Case 97-01

The George Washington University:

Helium Inductively Coupled Plasmas for Emission and Mass Spectrometry

A Case Study of the R&D Value Mapping Project

Institute for Policy Research and Development

School of Public Policy

Georgia Institute of Technology

Atlanta, GA 30332-0345

Unedited Draft

This case was written by David Roessner and is based on field work performed by David Roessner and Hans Klein. Comments or questions should be directed to David Roessner at david.roessner@pubpolicy.gatech.edu. The research was sponsored by the U.S. Department of Energy, Division of Basic Energy Sciences, Contract No. 45562. The views presented here are the case author’s and do not necessarily represent those of the Department of Energy, The George Washington University, or Georgia Institute of Technology.

The George Washington University: Helium Inductively Coupled Plasmas for Emission and Mass Spectrometry

I. Project description and technical focus

            Emission and mass spectrometry represent one of the primary tools available to the analytical chemist for identifying the composition of unknown materials. Not only is spectrometry important for investigation of fundamental phenomena as part of basic science, but it is also applied to a wide variety of practical problems such as detection of pollutants in air and water, identification of toxic substances in tissues and body fluids, detection of impurities in ultrapure materials, determination of the composition of food and drugs, and many others. Spectrometry thus finds application in law enforcement, environmental and energy research, biomedicine, and the semiconductor industry. Commercially available spectrometers made by firms such as Perkin-Elmer perform two basic functions: (1) transformation of the sample into a form suitable for analysis by mass or emission spectrometry and (2) analysis of the sample and display of the results. One type of these machines uses an inert gas inductively coupled plasma (ICP) to ionize the sample prior to introduction into the analytical phase of the process. The inert gas argon is used because it is relatively easy to work with and relatively immune to the formation of compounds that would produce unwanted spectral lines in the analytical output. Commercial argon gas ICP spectrometers cost in the range of several hundred thousand dollars.

            Use of the lightest inert gas, helium, as the basis for the ionizing process offers a number of advantages over argon, especially higher sensitivity, higher selectivity, and fewer byproducts to contaminate the analysis. But because of differences between Ar and He this presents formidable difficulties. Among the important differences are electrical resistivity, thermal conductivity, specific heat. Higher resistivity means less efficient power transfer into the plasma; higher conductivity means heat dissipates more rapidly toward the outer edges of the plasma; higher specific heat means that more energy is required to achieve the same plasma gas temperature.

            Since 1984, a research team at George Washington University under the direction of Dr. Akbar Montaser has been attempting to develop new high temperature plasmas and new sample introduction systems for rapid elemental analysis of solutions and solids using atomic emission spectrometry. Emphasis has been placed on:

   generation and fundamental investigation of annular, helium inductively coupled plasmas that are suitable for the excitation of high energy spectra lines, with the intent of enhancing the detecting powers of a number of elements;

   generation of plasmas that require low gas flows and low input power, with the intent of decreasing the cost of analytical determination;

   development and characterization of new sample introduction systems that consume microliter or microgram quantities of samples.

The work has included investigation of the fundamental principles behind the measurements, evaluation of the analytical potential of the devices developed, and demonstration of the analytical methods in representative samples. The GW project’s general objective is to use helium plasmas to take care of all the problems with argon.

            Over the course of the project, which began in 1984, 10 Ph.D.s have been produced; the team has generated 260 publications and presentations; three books were written; a network of some 50 collaborators worldwide has developed, including other university researchers in the U.S. and abroad, researchers in federal agencies and laboratories, and industrial researchers; and four patents and copyrights have been granted. The team also produced a number of research "firsts," including the first helium isotope torch, the first model of a helium plasma, and the first patent on a sonic nebulizer (vaporizer). Montaser and his students have won a number of awards for their research.

II. Project history

            Perhaps more than other cases, this case centers on a single individual: Akbar Montaser, Professor of Chemistry at The George Washington University. Montaser received his Ph.D. in analytical chemistry from Michigan State in 1974. He returned to the United States in 1979 after four years on the faculty of Mehr University of Technology in Tehran. He was visiting research scholar at Ames Lab in Ames, Iowa for two years and then joined the GW faculty in 1981. He accepted a lower rank and startup package from GW, a university without a strong reputation in research, over a much more attractive offer from another university for personal reasons related to family relationships in the Washington area. His doctoral work at Michigan State ("Fundamental Investigation of Nonflame and Flame Atomization with Computer-controlled Spectrometric Systems") investigated the use of inductively coupled plasmas as atomization devices for atomic fluorescence spectrometry, and this work was continued at Ames Lab.

