Anal. Chem. 1084, 56, 133R-156R (59) Palmer, G. fhys. Biolnorg. Chem. Ser. 1983, 2 ,43-88. (60) Blackburn, N. J. Electron Spln Reson. 1982, 7 , 340-81. (61) Villafranca, J. J. Methods Enzymol. 1982, 87, 180-97. (62) Villafranca, J. J.; Raushel, F. M., Adv. Inorg. Biochem. 1982, 4 , 289-319. (63) Beinert, H. Membr. Transp 1982, 1, 389-98. (64) Plbrow, J. R., B,,(twelve) 1982, l q 431-62. (65) Cohn, M.; Reed, G. H., Annu Rev. Blophys. Bloeng. 1982, 51, 365-94. (66) Dugas, H.;Rodrlguez, A. Can. J . Chem. 1982, 6 0 , 1421-31. (87) Dodd, N. J. F. Electron Spin Reson. 1982, 7 , 382-405. (68) Butterfleld, D. A. Biol. Magn. Reson. 1982, 4 , 1-78. (69) Symons, M. C. R. "Free Radicals, Lipid Peroxidation Cancer, (Proc. N.F.C.R. Cancer Symp.) 1st 1981"; McBrien, D. C. H., Slater, T. F., Eds.; Acadernlc Press, New York, 1982; pp 75-99. (70) Lai, C. S. Electron Spin Reson. 1982, 7 , 313-39. (71) Thomas, D. D. Membr. Transp. 1982, 1, 135-9. (72) Robinson, B. H. Electron Spin Reson. 1982, 7 , 293-312. (73) Ebert, B.; Elmgren, H.; Hanke, T. Stud. Biophys. 1982, 91, 19-22. (74) Dunham, W. R.; Harding, L. T.; et al. Dev. Biochem. 1982, 21,568-72. (75) Devaux, P. F.; Davoust. J. Membr. Transp. 1982, 1 , 125-33. (76) Devaux, P. F.; Davoust, J.; Rousselet, A. Blochem. SOC.Symp. 1981, 46,207-22. (77) Marsh, D. Tech. Llfe Scl.: Blochem 1982, 6 4 / 2 (B426), 44 pp. (78) Marsh, D.; Watts. A. Res. Monogr. Cell Tissue Physiol. 1981, 7 , 139-88. (79) Thomas, D. D. Clba Found. Symp. 1983, 93, 189-85. (80) Watts, A. frog. RetinalRes. 1982, 1 , 153-78. (81) Riesz, P.; Rosenthal, I.Can. J . Chem. 1982, 6 0 , 1474-9. (82) Hoff, A. J. Biophys. Strucf. Mech. 1982, 8 , 107-50. (83) Schritzer, M. R o c . Int. feat Symp. 1981, 17-44.
(33) Hyde, J. S.; Froncisz, W. Annu. Rev. Biophys. Bioeng. 1982, 1 1 , 39 1-41 7. (34) Upreti, G. C.; Saraswat, R. S. Magn. Reson. Rev. 1982, 7 , 215-37. (35) Mydosh, J. A. Lecf. Notes fhys. 1981, 149,87-106. (36) Ford, P. J. Confemp. fhys. 1982, 23, 141-88. (37) Barnes, S. E. Adv. fhys. 1981, 36,599-610. (38) Conard, J.; Estrade-Szwarckopf, H.;Lauginie, P.; Hermann, G. Sprlnger Ser. SolM-State Sci. 1981, 38,264-73. (39) Troup, G. J.; Hunon, D. R. J. Gemmol. 1983, 18, 421-31. (40) Howe, R. F. Adv. Colloid Interface Scl. 1982, 18, 1-55. (41) Clarkson, R. B. V I A , Varlan Instrum Appl. 1981, 15, 17. (42) Lunsford, J. H. Stud. Surf. Scl. Cafal. 1982, 12, 1-13. (43) Pinnavaia, T. J. Dev. Sedimenfol. 1982. 34, 139-81. (44) Tkac, A. Dev. Polym. Stab. 1982, 5 , 153-231. (45) Hik D. J. T.; O'Donnell, J. H.; Pomery, P. J. Electron Spln Reson. 1982, 7, 1-40. (46) Cameron, G. G., Pure Appl. Chem. 1982, 5 4 , 483-92. (47) Bullock, A. T. Electron Spin Reson. 1982, 7 , 280-92. (48) Kemp, T. J. Electron Spin Reson. 1982, 7 , 252-79. (49) Gilbert, B. C. Electron Spin Reson. 1982, 7 , 174-215. (50) Ayscough, P. 8. Electron Spin Reson. 1982, 7, 216-51. (51) Hudson, A. Electron Spln Reson. 1982, 7 , 58-68. (52) Moebius, K.; Plato, M.; Lubitz, W. fhys. Rep. 1982, 8 7 , 171-208. (53) Stock, L.; Wasielski. M. I n "Progress In Physical Organic Chemistry"; Tan, R. W., Ed.; Why: New York, 1981; Vol. 13, Chapter 4. (54) Freed, J. S. Kern.-Keml 1982, 9 ,50-1. (55) Symons, M. C. R. Electron Spln Reson. 1982, 7 , 124-73. (56) Bock, H.; Kaim, W. Acc. Chem. Res. 1982, 15,9-17. (57) Solodovnikov, S. P. Usp. Khim. 1982, 51, 1874-97; Chem. Ab&. 1983, 98,4584q. (58) Blumberg, W. E. Methods Enzymol. 1981, 76, 312-29.
.
Emission Spectrometry Peter N. Keliher,*' Walter J. Boyko, Joseph M. Patterson 111, and J. Wilson Hershey Chemistry Department, Villanova University, Villanova, Pennsylvania 19085
This is the 19th article in the series of biennial reviews in the field of emission spectrometry/spectroscopy and is the third written by the Villanova University author group. This year J. Wilson Hershey joins us as a new coauthor. This review article will survey selectively the emission spectrochemical literature of 1982 and 1983. By agreement, however, flame emission publications are reviewed in the section of this review issue entitled "Atomic Absorption, Atomic Fluorescence, and Flame Spectrometry" authored by Gary Horlick. This follows previous custom. Because of the late arrival of some journals appearing in December 1983, we may have missed some references of importance, and it is hoped that these will be discussed in the next biennial review. In general, we are following the format that we have used in the previous two reviews (18A, 19A),this is essentially the format that had been used by the previous author of this review, Ramon M. Barnes. Because of space considerations, however, we have had to be particularly selective and we have not attempted to provide an all-inclusivebibliography. In this fundamental review, the emphasis will be on developments in theory, methodology, and instrumentation. Applications will be cited only insofar as they advance the state of the art or have particular current relevance. References will be cited only if they are of particular importance to analytical chemists and spectroscopists; articles of primary interest to astronomers and/or physicists are not, in general (with some exceptions in Section B), cited. Readers should note that detailed and specific application information is available from Analytical Abstracts, Chemical Abstracts, and also the more specific Atomic Absorption and Emission Spectrometry Abstracts published by the PRM Science and Technology Agency (4A). In addition, the latest Application Reviews issue of Analytical Chemistry (3A) contains many recent spectrochemical application references. Readers should also note the excellent
annual series Annual Reports on Analytical Atomic Spectroscopy (ARAAS)(%A,49A) published by the Royal Society of Chemistry, Burlington House, London, W1V OBN, United Kingdom. These annual reports provide detailed information on emission spectrometry and atomic absorption spectrometry and are absolutely highly recommended to those with an interest in the field. Whereas our biennial selective review provides several hundred references, each of the ARAAS annual reviews provides over 2000 references including a wealth of information on meeting presentations. Volume 12, reviewing 1982, has just appeared (49A) and the Editors, L. Ebdon and K. W. Jackson, are commended for their outstanding effort. In going thro h the 1982-1983 literature, we have selected the following p3lications as being most relevant and most emission spectrometry papers published in these journals are cited in this review: Analyst (London),Analytica Chimica Acta, Analytical Chemistry, Analytical Letters, Applied Optics, Applied Spectroscopy, Applied Spectroscopy Reviews, Atomic Spectroscopy, Canadian Journal of Spectroscopy, CRC Critical Reviews in Analytical Chemistry, Environmental Science and Technology, Fresenius' Zeitschrift fur Analytische Chemie, ICP Information Newsletter, International Journal of Environmental Analytical Chemistry, Journal of Chemical Education, Journal o the Optical Society of America, Journal of Quantitative pectroscopy and Radiative Transfer,Microchemical Journal, Optica Acta, Progress i n Analytical Atomic Spectroscopy, Reviews i n Analytical Chemistry, Review of Scientific Instruments, Science, Spectrochimica Acta Part B, Spectroscopy Letter, and Talanta. Papers published in unreviewed magazines such as Americanllnternational Laboratory, Industrial Research and Development, Laboratory Practice, etc. are not generally cited. However, where we feel that a publication is of fundamental importance, it is cited whatever the source. A comment should be made regarding the citation of inductively coupled plasma mass spectrometry (ICP-MS) publications.
