Hiroki
Haraguchi
a and
Naoki
Furuta
*b
aAssociation of International Research Initiatives for Environmental Studies, 1-4-4, Ueno, Taito-ku, Tokyo 144-0001, Japan. E-mail: haraguch@airies.or.jp
bFaculty of Science and Engineering, Department of Applied Chemistry, Chuo University, 1-13-27 Kasuga, Bunkyo-ku, Tokyo 112-8551, Japan. E-mail: nfuruta@chem.chuo-u.ac.jp
![]() Hiroki Haraguchi |
![]() Naoki Furuta |
We would like to commence this review with the memorial event in 1985 in Japan. At the end of March, 1985, Keiichiro Fuwa, who was a great leader in spectrochemical analysis in Japan, retired from the University of Tokyo, and was promoted to the vice-director of the National Institute for Environmental Studies (NIES) (he became the director of NIES in 1987). The photo of K. Fuwa is shown in Fig. 1, which was taken on the memorial occasion of his retirement ceremony. As is well known, he made a great contribution to the progress of analytical atomic spectrometry not only in Japan but also in the world. One of the most famous works of Fuwa concerned the development of the long tube burner (often called “Fuwa-Vallee tube”) for flame atomic absorption spectrometry (AAS), which was developed during his stay in the USA. He stayed from 1955 to 1978 in the Medical School of Harvard University with Bert L. Vallee. Vallee was one of the pioneers to establish the biochemistry of metalloenzymes, especially concerned with zinc enzymes and metallothionein. The long-tube burner AAS of Fuwa provided very high sensitivities for Zn and Cd, enabling detection of key elements in metalloproteins. Thus, the long-tube AAS contributed to the progress of the early research on metalloenzymes.
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Fig. 1 Photo of K. Fuwa on the occasion of his retirement ceremony in 1985. |
After coming back to Japan from the USA, Fuwa was appointed first to the Department of Agricultural Chemistry, and then the Department of Chemistry at the University of Tokyo. In 1981, the Japan Society for Analytical Chemistry (JSAC) organized the XXII Colloquium Internationale Spectroscopicum (CSI), which was held for the first time in an Asian country. In this CSI, Fuwa served as the secretary general, and the conference was successful. It should be noticed here that Velmer A. Fassel gave his plenary lecture in XXII CSI, with a topic on Inductively Coupled Plasma Mass Spectrometry (ICP-MS) as a newly developed analytical method. This lecture took us by surprise, because, as will be described later, Japan was still in the early stage of Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) at that time. A lot of young scientists including Furuta were stimulated by the great chance to meet many prominent scientists at XXII CSI.
One more thing should be added to our history on this occasion. Cameron W. McLeod visited Japan as a postdoctoral fellow in Fuwa's laboratory at the University of Tokyo, but he preferred life in rural Japan and thus he was mostly at NIES located in the newly constructed science city, Tsukuba, where he worked with Naoki Furuta. We were so grateful that McLeod stayed in Japan for 3 years and gave us great stimulation in the development of AAS. According to the statistics in 2008, Hitachi High-Technologies (former Hitachi) shared 36% and Shimadzu 30% out of approximately 450 AAS instruments annually sold in Japan.
Thus in January, 1980, the Discussion Group of Plasma Spectrochemistry was established, in which Fuwa was elected as the president of the Group and Hiroki Haraguchi served as the secretary general. Kazuo Yasuda (Hitachi), Kenjiro Tohyama (Shimadzu), Masatoshi Morita (NIES), Taketoshi Nakahara (Osaka Prefectural University) and many other analytical and spectrochemical scientists joined as steering committee members. Since then, this Discussion Group has been continuously taking leadership in the progress of AAS, and contributing to the propagation of the instruments as well as the establishment of analytical methods for various samples. After Haraguchi moved from the University of Tokyo to Nagoya University in Dec., 1988, the activity of the Discussion Group stopped for five years. Taking the opportunity of Furuta's movement from NIES to Chuo University in 1994, the Discussion Group resumed. The following scientists have been the presidents of the Discussion Group; Keiichiro Fuwa, Hiroki Haraguchi, Taketoshi Nakahara, Naoki Furuta, and presently Koichi Chiba (National Metrology Institute of Japan, AIST).
It is worthwhile to introduce the management doctrine of the Discussion Group, which was agreed with the steering committee at the beginning; (1) it covers the whole area of analytical atomic spectrometry, (2) it is independent from any academic societies, (3) the steering committee of the Group is composed of the fundamental researchers (from the universities and national institutes), customers (users) and representatives from all instrument manufacturers. The Discussion Group has been organizing 3 or 4 meetings per year, including one seminar (so-called “Tsukaba Seminar”) as the annual event, and keeping the number of registered members over 350.