            At GW, Montaser wrote research proposals seeking support for work on helium ICPs from "lots of places," including the Navy, the National Science Foundation, and DOE. He received support only from DOE/OBES, and a small, unrestricted award from the American Chemical Society, beginning in 1984. In Montaser’s view, DOE was "willing to take a risk;" although his postdoctoral work at Ames with "good people" helped establish contacts and credibility. BES has continued to provide the core support for this work, with renewals every three years. The most recent proposal was granted for the period January 1, 1996 through December 31, 1998. The level of these awards has remained at about $100K annually, with periodic supplements for items such as the purchase of instruments.

            Work during the first award (January 1984-December 1986) focused, first, on forming three types of He ICPs at atmospheric pressure, devising and evaluating various torches to reduce the gas flow requirement of the He plasma, investigating the emission spectrum of the He ICP and comparing it with that generated by the Ar ICP, and investigating reduced-pressure He ICPs. Second, the team worked on developing a low power, low gas flow Ar ceramic torch that would avoid the need for external cooling. Third, they explored the promise and limitations of mixed-gas and molecular-gas ICPs. Finally, they explored new ways of introducing samples into plasmas (nebulization) in order to maximize the efficiency of measurement. During this period a patent for a He ICP torch was filed.

            The next period involved continuing work on He plasma generation and characterization, mass spectrometric studies of He ICP discharges, diagnostic studies of ICP discharges, and sample introduction systems. The team acquired a new ICP mass spectrometer with support from a supplemental award from DOE ($75K) and a smaller award from GW ($35K), and used the Fourier transform spectrometer facility at Los Alamos National Laboratory for several diagnostic studies.

            During 1990-1992, three students received Ph.D.s based on the DOE research and three postdocs were trained. A second edition of Inductively Coupled Plasmas in Analytical Atomic Spectrometry was published in September 1992, with Montaser as co-author and co-editor (with D. W. Golightly). This was a greatly expanded and updated edition of a book first published in 1987. ICP-MS studies focused on Ar and He ICP discharges; atomic emission studies yielded methods for improving the detection limits of several elements (some relying on the FTS facility at Los Alamos); a new project was started involving computer simulation of helium ICPs and mixed-gas plasmas, which if successful would greatly reduce the costs of identifying the properties of new plasmas; and studies of liquid sample introduction systems. Computer simulation studies involved collaboration with Professor J. Mostaghimi of the University of Toronto. During the award period a patent was issued (1992) for a low-cost, humidifier-based ultrasonic nebulizer. Work on the detection of selected platinum groups was conducted in collaboration with A. Dorrzapf of the U.S. Geological Survey; the impetus for these studies was rising demand for platinum group metals and the associated need for development of more sensitive analytical methods for exploring new reserves of these metals.

            In 1995 a new ICP-MS instrument, funded by NSF and Perkin-Elmer, was delivered to replace the nearly obsolete Delsi-Nermag instrument. (NSF provided $105K, Perkin-Elmer $62K, and GWU $37.5K.) One project carried out since 1992 has as its object elemental and isotopic analysis of nanoparticles and microparticles produced frm materials important in data storage and semiconductor industries and is being conducted mainly at IBM; support for this work was also sought from NSF. Another project, the subject of an EPA proposal, investigates reduced-pressure He ICP discharges as ion sources for the mass spectrometric detection of halogenated contaminants and metals/nonmetals in air, water, soil, and food. This latter work is conducted in collaboration with H. M. Watt, Professor of Environmental Sciences and Director of the DC Water Resources Research Center of the University of the District of Columbia. Computer modeling of discharges continued with the collaboration of Prof. Mostaghimi of the University of Toronto; these were directed in part toward improved predictions of the characteristics of He ICP discharges. Funding constraints at DOE caused curtailment of some sample introduction studies, but work was redirected as a result of support ($74K for two years) from J. E. Meinhard Associates (manufacturer of nebulizers). A phase-doppler particle analyzer was also acquired during this period with funds from an NSF equipment grant ($101K) and from the university ($49K).

            During 1992-95 the research produced three Ph.D.s and two MS theses; one postdoc, two visiting professors, and two undergraduate students received training in ICP spectrometry. A new book devoted to ICP-MS was prepared for publication by the end of 1995.