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'Reprints of t h i s review are available o n request. OOO3-2700/84/0356- 133R$06.50/0-1
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1984 American Chemical Society
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Although these papers do not normally involve optical emission spectrometry (the optical emission is replaced by the mass spectrometer), they are, nevertheless, cited in this review since they will be of importance to those interested in ICPs.
BOOKS AND REVIEWS Several important books have been published during the past 2 years. The Proceedings of the 9th ICAS 22nd CSI meeting held in Tokyo has been published (57 ) and this impressive book, edited by K. Fuwa, contains many important papers from the 1981 Tokyo conference. Alkemade and coworkers (2A) have written a magnificent book entitled “Metal Vapors in Flames” covering in one volume all of the main aspects of metal vapors in flames, such as excitation, radiation, dissociation, ionization, and diffusion. The bibliography of this book is over 70 pages long. This book is highly recommended for anyone with an interest in atomic spectrometry. Volume 2 of the MIT wavelength tables has now been published (113A) and lists wavelengths by elements. Van Loon’s book (147A) on the chemical analysis of inorganic constituents of water contains useful information on emission spectrometry as well as information on precautions associated with sample preparation. Valkovic (144A, 145A) has written a two volume book on the problems associated with the determination of trace elements in coal. There is much useful information in these two volumes and they are recommended for those with an interest in this area. Volume I1 has a useful section on environmental considerations. Weber has edited (150A, 151A) a two volume work on lasers and masers. Duley (44A),Evans (51A),and Garetz and Lombardi (58A)have all written books on lasers and their applications to chemical analysis. A most important book that has just been published is “A Handbook of Inductively Coupled Plasma Spectrometry” by Thompson and Walsh (138A). This book has some very useful chapters including (Chapter 5) Multielement Applications of the ICP in Applied Geochemistry, (Chapter 7) Discrete Sample Injection Methods for Solid Samples, (Chapter 9) The Analysis of Environmental Materials by ICPS, and (Chapter 10) ICPs Now and in the Future. Magyar (93A) has written a book entitled “Guide Lines to Planning Atomic Spectrometric Analysis”. The emphasis of this book is toward AAS but there is some mention of atomic emission and a discussion of the ICP. Albaiges (1A) has edited a book based upon the proceedings of the 2nd International Congress held in Barcelona, Spain, in 1981 and Denny (42A) has written a useful dictionary of spectroscopy. Several recent books on AAS will be of related interest in the field of emission spectrometry. Katz and Jenniss (79A) have written a useful book on regulatory compliance monitoring that has much useful information on environmental sampling, sample preparation, methods for compliance with air and water quality monitoring, and quality assurance. There is an extensive list of references. Ebdon (47A) has written a “self-teachin guide to AAS and Ottaway and Ure (11IA) have written a c o k entitled “Practical AAS”. Cantle (27A) has edited a book on AAS and some of the chapters in this book are quite useful. The chapter on marine analysis by H. Haraguchi and K. Fuwa is particularly well written. Volume I of “Atomic Absorption Spectrometry in Occupational and Environmental Health Practice” by Tsalev and Zaprianov (141A) has just appeared. The section on sampling, storage, and sample preparation is of particular interest. Grasshoff and co-workers (61A) have edited a book on methods of seawater analysis. This is the second edition of this book. There is a very good discussion of sampling and sampling techniques that will be of interest to emission spectroscopists. Hutley (70A) has written a fundamental book on the theory and use of gratings in spectroscopy. There is a discussion of both classically and holographically ruled gratings. Marshall (96A) has edited a book on Fourier, Hadamard, and Gi!bert transforms in chemistry and Mittleman (105A) has written a book on the theory of laser-atom interactions. Ohno and Morokuma (109A) have written a book containing more than 2500 full references to the literature on ab initio calculations gathered by quantum chemists from 19 well-known international core journals. This is a fundamental book. The 2nd edition of ”Light Transmission Optics” (94A) has now been published and Lowdin and Ohrn (92A) have edited a book based upon the proceedings of the international symposium
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on atomic, molecular, and solid-state theory. Johnson (75A) has written a book entitled “An Introduction to Atomic and Molecular Collisions” that is quite readable and Minczewski et al. (104A) have written a useful book entitled “Separation and Preconcentration Methods in Inorganic Trace Analysis”. There are a few instances of “awkward translations” from Polish to English in this book but this does not detract from the book’s scientific merit. Several fundamental books have useful sections on emission spectrometry. The 4th edition of Skoog and West (129A)has just been published. Robinson’s book (119A) entitled “Undergraduate Instrumental Analysis” contains a lot of fundamental information on emission spectrometry in a very readable format. Marr and Cresser (95A) have publisbed a book called “Environmental Chemical Analysis” and Brown (23A) has written “Introduction to Chemical Analysis”. “Instrumentation in Analytical Chemistry” edited by S. Borman (16A) of the Analytical Chemistry staff is an anthology of review articles on analytical instrumentation that appeared in the journal from 1972 through 1982. This very reasonably priced book (available in hard or soft cover) is highly recommended. Many important articles are “put under one roof”. Computers in analytical chemistry have become even more important during the past 2 years. The 2nd edition of Cooper’s book (34A) on the minicomputer in the laboratory has been published and Barker (6A) has written a book entitled “Computers in Analytical Chemistry”. Heller and Potenzone (66A) have edited a book based upon the proceedings of the 6th International Conference on Computers in Chemical Research and Education held in Washington, DC, in 1982. Kopanica and Stara (84A) have also written a book describing applications of computers in analytical chemistry. Two excellent reviews on computers in the analytical laboratory have recently been published. O’Haver (108A) describes “The Microcomputer Revolution” while James (74A) discusses “Microcomputers in the Research Laboratory”. Of related interest is Caulcutt and Baddy’s (30A) “Statistics for Analytical Chemists”. Chakrabarti continues to edit “Progress in Analytical Atomic Spectroscopy”; Volumes 4 (31A) and 5 (32A) have now been published. These are bound volumes of the journal. They are sold, however, separately from the journal. Several excellent reviews in Progress in Analytical Atomic Spectroscopy have appeared during the past 2 years. Cresser (37A) has written an in-depth paper describing theoretical aspects of organic solvent enhancement effects in atomic spectroscopy and Falk (53A) has discussed the limiting factors for intensity and line profile of radiation sources for AAS. There is an interesting section on line broadening by diffusion of resonance radiation. Zimmer and co-workers (157A) have evaluated emission spectrograms and Nakahara (106A) comments on hydride generation techniques in AAS, AFS, and plasma AE spectrometry. Sacks and co-workers (123A)describe exploding conductors as atomization cells and excitation sources for atomic spectroscopy and Robin (118A) has published a philosophical paper entitled “ICP-AES at the Beginning of the Eighties”. Mermet and Hubert (102A) have reviewed the analysis of biolo ical materials with plasma atomic emission spectrometry. ealokerinos and Townshend (26A) have reviewed some practical applications of Molecular Emission Cavity Analysis (MECA). Caroli (28A) surveys the hollow cathode emission source and comments on the past and the potential future for this device. In a related paper, Caroli and co-workers (29A) discuss the applicability of this device for the determination of aluminum in biological samples. Of related interest, Facchetti (52A)has edited a book describing analytical techniques for the determination of heavy metals in biological fluids. ICP-MS will certainly prove to be a very important analytical technique as we continue into the 1980s and there is a great deal of interest in this area as evidenced by some popular (nonauthored) articles that have recently been published (50A, 71A). The best beginning paper to describe the importance of this technique is Alan Date’s article (40A) entitled “An Introduction to ICP-MS”. Another useful review article describing current trends (no pun intended) is entitled ”Progress in Plasma Source Mass Spectrometry” by Date and Gray (39A). The same authors have also recently published (62A) another ICP-MS review. Interested readers may also
EMISSION SPECTROMETRY
mi Warnisby (ACS) h a 1978 thagh 1982 and is presently an Alternate CaMcllDl l Exhibn m a n of #m FACSS Oavmim Board in 197Ci & is p r e ~ n l hFACSS
sterdam in June of 1983. In conjunction with the CSI ICAS meeting, they also published a special issue entitled "Atomic Spectrmopy in the Netherlands and Countries Historically Linked to the Netherlands: Belgium and South Africa" (134A). This particular issue was dedicated to the Editor, P. W. J. M. Boumans, to celebrate his 25th anniversary in atomic spectroscopy. In view of Paul Boumans' tremendous contributions to atomic spectroscopy, this dedication was certainly most appropriate. In this issue, Boumans ( I 7A) reviews the history of the low countries and South Africa while DeViUiem (43A) discusses a century of spectroscopy in South Africa. Another special issue related to the most recent CSI ICAS was entitled "Analytical Spectroscopy: A Polychrome l4ranch of Science" (135A). This contains several of the invited talks resented a t the 23rd CSI/lOth ICAS including Alkemade's rilliant ' talk (5E)contrastin atomic physics and atomic spectroscopy and Hieftje's afdress (126E) describing new directions for ICP torches. A special issue of Spectrochimica Acta entitled "Plasma Spectrochemistry" (Guest Editor Ramon M. Barnes) (133A) contains the Proceedings of the 1982 Winter Conference on Plasma Spectrochemistry held in Orlando, FL, from January 4 to 9,1982. There are many important papem in this issue. Of related interest, Barnes (8A) has edited a book entitled "Developments in Atomic Plasma Spectrochemical Analysis". This book contains 65 papers presented at the 1980 Winter Conference on Plasma Spectrochemistry held in Puerta Rico. In an important Spectrochimica Acta publication, Strasheim (137A) has outlined nomenclature, symbols, units, and their usage in spectrochemical analysis with a specific discussion of radiation sources. Broekaert continues to write a very useful instrument column for Spectrochimica Acta discussing modem instrumentation; some typical columns are cited (21A,
E.
Z2A).
wish u)consult the 'landmark" paper in this field published by Houk and co-workem in 1980 (MIA). Research papers in this field will be discussed in the Instrumentation section of this review. Spectrochimico Acto, Port B continues to be a very major journal in the field of Emission Spectrometry and several "special issues" should be noted here. In late 1981 (too late for inclusion in our previous review). Spectrochirnrca Acta uhllahed a special issue on 'Spectrochemical Analysis in the SSR" (131A). Guest Editor S. L. Mandelstam selected 12 imponant papers as representing the most significant recent work in the field from the Soviet Union. Spertrnrhirnica Acta has published (asa s cia1 supplementary issue) (132A) the abstracts of the 23r&SI/lOth [CAS meeting held in Am-
e
Barnes has commented (1OA) on the explosive growth of plasma publications with an increased emphasis toward the ICP. There has also been an explosive growth in ICP review articles. We have recently become aware that the ancient Romans were the first to describe review articles about the ICP. According to Kahn and Chase (78A), the Roman historian Tacitus was clearly thinking of ICP reviews when he stated "Piscis crastinus, Papyro qui sapientiam hodiernam continet". Recognizing that a few of our readers may not he fluent in Latin, we have provided a translation of the statement following the Kahn and Chase reference (78A). The Tacitus statement notwithstanding, we do feel that there have been at least several important ICP review articles during the past 2 years and we specifically cite reviews by Barnes (7A, SA), Cope and Kirkbright (35A), Fassel (55A, %A), Gustavsson ( M A ) ,Haraguchi (65A),Imai (72A),Kirkbright (82A), Kubota ( S A , %A), MacDonald (98A), Newman (107A).and Sermin (126A). In addition, Browner (24A) has written an excellent review describing sample introduction into lCPs and flames and Ehdon and Cave (48A) have compared pneumatic nebulization systems for the ICP. Kahn (76A, 77A) has written two "fun type" articles comparing AAS with the ICP, these articles are written in Kahn's singular style. McCeorge and Salin (IOOA) have reviewed detection systems for multielement analysis with the ICP. In a more general review article, Walter Slavin (130A) discusses the present and the future of atomic spectroscopy with an emphasis on AAS. The ICP around the world is the subject of several recent reviews: Australia and New Zealand (91A), Canada (99A). China (IZA, 13A),France (IOIA), Germany (20A), Hungary (59A),Israel (60A). Italy (IZOA),Japan (SOA), South Africa (149A). Soviet Union (156A),and the United Kingdom (63A). A recent issue of Reuiews in Analytical Chemistry (edited by T. S. West) is devoted entirely to a discussion of the progress of analytical chemistry in the People's Republic of China during the past 3 decades (116A). Although the emphasis of this issue is on electroanalytical chemistry, there is a useful discussion by Shutian (127A) on optical methods of analysis including emission. Of related interest is "Chemistry in a Chinese University" by Atkins (5A). Sloane Audio Visuals for Analysis and Training (SAVANT) has recently introduced (125A) a very high quality audicr visual ICP program. The program is presented in such a way that it will certainly be useful in academic programs as well as in training sessions for people who will actually operate plasma instrumentation. The program is available either in ANALYTICAL CHEMISTRY. VOC.