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Fig. 2 Photo taken on the occasion of Durham Conference in 1992. From left to right; K. Tanaka, N. Furuta, S. Yamazaki, N. Nonose, and Y. Takaku. |
Hitachi started to sell a high power N2-Microwave Induced Plasma (MIP)-MS in 1990, and ICP-ion trap MS in 1997. Hitachi instruments were commercially available only inside Japan. They did not sell the instrument outside Japan because of maintenance problems. Scientists actively involved in the development of ICP-MS instruments at Hitachi were Konosuke Oishi, Toyoharu Okumoto, Yasushi Terui et al.4 At present Hitachi High-Technologies have stopped selling both ICP-OES and ICP-MS instruments, and only deal with the sale of a solid-phase extraction resin, so called NOBIAS, for sample preconcentration. Yokogawa Analytical Systems succeeded in selling their instruments abroad in cooperation with international companies. Yokogawa Analytical Systems launched HP 4500 ICP-MS to the world market in 1994 in cooperation with Hewlett-Packard. The instrument was of a smaller size and easy to operate, and the detection capability was improved by one order of magnitude. In order to respond to the request of further sensitivity improvement from semi-conductor industries in Japan, Yokogawa Analytical Systems developed a shield torch and cool plasma ICP-MS in 1995–1996. Scientists actively involved in the development of such an instrument at Yokogawa Analytical Systems were Kenichi Sakata, Katsuhiko Kawabata et al.5 From 1996 to 1999 a collision-reaction cell was developed to alleviate spectral interferences in the ICP-QMS instrument using a hot plasma, and Agilent 7500 was launched in 2000. A collision cell for the Agilent 7500 proved very effective at reducing spectral interferences due to poly-atomic ions and the S/N improvement was also achieved. Noriyuki Yamada, Junichi Takahashi et al. were deeply involved in the development of the Agilent 7500. The semiconductor industry is one of the important industries in Japan, so that high resolution ICP-MS is used widely for analysis of ultra-pure materials and reagents. According to a reference in 1999,6 the number of high-resolution ICP-MS instruments installed in Japan was 57, and this amounted to one fourth of the total number of instruments (227) worldwide. According to the statistics in 2008, the market share of Agilent Technologies was 55%, and Perkin Elmer 22%, out of approximately 200 ICP-QMS instruments annually sold in Japan.
From 2000 to 2010, ICP-MS instruments were installed in many universities, national institutes and industries, and were applied to environmental and geological sciences; biological, clinical and pharmaceutical; industrial materials; high purity materials including semiconductors; food, agriculture and nutrition; and nuclear. Some recent activities in Japan will be introduced further here. Akitoshi Okino (Tokyo Institute of Technology) is developing an alternative plasma source which is operated by a pulse mode using gases other than Ar such as He, N2, CO2 and Air. Takafumi Hirata (Kyoto University) is conducting precise isotope ratio measurements of geological samples and recently, biological samples, too, using a laser ablation system combined with a multi-collector ICP-MS instrument. Furuta is monitoring concentrations of trace elements in size-classified airborne particulate matter and is investigating the role of selenium in biological samples by using selenium speciation analysis. Koichi Chiba (AIST) is developing certified reference materials of industrial and environmental samples. Yuichi Takaku (Institute for Environmental Sciences) is investigating environmental cycles of actinide elements, strontium, cesium and iodine, which have the possibility of being released from a nuclear reprocessing plant, located at Rokkasho village in Japan. These active scientists are the current steering committee members of the above mentioned Discussion Group for Plasma Spectrochemistry in Japan and are contributing to dissemination and development of plasma spectrochemistry in Japan. Young scientist participation is growing steadily. Intensive discussion is taking place in the atomic spectroscopy sessions at annual meetings (twice in a year, in spring and in autumn) organized by JSAC. The Discussion Group for Plasma Spectrochemistry organized the Third Asia-Pacific Plasma Winter Conference in 2008 (2008 APWC) and invited many prominent scientists from abroad. Young scientists attending the conference were stimulated and will contribute to the future development of atomic spectrochemistry in Japan.