            Although DOE/BES has provided the core funding for this project throughout its existence, Professor Montaser points out that the results from DOE-funded research during earlier portions of the research have "enabled" support from other sources, particularly industry and other federal agencies (e.g., IBM, Perkin-Elmer, NSF). Of a total of 260 publications and presentations resulting from the research, about 70 are the products of DOE funding. Support for investigations of the central questions posed initially continues to come from DOE, although Professor Montaser expresses considerable frustration at the inadequacy of DOE support for the number of graduate students and instrumentation requirements involved in the core research.

            The substantial network of collaborators developed in this project--numbering about 50--was generated in part because of the subjects of research and their potential applications (e.g., IBM, Meinhard, District of Columbia, FDA, USGS), others flow from the demands of the research itself (e.g., computer simulation with the University of Toronto, use of the Los Alamos Fourier transform spectrometer). Collaborators also resulted from, or where suggested by, the requirements of the three books produced during the last 13 years. These edited volumes presented the state of the art in inductively coupled plasma spectroscopy, and so brought the top researchers in the field into close contact with the GW research team. In Professor Montaser’s view, without DOE support and the reputation that support engendered, he would not have been able to attract these collaborators and achieve the recognition he now enjoys. "DOE enabled us to study these processes at a fundamental level. Only then can you design the system."

            The environment at GWU had not been one typical for a highly productive and internationally recognized research activity. The university lacked a tradition of research when Montaser joined the faculty, but did have a medical school and an engineering school. When he obtained DOE funding in 1984 he was the only funded principal investigator in the department. The Vice President for Research was a strong supporter, and according to Professor Montaser the situation has improved considerably since 1984. During the early years of his research, Professor Montaser made full use of his geographic location in the District of Columbia. He obtained support from other federal agencies such as the FDA and NIH, and without that interaction "I would not have made it; if GW were in Ames, Iowa, I couldn’t have done it." GW did not exactly foster collaboration, but they did not impede it. If cost sharing was needed, the university usually came through.

            Professor Montaser has a positive view of the DOE/BES proposal review process. Reviews of proposals were made available for comment, and in some cases generated a "dead wrong!" response from him. Program managers from DOE did appear periodically at GW but not frequently. Professor Montaser contrasts this with his experience at NSF, where he was a part time program officer during 1991-1996. While there, he reviewed 700 projects, whose average size was larger that those of BES. He noted that the NSF experience stimulated him to pursue collaboration with industry.

            The project has involved a number of collaborators from widely varying fields and institutional locations over the years. The GW project is the only one worldwide working on He ICP spectrometry, although there are approximately 50 groups working on ICP spectrometry. Current participants in the project from GWU include seven Ph.D. students, one of whom has already been hired by MEMC Electronic Materials, Inc., an M.S. student who works for the FDA, an undergraduate honors student, two professors from the Pharmacology Department, one from Forensic Science, and one from Geology. Project participants from outside GWU include the president of Meinhard Associates, Inc. (a manufacturer of nebulizers), two researchers from Sciex-Perkin Elmer, Prof. Mostaghimi at the University of Toronto, the Director of the DC Water Resources Research Center, and a scientist with StorMedia, Inc. The current collaborators on the project are basically authors or co-authors of the current book, edited by Montaser, Inductively Coupled Plasma Mass Spectrometry: From A to Z (Wiley, 1997). Former collaborators include 22 postdocs, graduate students and undergraduate students; 10 collaborators at other institutions; and 27 authors or coauthors in the first and second editions of Montaser and Golightly, eds., Inductively Coupled Plasmas in Analytical Atomic Spectrometry, VCH Publishers, 1987 and 1992. Lists of these collaborators are appended to this case.

III. Project outputs and impacts

            Montaser himself has published and presented approximately 260 papers, is the co-author and co-editor of the 1987 and 1992 editions of one book and editor of the 1997 book published by Wiley. Seventy of these papers resulted directly from DOE-supported research. Many of these papers were published in Analytical Chemistry, Spectrochimica Acta, and the Journal of Analytical Atomic Spectrometry. The 1987 and 1992 books were the most successful books ever published by VCH Publishers. A review of the 1992 edition in the Journal of Analytical Chemistry describes it as the "ICP bible" and "probably the most important contribution to the field." Montaser serves on the editorial boards of Spectrochimica Acta (part B) and Spectrochimica Acta Electronica. During 1991-1996 he was asked by NSF to serve as a part-time program director in the Division of Materials Research. At GWU, Montaser has received two awards for his research: the 1990 Columbian College Award for Excellence in Research, and the 1997 Oscar and Shoshana Trachtenberg Prize for Faculty Scholarship. Since 1985, five of his graduate students have received national and international awards for their graduate research sponsored by DOE.