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slide/audiocassette format or in videotape (Beta or VHS) format and is also available in three different languages, English, French, or German. This program is a successor to the previously available SAVANT AAS training programs and is highly recommended. Several recent flow-injection analysis (FIA) reviews (121A, 122A, 136A, 153A) will be of interest to emission spectroscopists. Several specialized reviews discuss new frontiers in laser spectroscopy (11OA,140A, 148A). Dumke and Niemann (45A)have reviewed new spectrometer and sample techniques for deuterium analysis and Kuehn et al. (87A) have described sealed electrode configurations for gaseous plasmas. Image reproducing detectors have been reviewed by Boksenberg (15A), Tolmacher (139A) has discussed the population of excited ionic levels, and Rentzepis (115A) has reviewed new advances in picosecond spectroscopy. Parsons and co-workers (112A) have published an outstanding review article comparing various methods of atomic spectroscopy. This is easy to read and very enlightening! Leyden et al. (89A) have discussed the effect of naturally occurring organic materials upon the preconcentration of metal ions and upon their determination by spectrometric methods. Kolbe and Leskovar (83A) have reported on sensitivity and response time improvements in a millimeter-wave spectrometer and, in a particularly interesting review article, Horlick and co-workers (67A) have described atomic emission spectrochemical measurements with a Fourier transform spectrometer. Duursma et al. (46A) have used a micro mini main frame computer network and Learner (88A) has described a simple (and unexpected) experimental law relating to the number of weak lines in a complex spectrum. McCrory-Joy and Joy (97A) have reviewed chemical and instrumental analysis of ferrites and Hughes (69A) has reviewed some applications of optical emission source developments in metallurgical analysis. Busch and Benton (25A) have reviewed multiplex methods in atomic spectroscopy and Zolotov and co-workers (158A) have discussed the application of extraction methods for the determination of small amounts of metals. Van Grieken (146A) has described some preconcentration methods for the analysis of water, Bastien (11A)has discussed spectroscopic diagnostics in gas discharges, Sanz-Medel et al. (124A) have performed a critical comparative study of atomic spectrometric methods for the determination of strontium in biological materials, Skidmore and Greetham (128A) report on trace metal determinations in concentrated electrolyte solutions, and Williams and Mason (152A) have reviewed the ICP in the petroleum industry. I n a very important publication, Risby and Talmi (117A) discuss microwave induced electrical discharge detectors for gas chromatography. This review discusses all of the instrumentation associated with this detector and also provides sufficient information to enable a beginner to initiate research in this area. There is an excellent section of this review discussing the mechanisms which lead to the response of the detector. Zander (154A, 155A) has a two-part detailed review of the direct current plasma (DCP), the DCP has also been reviewed by Keliher (81A). Corney (36A) has published a review with 45 references on the techniques of Doppler-free spectroscopy based on the creation and detection of Hertzian coherence in atomic and molecular systems and Ottaway and his research associates (14A) have reviewed platform atomization in carbon furnace atomic emission spectrometry. Foil Miller’s review entitled “History of Spectroscopy as Illustrated on Stamps” (103A) can only be described as “beautiful” with respect to the illustrations. Philatelists will love this review and will also enjoy Ullman’s review (143A) entitled “Analytical Chemists on Postage Stamps”. Chalmers has edited a book (33A) entitled “Gains and Losses-Errors in Trace Analysis“; this originally appeared as a special issue of Talanta. Turk and Kirkman (142A) have written a practical book entitled “Effective Writing”, Denney (41A) comments on the “Traumas of Technical Writing” in a well-written review article, and Reif-Lehrer (114A) has written a very practical book (at least for academics) entitled “Writing a Successful Grant Application”. “Optical Anecdotes” was written by D. J. Love11 (9OA) and published by the International Society for Optical Engineering. It lists 36 anecdotes which cover the history of optics from the earliest times up to the 1960s. Anyone interested in the I
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history of optics will find this to be a fascinating book. Isenhour’s recent review article (73A) entitled “The Future of Analytical Chemistry: Will There Be One?” is recommended reading. Lastly, our 1984 award for the “most fun” article is given to P. J. Farago for his review (54A) entitled “Peek, Poke and Run”. The world of microcomputers is indeed fiercely competitive and Farago makes some fascinating points.
SPECTRAL DESCRIPTIONS AND CLASSIFICATIONS Tang (94B) has reviewed the methods of obtaining atomic spectral terms while Musiol and Stanek (78B)have calculated the atomic partition functions of bismuth 1-111. Boumans (19B) has assessed 598 prominent lines in the ICP. One of several objectives is the comparison of detection limits and sensitivities with literature values, particularly the authors’s “Line Coincidence Tables for ICP-AES”. Kelly (56B) has presented atomic and ionic spectral lines below 200 nm for the elements hydrogen through argon. Schneider and Roxey (9OB) have presented wavelengths for uranium I-IV while Michaud and Mermet (72B) have reported 100 new lines for iron I in the 200-300 range. Amin (5B) precisely measured three neon I wavelengths by using crossed-beam spectroscopy while Childs et al. (21B)gave new line classifications for atomic holmium based on hi h-precision hyperfine structure measurements. Baird (9BT has reviewed present and perspective wavelength standards. While not strictly in the atomic category, Frank and Krauss (34B) have contributed to explaining the origin of the green and orange bands in the “CaO” spectrum. They have demonstrated that hydrogen cannot be a constituent of the emitting s ecies. Chaghtai and Ahmad (2OBTdiscussed the spectra of molybdenum I-XLII and present information on transitions and energy levels along with level diagrams. Energy levels are presented for silicon I-XIV by Martin and Zalubas (70B)and for iron I-XXVI, along with intensities and oscillator strengths, by Corliss and Sugar (25B). Kwela and Zachara (64B) have measured the intensity ratio’s of two pairs of bismuth I1 lines. Blackwell et al. (13B-18B), have reported precision measurements of relative oscillator strengths for iron I and titanium 1-111 by using the Oxford furnace technique. Cowley (26B)has discussed the use of precision oscillator strengths to obtain large numbers of moderately accurate gf values. In a continuation of this work Cowley and Corliss (27B) calculated oscillator strengths for iron, cobalt, nickel, and titanium atoms and for zirconium, yttrium, sodium, and uranium ions. Ganas (36B)has presented oscillator strengths for the sulfur isoelectronic sequence while Hartmetz and Schmoranzer (44B)reported absolute transition probabilities in the neon fine structure by beam-gas-dye laser spectroscopy. Rudolph and Helbig (86B) have used a new double cage source to find the radiative lifetimes for niobium I and molybdenum I. Lifetimes were reported by Pegg et d. (79B)for xenon I1 and by Musiol, Jones, and Wiese (77B)for argon I. Heilig (45B) has compiled a bibliography on experimental isotope shifts covering November 1976 through October 1981. In a related work, Ahmad, Venugopalan, and Saksena (2B) have presented isotope shifts and electronic configurations for 166 lines of the gadolinium atom, electronic configurations for the dysprosium atom (3B),and, including isotope shifts, configurations for singly ionized dysprosium (4B). Table I presents selective references to the atomic spectra including lifetimes, oscillator strengths, transition probabilities, and hyperfine splittings. As in our previous reviews (18A, 19A), values for molecules and highly ionized species are excluded. Shimizu (91B)has reviewed recent progress in the atomic and molecular spectroscopy on using a laser source for obtaining absolute spectroscopic values. Knystautus (59B) has reviewed the recent progress in fast ion beam spectroscopy while Andrac (6B) has reviewed the use of fast beam-laser devices for performing precision experiments. Le Gouet (67B) discusses time-resolved coherent laser spectroscopy for the study of atomic collisional processes. Beam-foil spectroscopy has been extensively reviewed by Berry and Hass ( I I B ) and Martinsor (71B)while Pinnington et al. (82B)have used this technique to study the copper and zinc isoelectronic series. Zimmermann (I04B)has discussed time-resolved fluorescense for measuring the lifetimes of atomic states, and Winefordner
EMI SS ION SPECTROMETRY