After the development in sensitivity by analytical atomic spectrometry, a new trend from total analysis to speciation analysis was initiated in the late 1970s. As is well known, the biological functions or toxicities of the elements mostly depend on the chemical forms (species), not on their total contents. Then, species analysis, i.e., chemical speciation, became a hot topic in analytical atomic spectrometry since the early 1980s. The review paper by T.M. Florence and G.E. Batley, entitled “Chemical speciation in natural waters”, provided great impact on the establishment of the concept of chemical speciation.7 In chemical speciation analysis, analytical atomic spectrometric methods such as AAS, ICP-OES and ICP-MS, which are highly-sensitive and element-selective detection methods, are generally combined with various separation methods such as GC (Gas Chromatography), LC (Liquid Chromatography), CE (Capillary Electrophoresis) etc. Since no more details about chemical speciation are described here, it is recommended to refer to some important references8,9 about the fundamentals and application in chemical speciation.
Here, we will briefly introduce the early contribution to chemical speciation by Japanese scientists. In 1980, K.T. Suzuki published the paper entitled “Direct connection of high speed liquid chromatography equipped with gel permeation column to atomic absorption spectrophotometer for metalloprotein analysis: metallothionein”.10 In this work, the hyphenated system of HPLC and AAS was used to identify the isomers of metallothionein containing Cd, Cu and Zn. It can be noted that this paper by Suzuki is a sort of classical paper in speciation of metallothionein and so often cited even now. After the pioneering work, Suzuki made a great contribution to the development of chemical speciation of metals and metalloids.11 His work on the metabolisms of arsenic and selenium elucidated several unknown metabolites of arsenic and selenium in human and animals. Sadly, Suzuki passed away on July 15, 2008. It was soon after his retirement from Chiba University. He was formerly based at NIES, Tukuba.
Morita and his co-workers at NIES developed speciation methods of arsenic compounds in various biological samples such as seaweeds, fish and shellfish, where they used LC/ICP-OES12 and LC/ICP-MS.13 These works by Morita et al. provided a kind of classical standard method for speciation of arsenic compounds. In addition, Hiroaki Tao (AIST) developed speciation methods using GC/ICP-MS, which was successfully applied to speciation of mercury and tin compounds in environmental samples at the femtogram level.14
• International Conference on Analytical Chemistry 1991 (ICAS 1991), Makuhari, Japan, August 25–31, 1991. The 1st Asian Conference on Analytical Chemistry (Asianalysis I) was co-organized.
• International Conference on Analytical Chemistry 2001 (ICAS 2001), Tokyo, Japan, August 6–10, 2001. Asianalysis VI was co-organized.
• International Symposium on Bio-Trace Elements 2002 (BITREL 2002), Wako, Japan, October 28–November 1, 2002.
• The 11th International Symposium on Biological and Environmental Reference Materials (BERM 11), Tsukuba, Japan, October 29–November 2, 2007.
• International Symposium on Metallomics 2007 (ISM 2007), Nagoya, Japan, November 28–December 1, 2007.
• 2008 Third Asia-Pacific Winter Conference on Plasma Spectrochemistry (2008 APWC), Tsukuba, Japan, November 16–21, 2008.
In addition to the above conferences held in Japan, several international conferences related to analytical atomic spectrometry have been held in Asian countries. Some of them are as follows;
(1) 2005 First Asia-Pacific Winter Conference on Plasma Spectrochemistry, 2005 (2005 APWC), Chiang Mai, Thailand, April 25–30, 2005.
(2) 2006 Second Asia-Pacific Winter Conference on Plasma Spectrochemistry (2006 APWC), Bangkok, Thailand, November 27–December 2, 2006.
(3) XXXV Colloquium Spectroscopicum Internationale (XXXV CSI), Xiamen, China, September 23–27, 2007
(4) The 9th Asian Conference on Analytical Chemistry (Asianalysis IX), Jeju Island, Korea, November 4–8, 2007
(5) The 10th Asian Conference on Analytical Chemistry (Asianalysis X), Kuala Lumpur, Malaysia, August 11–13, 2009.
The first lecture was given at the Tokushima Seminar on Chemical Engineering, June 14, 2002, Tokushima, Japan. In this lecture, he hopefully proposed the establishment of a new scientific world “metallomics” for the first time, based on the progress of analytical atomic spectrometry, as follows.
