark-reacting unexposed SH-groups appear to be different from the photo-exposed SH-groups which are not directly involved in the 500-nm chromophore.

Carcinogenic hydrocarbons benz[ a ]anthracene (BA), 7,12-dimethyl-BA (DMBA) and 3-methylcholanthrene (MC), bound non-covalently to bovine serum albumin (BSA), are photo-oxidized and become covalently bound to the protein as a result of irradiation at 365 nm. BSA with covalently-bound hydrocarbon photoproducts can be isolated by SDS-gel filtration after repeated ether extraction. In this photo-oxidation, BA and DMBA are converted apparently to phenanthrene-type products together with some other photoproduct in the case of BA, whereas MC produced a naphthalene-like photoproduct and an intact molecule bound to BSA. Our findings suggest that these hydrocarbons can undergo photo-activation and macro-molecular binding as in metabolic activation.

Acid-soluble collagens isolated from young and old rat tail tendon were fluorescent-labeled with dansyl hydrazine, which is capable of reacting with aldehyde groups in collagen. The dansyl fluorescence of aged collagen exhibited a weak peak at 525 nm, whereas that of young collagen had a stronger broad peak at 500 nm. Fibril formation in vitro was partially inhibited in these dansylated collagens. During the turbidity lag phase, the dansyl fluorescence was found to increase (30–50%), also shifting to 485 nm. These changes reveal the telopeptide conformation changes occurring during this period. A new fluorescence peak at 420 nm also increased during fibril formation. When the dansylated collagen was irradiated in air with uv light (340 nm), a rapid decrease of the dansyl fluorescence with a concurrent shift to 490 nm occurred. Also, the formation of fibrils was further inhibited. With increasing temperature, the dansyl fluorescence of young collagen decreased, whereas that of old collagen substantially increased, particularly at the denaturation temperature around 38°C. After denaturation, both fluorescences became similar in their intensity and position (490 nm). These findings are discussed in connection with both age-related structural changes of collagen and the mechanism of fibril formation.

The pyrene-labeling of acid-soluble (type I) and acid-insoluble collagens from young and old rat tail tendon has been investigated. The pyrene excimer fluorescence is associated with stabilized pyrene labels bound to two adjacent aldehydes in monomeric young collagens. Polymeric young collagens, as well as monomeric and polymeric old collagens, tend to lose this specific arrangement. This is shown by salt and new chromatographic fractionation of monomeric and polymeric collagens. During denaturation, pyrene labels are released from saturated aldehydes in both alpha 1 and alpha 2 chains. This unstable pyrene-labeling is stabilized by NaBH4 reduction of the hydrazone bonds between aldehyde groups and pyrene-containing hydrazines. This stabilization reveals that alpha 1 contains more aldehyde groups than does alpha 2 in young collagen. Pepsin-solubilized, acid-insoluble collagens are partly cross-linked and, like acid-soluble collagens, exhibit the fluorescence of pyrene aggregates probably located at unidentified cross-links, different from unsaturated aldehyde-containing cross-links in acid-soluble collagens.