Table I. Selected References t o Atomic Spectra' ionization ref element level type h 88B 3H I 7 58B N I1 22B A 0 I h 81B IIr f 27B I1 Na 7 23B, 35B I Ne 44B, 69B A I 5B h 20Ne I f 9 6B I Mg 7 24B A1 I11 E 7 OB I-XIV Si 7 51B I Ar 7 8 5B Ti I f 2 7B I f 13B, 14B, 15B, 16B 1-111 7 8 5B V I 7 6 5B Mn I1 A I1 103B I - - X X V I E,I, f Fe 25B f 17B, 18B, 27B I f 27B I co f I 2 7B Ni I cu 6 2B 7, A 7 I 9 9B I1 61B 7, A I 7 , hfs, is0 53B Ga 7 I, I11 68B Kr A I1 32B Y f I1 2 7B f Zr I1 2 7B 7 Nb I 86B E Mo 20B I-XLII 7 86B I f 89B I, 7 Xe I1 3 3B Nd I, I1 is0 1B f Sm I 8OB Gd I is0 2B E I 3B DY is0 4B I1 Ho I 21B A, hfs 7 Er I1 1OB 7 I 42B, 73B Hg 7 T1 I, I11 6 8B I Pb is0 74B 202Pb I is0 7 5B Th I is0 3 1B U h 111, I V 9 OB f I1 2 7B ' Key: wavelengths, A ; energy levels, E; ionization energies, I, lifetimes, 7; oscillator strengths, f ; hyperfine splittings, hfs; isotope shifts, iso; and transition probabilities. A. and co-workers (95B)have used this technique to determine lifetimes in an argon ICP. Russo and Hieftje (87) have determined excited-state lifetimes of atoms and molecules in flames by using an optoelectronic cross-correlation method. They believe these measurements could be extended to an ICP by using higher laser power. Verolainen (98B)has reviewed the radiative lifetimes of the excited states of atoms. Hubeny and Oxenius (47B,48B)have discussed the absorption and emission line profile coefficients of multilevel atoms while Arbuzov (7B,8B)has reviewed the study of the shape of spectral lines. A nonadiabatic theory of collisionbroadened atomic line profiles has been published by Julienne (54B).The theory of collision-induced line shapes in terms of absorption and light scattering at low density has been extensively reviewed by Birnbaum, Guillot, and Bratos (12B). Jamelot, Jaegle, and Carillon (52B)have discussed the role of radiative transfer in the shape of plasma-emitted spectral lines while Iglesias (50B)has discussed correlations in the plasma broadening of ion spectral lines. Humlicek (49B)used rational approximants to investigate spectral profiles in the
presence of severe broadening effects. The general method is illustrated for Lorentz, Doppler, Stark, and apparatus broadening. Verges (97B)has reviewed the study of collisional processes using Fourier transform spectroscopy, including laser-induced fluorescense, pressure shifts, and pressure broadening effects in absorption and emission spectroscopy. Gelfand (37B)has reviewed new theoretical and experimental methods for interpreting pressure-broadened line widths. While the emphasis is on studying planetary atmospheres, some of the information may be of interest to atomic spectroscopists. Pianarosa et al. (83B) have presented the determination of self-absorption in the emission lines from some optically thick plasmas. Eicher and Allen (30B)have examined self-reversed line profiles by use of scanning laser excitation while Koizumi, Oishi, and Yasuda (60B) have used inverse Zeeman scanning to measure emission line profiles for the zinc 213.9-nm and the cadmium 228.3-nm atom lines. Kawaguchi, Oshio, and Mizuike (55B)have interferometrically measured spectral line widths in an ICP while Walters (IOOB) has studied the emission line profile in an electronically modulated inductively coupled excited rf electrodeless discharge lamp plasma. Williams and Coleman (102B)have used a photodiode array spectrometer to obtain the hydrogen line broadening for measuring electron concentrations in the twoand three-electrode direct coupled plasma. Collision broadening and shifts in the argon 811.5-nm line have been measured by Tachibana, Harima, and Urano (93B)with a tunable GaAlAs diode laser. Hollander, de Leeuw, and ter Horst (46B) have determined line broadening parameters for the chromium lines while Kotlikov and Tokarev (63B) have examined the broadening of the neon 632.8-nm line at various velocities of colliding particles. Sulzmann (92B)has presented a simple method for calculating Voight profiles by using a HP-34C programmable hand calculator. Kleppner (57B)has reviewed the structure of atoms in strong electric and magnetic fields and ionization processes in a static electric field. Greene (4OB,41B)has discussed a relaxation theory of Stark broadening by ions while Harmin (43B)examined the theory of the non-hydrogenic Stark effect. A comprehensive examination of the regularities and similarities in the Stark widths of plasma-broadened spectral lines was performed by Wiese and Konjevic (101B).Murakawa (76B)has measured the Stark shift of the He I1 468.6-nm line. Goly and Weniger (39B) have examined Stark widths and transition probabilities for some carbon I1 lines in a helium carbon dc arc plasma and, with Rakotoarijimy (38B),have presented Stark parameters for some lines of carbon I, oxygen I, and sulfur I. Lakicevic, Puric, and Cuk (66B)have measured the Stark width and shift of the cesium I 852.1-nm resonance line. Dimitrijevic and Konjevic (29B)have given the results of semiclassical calculations for the Stark broadening of spectral lines for some heavy elements in plasmas. Czernichowski and Chapelle ( B B )have experimentally studied the Stark broadening of the argon 1430.0-nm line in argon-hydrogen plasmas with and without additional helium. Studies of this type promise to be useful for plasma diagnostics. Finally, Prost (84B)has presented part 1of the theoretical mathematical considerations for converting side-on experimental data in plasma spectroscopy by using the Abel integral equation. This first part covers study of the basic analytical solutions.
INSTRUMENTATION Sample Introduction. There has been a lot of activity in this area during the past 2 years and it seems appropriate to begin this section with a discussion of recent activities in this area. Kirkbright and his research associates at the University of Manchester Institute of Science and Technology (UMIST) in England continue to do pioneering work in this field. Kirkbright and Walton (71C)and Kirkbright and LiXing (69'2) have developed an instrumental assembly in which microliter volumes of liquid sample are applied to a graphite rod which is then desolvated and inserted axially into a continuously operating low-power ICP. Kirkbright and Snook (70C)have used this graphite rod sample introduction technique for the determination of trace elements in uranium using 10-pL samples. Cope, Kirkbright, and Burr (24C)compared this electrothermal vaporization device for the ICP with electrothermal AAS for the analysis of doped cadmium telluride. Both systems were found acceptable. In a related ANALYTICAL CHEMISTRY, VOL. 58, NO. 5, APRIL 1984
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publication, Li-Xing, Kirkbright, Cope, and Watson (76C) described a microprocessor-controlled raphite rod direct sample insertion device for an ICP anfhave given details regarding the accompanying software. In related techniques, Kitazume (72C)has described the application of a wire filament electrothermal vaporization technique for sample introduction into an ICP and Ng and Caruso (93C) have reported results for the determination of trace metals in synthetic ocean water by using electrothermal carbon cup vaporization into an ICP. Ng and Caruso (92C) also described volatilization of zirconium,vanadium, uranium, and chromium by using an electrothermal carbon cup. In this technique, the above elements react with ammonium chloride when heated in the carbon cup formin their corresponding chlorides. These metal chlorides are sugbsequently vaporized into an ICP. McCaffrey and Michel(83C) and Rossi and co-workers (25C) have also reported on the utility of using a carbon furnace for sample introduction. Rossi and his research associates modified a Perkin-Elmer HGA-500 graphite furnace and reported an order of magnitude better detection limits (for several elements) than can be achieved by conventional pneumatic nebulization into an ICP. McCaffrey and Michel investigated the determination of chromium in aqueous solution by using a metastable nitrogen plasma. Broekaert and co-workers have determined various metals in biological samples by using a graphite furnace in conjunction with an ICP ( 4 C ) and an MIP (5C). In a related publication, Broekaert, Wopenka, and Puxbaum (14C) used cascade impactors for the analysis of aerosol samples. A multielement ICP system was used. Eleven elements were determined simultaneously in size-separated aerosol samples (0.1-1.0 mg) after digestion with HF/HN03 at 170 "C. It was possible to do 30 multielement determinations per hour. This important paper discusses detection limits, signal stability, background correction, the optimization of the aerosol carrier gas flow, analytical precision, and accuracy. Coleman and Allen (23C) have also re orted on the effects of aerosol introduction, but in their stu& a DCP was used. They demonstrated that the use of excited ion emission lines for analysis circumvents most of the adverse effects caused by large aerosol introduction tubes. Mattoon and Piepmeier (82C) described a three-phase argon plasma arc where desolvation of the sample aerosol prior to reaching the plasma enhances the emission signal by 30%. A Babington-type nebulizer with a split sample aerosol flow stream was constructed and used to supply sample aerosol to the three-phase plasma arc. Barnes and Fodor (7C) have analyzed urine with an ICP in