The second lecture concerned with metallomics was given in the International Symposium on Bio-Trace Elements 2002 (BITREL 2002), October 28–November 2, 2002, Saitama and Yamanashi, Japan, which was organized by Shuichi Enomoto in RIKEN (Institute of Physics and Chemistry). In this lecture, Haraguchi formally proposed metallomics as a new scientific field in order to integrate the research fields related to bio-trace metals, with emphasis on the importance of chemical speciation analysis.16
In the BITREL 2002, Ryszard Lobinski from France was one of the invited lecturers. He noticed this proposal and strongly recommended to write a paper in the special issue about “Metals in Biology” in JAAS, in which he was planning to publish at that time. Then, the first paper on this topic was published in JAAS in 2004. At the same time, Bibudhendra Sarkar from Canada was also there, and he enthusiastically encouraged Haraguchi to organize the International Conference on Metallomics. Accordingly, Haraguchi organized the first ISM 2007 in Nagoya through November 28–December 1, 2007 (see Fig. 3). Thus, it can be said that BITREL 2007 was an epoch-making symposium for the establishment of metallomics.
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Fig. 3 Photo taken on the occasion of ISM 2007 (from left to right). First row: K. Tsunoda, J. Takahashi, Mrs. Suzuki, H. Haraguchi, C.W. McLeod, Second row: K. Chiba, K. Okamoto, Third row: H. Tao, K. T. Suzuki, Mrs. Haraguchi. |
As is well known, the Royal Society of Chemistry (RSC) launched the journal “Metallomics” in January, 2009, and the second ISM (ISM 2009) was held in Cincinnati, USA, in 2009, under the organization of Joseph A. Caruso, Gary M. Hieftje and David W. Koppenaal. The third ISM will be held in Munster, Germany, in 2011. In addition, recently the IUPAC guideline for terminology in metallomics was published by the effort of Lobinski et al.17
Metallomics has been receiving great attention among Japanese scientists, and several domestic symposiums have been organized in the various academic societies of chemistry, pharmacy and bio-medicine. In 2008, the Metallomics Research Forum was instituted, and it was agreed by the participants that this forum will be held every 2 years.
“Many events and great attention oriented to metallomics since 2004 are much more than I expected and everything is so surprising to me.” This is Haraguchi's impression at the current time, but he is still expecting further progress of metallomics, in symbiosis with genomics, proteomics and other omics-science.
In Table 1, the requirements for ideal spectrochemical analysis is summarized, which was proposed by Haraguchi in 1980 on the occasion of the first seminar of the Discussion Group for Plasma Spectrochemisty in Japan. If the table is carefully inspected, one can reflect “what has changed?”, “how much progress?”, “what is still a problem?” and so forth. It seems that various instrumentation and analytical techniques/methods have been explored to fulfil the research targets listed in Table 1 owing to the efforts by many scientists and instrument companies over the last 30 years, although we do not give concrete examples here.
Requirements proposed in 1980 | Future-oriented analysis | |
---|---|---|
a This table was presented by H. Haraguchi on the occasion of the first seminar of the Discussion Group for Plasma Spectrochemistry in Japan, held on January 31, 1980 at the University of Tokyo. | ||
1. | Quantitative and qualitative analysis of all elements are possible | All-elements analysis |
2. | Simultaneous mulielement analysis of the elements at the major, minor, trace and ultratrace concentration levels can be performed | Multielement profiling analysis |
3. | Inter-element interferences are negligibly small | Matrix-free analysis |
4. | Applicable to the small volume or amount of sample | Single particle/liquid analysis |
5. | All states of samples, i.e., in solid, liquid (solution) and gas, can be analyzed with minimum sample pretreatment | Direct and in-situ analysis |
6. | Rapid analysis is possible (e.g., applicable to process control) | Process control analysis |
7. | Accuracy and precision are guaranteed | Good laboratory analysis |
8. | Non-destructive analysis is desirable | Chemical speciation and 3D imaging analysis |
9. | Compact-type of instruments should be designed | Microchip instrumentation |
10. | Commercial instruments with proper price should be sent to the market | Cost-performance instrumentation |
Then we need the next research targets which are expected in analytical atomic spectrometry. In the second column of Table 1, the future-oriented analyses are listed in the terminology of modern analytical chemistry in parallel to the requirements proposed in 1980, they are: (1) all-elements analysis, (2) multielement profiling analysis, (3) matrix-free analysis, (4) single particle/liquid analysis, (5) direct and in-situ analysis, (6) process control analysis, (7) good laboratory analysis, (8) chemical speciation and 3D imaging analysis, (9) microchip instrumentation, and (10) cost-performance instrumentation. We hope that the targets listed in Table 1 will give a good guideline for the future development of analytical atomic spectrometry and various new technologies will be explored not only for analytical chemistry, but also for science of humans and nature.
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