            Professor Montaser identifies the following results as among the key contributions of the research project:

   the first published accounts of the successful formation and operation of annular helium ICP discharges.

   the first analytical and fundamental studies of He plasmas by interfacing them with atomic emission spectrometers and mass spectrometers.

   the first models for the simulation of He ICP discharges (with Prof. Mostaghimi).

   a 1989 patent on the fabrication of inexpensive ultrasonic nebulizers.

   an inexpensive, easy-to-use device for injection of micro- and nanoliter volumes of test solutions into plasmas (in collaboration with J. Meihhard Associates); a 1997 patent was applied for.

   several original diagnostic studies of aerosols using light-scattering interferometry.

Three patents (1989, 1992, 1997) and one copyright (1989) have resulted from the project. The work served as the foundation for development of the next-generation plasma source mass spectrometers, a project funded in 1995 jointly by NSF and Perkin-Elmer.

            According to Prof. Montaser, the DOE program of research has enabled the GW team to attract additional funding from other federal sources and industry. For 1995-96, the total size of the group’s grants and contracts was $570K from DOE, NSF, the District of Columbia, Perkin-Elmer, CETAC Technologies, Inc., and J.E. Meinhard Associates.

IV. Conclusions

            There are several major themes to this case. First, the case represents a successful effort by an entrepreneurial professor to make the most of a research environment possessing serious limitations. Second, it seems clear that DOE support has proven critical, perhaps essential, to the realization of the research results and impacts described in the case. Third, related to the first theme, the case centers on an individual researcher, his students, and collaborators rather than on a large or continuing research team. Each of these themes will be elaborated in the following paragraphs.

            In 1981 Professor Montaser chose to join George Washington University, a university with little history of research activity, largely for personal reasons. It took three years of proposal writing and persistence despite denials from several agencies, but DOE/BES was willing to take a risk, perhaps influenced by Montaser’s previous work and contacts at Ames Lab, a DOE facility. Nonetheless, Montaser’s objectives were not considered to be particularly likely to bear fruit at the time, and even today the GW team is the only one working on He ICP. Montaser established relationships with federal agencies in the DC area with potential interest in his work (FDA, FBI, DC Dept of Water Resources Research) and used these contacts to bring in students and a small amount of support. While certainly not actively impeding Montaser’s work, GW has not presented the stimulating intellectual atmosphere that would be found at a major research university. Also, GW has provided significant cost sharing on requests for instrumentation and other external awards.

            DOE support enabled the GW team to produce research results sufficiently promising to attract the attention of other federal agencies and industry, and Montaser was able to convert that interest into financial support. Once sufficient funds were available to conduct research in several areas and generate results, the GW He ICP work, modeling, and new sample introduction methods became known through a steady stream of publications and numerous collaborations. Montaser overcame whatever limitations existed because of his home institution’s lack of research emphasis by aggressively publishing and presenting results, and establishing links with people and institutions in the larger field of ICP spectrometry. The 1987 and 1992 books appear to have served these purposes well, first by increasing the number of collaborators and stengthening existing ones, and via the books’ publication and popularity extended his reputation. The 1997 book seems likely to further extend that reputation.

            As the previous paragraphs suggest, the continuing project on He ICP spectrometry is almost entirely attributable to the efforts of one person. If Professor Montaser were to move to another institution, the work would all go with him. Montaser is constantly thinking of how his work might be applied; as he said to us, he is not interested in simply publishing papers, but in having an impact on analytical chemistry. This awareness of application must have had a positive affect on his ability to identify and attract collaborators from industry and other federal agencies.

            It is interesting to note that the GW research has not spawned Ph.D.s who have gone to other universities to expand the set of people working on He ICP. Montaser’s students have gone to industry and organizations that use ICP spectrometry or make the instruments themselves (or a part of them). As Montaser said several times during our interview, his work is at once both fundamental and applied. Industry finds the improved performance of He ICP valuable for certain applications, and if the new NSF/Perkin Elmer project bears fruit, He ICP spectrometers may represent the next generation of machines. Patents and copyrights were generated as early as 1989, but new machines embodying the knowledge generated by Montesar and his collaborators are still years away. Perhaps this interplay of fundamental and applied work is characteristic of research on instrumentation in science--new knowledge is sought because it is needed to solve problems arising from moving the next step in instrument performance.