conjunection with a graphite rod electrothermal atomizer. A custom graphite rod electrode and a novel electrode enclosure were used to minimize loss of vaporized samples. Farnsworth and Hieftje (37C) have used an rf arc for the analysis of solids with an ICP. In this novel system, the sample is not transported to the plasma but, instead, the plasma is brought t o the sample! Keilsohn, Deutsch, and Hieftje (67C) have described the utilization of a microarc atomizer for sample introduction into an ICP. The microarc is a highvoltage, low-current, pulsating dc discharge; 0.5-1.0 pL volumes are efficiently vaporized and desolvated during sample introduction. Long and Snook (78C) have compared pneumatic nebulization with vaporization of slurries of capsule contents of pharmaceutical preparations from a resistively heated graphite rod into an ICP. In a related publication, Long and Snook (77C) developed an electrochemical preconcentration technique for use with an ICP. The use of a wall jet electrochemical cell for preconcentration of trace metals from flowing streams prior to their determination by ICP-AES is described. The metal of interest is deposited on a glassy carbon electrode held at the reduction potential of the metal. After collection, the metal is stripped back into solution by applying an anodic-stripping potential. The resulting metal solution is then introduced into the ICP. Papp (96C) has developed an electrothermal graphite furnace excitation source adapted to an emission spectrograph. This system is capable of simultaneous multielement determinations of analytes in 50-100 pL samples. Marks and co-workers (79C)have described a novel solid sampling device used in conjunction with an ICP multielement spectrometer. The incorporation of the device required only minor modification to the instrument. Layman and Lichte (75C) have developed an interesting nebulization technique consisting 138R
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of a porous glass frit which produces a smaller droplet distribution (mean size 0.1 pm). Hulmston (55C) has described a pneumatic nebulizer system for small sample volumes. Barnes and Mahanti (8C) described an HF-resistant sample introduction system for the ICP comprising a graphite injector tube, poly(tetrafluoroethy1ene) (PTFE) spray chamber, and a cross flow nebulizer containing PTFE capillaries. In a related publication, Barnes and co-workers (6C) analyzed aluminum samples with the system. Twenty-one elements were determined in primary refined alloy aluminum. The PTFE capillary tubes and spray chamber were required for the HF solutions. Wallace (11OC) has discussed some factors affecting the performance of an ICP sample introduction system. The nebulizer, spray chamber, and torch are each considered. Summerhays and co-workers (108C) have investigated sample introduction involving formation of volatile species and subsequent pneumatic nebulization into an ICP. Dobb and Jenke (29C) characterized and then corrected memory effects produced by pneumatic nebulizers for ICP sample introduction. Nobile et al. (94C) have described a modified ICP torch for use with methanol solvents. Alexander et al. ( I C ) investigated rapid flow analysis with the ICP using a microinjection technique which permitted the injection of 5 to 500 pL volumes into a rapidly flowing carrier reagent stream leading to a nebulizer. The effect on the analyte signal was studied as a function of flow rate, injection volume, and sample concentration. Stieg and Dennis (106C) described a detachable hydride introduction device for the ICP which continuously introduces hydrides through the nebulizerlspray chamber. Hutton and Preston (56C) have also described a simple versatile hydride-generation configuration for the ICP. In a particularly significant paper, Smith and Browner (103C) have measured aerosol transport efficiency by direct aerosol collection. A comparison of different direct methods, using cascade impactor, filter, and silica gel trap collection with indirect methods, using analyte waste collection was made. The transport efficiency for a typical atomic absorption nebulizer/spray chamber burner head was found to be 6.6 f 0.3% and for a typical I Plnebulizerlspray chamberltorch combination values of 1.1f 0.1% were observed. In another very significant paper, Browner, Boorn, and Smith (15C) explain aerosol transport in terms of the interaction of a primary generation process, with various secondary and tertiary aerosol modifying steps. A direct consequence of these studies giving a greater understanding of aerosol transport mechanisms should be more accurate and precise measurements and could lead to improved detection limits for certain elements. Goulden and Anthony (44C)have determined trace metals in freshwaters by using an ICP in conjunction with a heated spray chamber which produced a stable aerosol. Brackett and Vickers (13C)have described a fascinating new glow discharge device with continuous flow sample introduction. A chain conveyor is used for sample transport. The device is shown to possess many useful features and its potential utility as an element selective detector for liquid chromatography is suggested. Stanley B. Smith, Jr., and his research associates (104c) have published a very interesting paper discussing some considerations in the design of sample introduction systems for the ICP. Moore et al. (88C) have described an on-line dilution system for ICP spectrometry and Olsen and Strasheim (95C) have used a Mie scattering technique to study droplet-size distributions of the aerosols produced by different ICP nebulizers. Schmidt and Sacks (101C) have characterized a hybrid flamelarc excitation source using monodisperse aerosol introduction and Greenfield (46C) has evaluated the possibilities of FIA-ICP for "instant" signal-to-background measurement, calibration by standard additions and exponential dilution, and separation methods. Gustavsson (47C) has reviewed the theory of flow processes of compressible and incompressible media in nebulizers and Fujinaga et al. (38C) have used a sample injection method for introducing metal 0-diketonates into an ICP. Carr and Horlick (19'2) have developed a laser vaporization-ICP system for the direct analysis of solid metal samples. In this system the sample is vaporized utilizing a pulsed ruby laser and the vaporized material is swept into the ICP. Multichannel spectral data are simultaneously acquired by a photodiode array spectrometer. In a related paper, Ishizuka and Uwamino (58C) report on a laser-ICP system for the direct analysis of solid
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samples. Their system was constructed by combining a Qswitched or normal laser and an ICP. Emission signals of various elements were measured with an multichannel analyzer. Ottaway and co-workers (80C) have recently described a graphite probe atomization technique for carbon furnace atomic emission spectrometry. Na and Niemczyk (9OC) have studied the interference problems that can exist with Metastable Transfer Emission Spectrometry (WES).Interference processes were reported to be very similar to those seen in electrothermal atomization AAS. One major difference, however, is that the reactive nature of the nitrogen plasma can contribute to the elimination of interferences due to the vaporization or formation of molecular species involving the analyte. There is a fundamental limit to the amount of material, analyte, and matrix combined that can be introduced to the MTES system before the intensity vs. analyte mass relationship breaks down. Gratings. Engman and Lindblom (33C) have described a new spectrometer mounting that uses several echelle gratings as dispersive elements. The gratings are mounted so that a resolution equal to the s u m of the resolution of the individual gratings is obtained. In the mounting the dispersions from the gratings coact, resulting in very high dispersion in the focal plane. The multiechelle grating mount can be used to build compact spectrometers with higher resolutions that can be obtained with the widest gratings ever ruled. Some results from an experimental test of the multiechelle grating mounting are given. In a related paper, Engman and Lindblom (32C) described a new model for the blaze function of the two inplane mountings of echelle grating. They also discuss a simple method to measure the blaze angle and to get an estimate of the quality of the groove profile. Kaye (65C) has measured stray radiation in a spectrophotometer equipped with a holographic grating by using a convolution test. The stray radiation was found to vary with wavelength and polarization of the incident radiation because of plasmon scattering at the grating. When plasmon scattering exists, the convolution test is best conducted by using a number of slit functions scanning the interval of primary radiation. In a related publication, Kaye (66C) discusses stray radiation from ruled gratings. Gil and Simon (42C) have described a new plane grating monochromator with off-axis parabolical mirrors. Optics. Jolly and Stephens (63C) have determined the suitability of a flame atomizer in a Voight effect optical filter and Chisholm and Stephens (21C) have described the tuning of a Voight effect optical filter around the sodium 589.0-nm line. Barnhart and Walters (9C) have reduced the rf interference from a high-voltage spark source through fiber optic signal transmission and Carr, Blades, and Hieftje (18C) have used a separated impedance matcher/load coil assembly for convenient spatial translation of an ICP torch. Davie (27C) has determined the collection efficienty of a spectrograph for distributed sources. McDowell and Bouwer (86C) have optimized a dual mode Rowland mount spectrometer used in the 120-950 nm wavelength range. The theoretical imaging properties of this configuration are considered. Strasheim and co-workers (107C) have developed a new computer-controlled direct reading emission spectrometer. Their paper describes the design, implementation, and evaluation of a 20-channel direct-reading 1.5-m Paschen Runge type vacuum spectrometer. Computer control allows the changing from one analytical program to another in a relatively short time with ease and also allows the instrument to function as a dual scanning monochromator. Optical Detectors. Kubota, Fujishiro, and Ishida (74C) have described some characteristics of an intensified photodiode array spectrometer system for use in plasma emission spectrometry. Used in this study was a 1024-element silicon photodiode array coupled with a microchannel plate image intensifier used with a 2.25-m Czerny-Turner spectrometer. Zalewski and Duda (113C) described a silicon photodiode device with 100% external quantum efficiency. This device has not yet been used in an atomic spectrometer. Kennedy (68C) has discussed rf interference spark excitation with a commercially available (Baird) direct reader. Haisch et al. (49C)compared photographic and photoelectric measurement of radiation in the determination of very low concentrations
of metals in emission Spectrometry. Tait (109C)has described the optimization of stability in the output of a 1-m scanning monochromator. Brackett, Mitchell, and Vickers (12C) have described a simple low cost photographic attachment for a commercially available (BeckmanlSpectraMetrics) echelle spectrometer. Nash (91C) has some interesting comments on the use of X-ray film for emission spectrographic analysis. The effects of prefog ing on film speed are discussed. Schoaeb and coworkers r102C) state that a most significant source of imperfection in emission spectrography is the limited applicability of photographic tfansformation functions in the region of the emulsion characteristic below the point of inflection. Ag an alternative approach, they investigated the use of simple parametric equations. These require only a few mathematical operations. McGeorge and Salin (87C) comment on the control and dynamic range extension of linear photodiode arrays using a single board computer. Computer Interfacing. Mathews, Ekimoff, and Walters (81C) have described computer control of basic and applied experiments in spark emission spectrometry. The hardware system is described and software outlines are provided. The use of an optical coupler and a fiber optic is shown to improve system performance. Barrett, Fisher, and Barnard (10C) have described data acquisition in a sequential scanning ICP. Ediger and Barrett (31C) presented a data management system for an ICP using a main frame computer. Choi and Kim (22C) described Abel inversions of emission data from an ICP. Erickson and Monnon (3%) have discussed the problems of monochromator/microcomputer interfacing. As an example, a 0.5-m Ebert monochromator is coupled to a PET microcomputer to provide photon counting (15 MHz max), wavelen h readout (0.004 nm resolution), and scan control. Detaile circuit diagrams and supportive software are presented and suggestions for adaptation to other monochromator/computer combinations are given. McDonald and Neil (850have interfaced a PET microcomputer to a Varian AA-6 atomic absorption unit for processing and recording the resulta of atomic absorption and emission measurements. This interface could easily be adapted to plasma emission systems. Janssens et al. (59C, 60C) have developed a totally computer controlled monochromator for ICP-AES analysis and, in a related paper, Garbarino and Taylor (39C) have recently described a totally automated ICP spectrometer for routine water quality testing. Anderson and Munter (3C) have reported on the use of a microcomputer to improve sample handling on an automated ICP. The system was stated to increase the utilization of existing hardware and software for the analysis of samples and to reduce the operator workload. Adams and co-workers (2C) have recently described a microcomputer system for processing data from a three-channel AAS. This could also be useful in plasma emission spectrometry. Chromatographic Detector Systems. The interfacing of atomic spectrometry with chromatography (both gas and liquid) continues to be of interest. Estes, Uden, and Barnes (36C) have determined n-butylated trialkyllead compounds by GC-MIP using fused silica capillary columns. Trialkyllead chlorides were converted to n-butyltrialkyllead derivatives. Uden and co-workers (100C) have used an MIP detector for pyrolysis/gas chromatography for the determination of phosphorus and carbon in polyphosphazene pyrolysis and boron in carbonane-silicone pyrolysis. Cerbus and Gluck (20C) have described the design, optimization, and utilization of GC-MIP in an industrial laboratory. Jordan et al. (64C) have determined catechol derivatives via boronate ester formation and GC-MIP. Cammann et al. (17C) have described a power modulated MIP as an element-specific GC detector. Goode and co-workers (43C) have given a critical evaluation of the tangential flow torch MIP detector for GC. Qing-Yu et al. (97C)have investigated a microwave plasma spectrometric system as a quantitative detector for glass capillary GC. Caruso and co-workers (89C) have developed a rapid scanning spectrometer for GC-MIP which permits up to 20 spectra per second. Hagan et al. (48C) characterized fluorine containing metabolites in blood plasma by using capillary GC with MIP detection. Rice, Richard, D'Silva, and Fassel(99C) have compared analytical figures of merit of an active nitrogen afterglow and a flame ionization detector (FID) for GC.
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Calkin, Koeplin, and Crouch (16C) have described a highvoltage spark atomic emission detector for GC. The spark is formed between two thoriated tungsten electrodes by the discharge of a coaxial capacitor. The spark detector is coupled to the GC by a heated transfer line. Multiple sparks are computer averaged to improve the signal-to-noise ratio. Whaley, Snable, and Browner (111C) have commented on the properties of a pneumatic nebulizer/spray chamber as an interface for HPLC-ICP. A comparison was made of alternate spray chamber locations with respect to the column and plasma, and transport mechanisms of liquid and aerosol were contrasted. Placement of the spray chamber external to the plasma box was found to result in peak heights largely independent of the mobile phase flow rate. Jinno and coworkers (62C) have inve%tigateda micro HPLC-ICP combination technique in the analysis of organometallic compounds and Jinno and Tsuchida (61C) determined organically bound metals by using the same technique. DeGalan and co-workers ( I l C ) measured deuterium oxide elution data in reservedphase LC with an MIP 88 optical detector. Irgolic et al. (57C) have determined arsenic, selenium, and phosphorus compounds by HPLC with ICP detection. Gardner and Landrum (41C) used size exclusion chromatography with ICP detection to fractionate metal forms in natural waters and Gardiner et al. (40C) used a DCP detector in the gel filtration chromatographic determination of biological fluids. Plasma Emission/Mass Spectrometry. As noted previously, ICP-MS may be the “sleeper technique” of the 19809 and this sleeper technique may be awakening. Barnes has stated that (71A) “Because its price is competitive with the multichannel optical systems, and because of its added capabilities, the ICP-MS will challenge and may eventually replace the ICP-optical system”. At this point in time, two companies (Sciex in Canada and VG Isotopes in England) are selling commercial ICP-MS systems. As noted by Douglas and co-workers (30C), plasma/MS has two potential advantages over optical emission methods: (i) isotope ratio information (facilitating isotope dilution) and (ii) a greatly simplified spectrum, with fewer potential spectral interferences than optical spectra-ICP. Douglas et al. studied both an ICP and an MIP as ion sources for MS. Both sources demonstrated the two potential advantages for plasma/MS. Some matrix effects were noted with the MIP but these were not observed with the ICP. Date and Gray (39A, 26C) have recently discussed their development work in the application of ICP-MS. Two modes of operation were identified, boundary layer sampling and continuum (or bulk plasmas) sampling. Boundary layer sampling was reported to be characterized by very high signal-to-backgroundratios, giving detection limits better than 1 ng/mL (ppb) for a wide range of elements. The technique was applied to solution samples, nebulized a t approximately 2.5 mL/min. Samples may be processed at a rate of one every few minutes. In a related paper, Gray and Date (45C) discuss ICP source mass spectrometry using continuum flow ion extraction. The American “ICP-MS Center” is certainly Ames, Iowa, where Houk and his research associates are continuing their pioneering work in this area. In a very important paper, Houk, Fassel, and Svec (50C) have given a detailed account of sample introduction, ionization, ion extraction, and analytical results with the ICP-MS. In a related paper, the same authors (51C) discuss the mass spectra of organic compounds in aqueous solutions introduced into the ICP-MS. Houk and Thompson (52C) have described an ion sampling interface that extracts gas from the ICP into a vacuum system where the ions are mass analyzed and detected. Samples are directly introduced into the plasma ionization source and can be changed in approximately 2 min by simple procedures performed completely outside the vacuum system. Dissolution and nebulization are the only sample preparation procedures required. In another recent publication, Houk and Thompson (53C) described a system for the trace metal isotopic analysis of microliter solution volumes by ICP-MS. Houk, Montsser, and Fassel(54C) have extracted positive ions from the axial chamber of an ICP in which the outer gas flow was argon, nitrogen, or a mixture of argon and nitrogen. This paper is an excellent example of the use of ICP-MS as a diagnostic tool for the ICP. Kovacic and Ikonomov (73C) have recently analyzed reactions between carbon and hydrogen in a horizontal arc 140 R
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plasma with a mass spectrometer. The authors studied the formation of C2H2and C2H4in the plasma of an arc discharge in a mixture of argon and ethanol. Miscellaneous. Wunsch and co-workers (112C) have recently published a very interesting paper showing that the capacitively coupled microwave plasma (CMP) with nitrogen as a working gas is suitable as an atomizer for AAS. The type of CMP used has an excitation temperature of 4750-5600 K and a kinetic temperature of 4450 K. The authors state, however, that a high kinetic temperature alone is not sufficient; better degrees of atomization will only be achieved if plasmas with much higher analyte residence time or with reducing chemical properties can be developed. McCaffrey, Wu, and Michel (84C) have described a new method to discriminate against atomic emission spectral interferences in continuum source flame AFS and Ensman, Carr, and Hieftje (34C)modified a Plasma-Therm ICP power supply to enable rf power modulation. A simple modification was described to enable amplitude modulation of the output of the 5.0-kW ICP supply. In a related paper, Hieftje and coworkers (98C) described the design and construction of a low-flow, low-power torch for an ICP. Sobel (105C) has used an extended torch with an ICP for the determination of nitrogen in aqueous solutions.
STANDARDS, SAMPLES, NOMENCLATURE, CALIBRATION, CALCULATIONS Forster, Anderson, and Parsons (180)have tabulated the background spectra originatin from an ICP excitation source by using a standard set of con&tions. The data were acquired with a high-resolution scanning echelle monochromator capable of measuring wavelength position to 0.01 A. In a related publication, the same authors (20) classified and tabulated the spectra originating from alkaline-earth elements. The spectral range observed was 2075 to 6005 A. They observed almost all expected transitions for both atomic and singly ionized species in this spectral range. Several transitions were reported which were not in the MIT tables. Fassel and coworkers (500) have published information on the selection of analytical lines, line coincidence tables, and wavelength tables. Their paper includes a survey of the spectral information contained in their new book “Atlas of Spectral Information for ICP-AES” (to be published by Elsevier in late 1984) and provides the analyst with analytical capabilities and the potential spectral interferences of the prominent spectral lines of 70 elements. The “Atlas” will certainly be a major 1984 book and will contain 232 wavelength scans of 70 elements covering the range of 189 to 517 nm. The “Atlas” will also contain a listing of 973 prominent lines with estimated detection limits and a detailed collection of coincidence profiles for 281 of the most prominent lines, each with profiles of ten of the most prevalent concomitant elements superimposed. Capelle, Mermet, and Robin (90) have investigated the influence of the generator frequency (5-56 MHz) on the spectral Characteristics of an ICP. Higher frequencies tended to yield decreased line and background continuum intensities. Precision, linearity, interferences, and the ability to atomize high salt concentration samples were unaffected by frequency. Mahanti and Barnes (320) have discussed spectral line interference, limit of detection, and spike recovery in the determination of rare-earth elements in aluminum. Montaser and Fassel(350) have compared electron densities in argon and argon-nitrogen plasmas. In another publication, the same authors (340) describe a skimmer located below the usual observation height of an ICP that allows the axial channel region of the ICP to flow through the central hole of the skimmer while the outer argon flow is deflected. Signal-tonoise ratios and detection limits were 5- to 20-fold better in many cases. Winefordner and co-workers (290) have commented on the reduction of electronic noise in ICP atomic emission and fluorescence spectrometric measurements and Roederer et al. (420) have discussed the spatial distribution of interference effects in ICP emission analysis. The emissions of atoms, ions, and molecules were resolved on both a vertical and radial basis. Koirtyohann and co-workers (430) have reported that alkali-metal matrix elements enhance atomic and ionic emission in the lower portions of the ICP. Nonthermal excitation enhancement was reported as the apparent mechanism. Svehla and Dickson (470) have developed a simple mathe-
EMISSION SPECTROMETRY
matical model for the evaluation of analytical results which are subject to slow linear drift. The scheme was found to be very helpful in spectroscopicexcitation with the DCP. Myers and Tracy (370)have reported that noise and drift are reduced when an internal standard line is used. Xu, Kawaguchi, and Mizuike (510)have examined spectral interferences in the determination of phosphorus in steel and Schramel and Li-Qiang (460)have reported on the determination of beryllium in standard reference materials (SRMs). In a related paper, the same authors (450)have determined 14 elements in botanical samples by using SRMs as a multielement standard. Three National Bureau of Standards (NBS) “A” page Analytical Chemistry reports are of particular interest. Alvarez, Rasberry, and Uriano (ID)have given us a 1982 update on NBS SRMs with particular comments on inventory status, technology of certification, and recently introduced SRMs. Moody (360)comments on the need for clean laboratories when doing trace element analysis. There is a specific discussion of the NBS designed laboratories. Validation of analytical methods is, of course, a subject of considerable interest and Taylor at the Center for Analytical Chemistry at the NBS has written a very useful review (480)on the subject. The validation process is discussed in some detail. In a very important related paper, Cairns and Rogers (80) at the Food and Drug Administration discuss proposals for acceptable analytical data for trace analysis. This paper is based upon a talk given at the recent NBS symposium “Improving the Analytical Chemistry/Regulatory Interface”. This symposium was held in October 1982. The use of internal standards, matrix effects, and matrix matching has been the subject of several reports. Schmidt and Slavin (440)have reported a 25-fold improvement in precision with internal standardization in the determination of manganese in a 5 % sodium chloride solution. Marathe et al. (330)have developed a new method of internal standardization which they used to determine trace elements in rocks. Christian and co-workers (220)have described the use of internal standards for simultaneous multielement analysis (with an ICP) while using an electrothermal atomizer for sample introduction. Precisions for some elements were improved by 40% Belchamber and Horlick (30)have reported a factor of 2 improvement in precision when suitable internal standards were used. Thompson et al. (490)have developed a new method of correcting interference effecta in an ICP. For a given matrix and spectral line, a constant additive interference is produced that is independent of the trace analyte concentration. Interactive matrix matching allows interference correction. Bowker and Manheim (40)have commented on the determination of barium and strontium in sediments. Both alkali and lanthanum salts were needed in the final solution to achieve freedom from matrix effects. Faires et al. (170)have studied intra-alkali matrix effects in the ICP. Analytical correction for the interference is recommended. Jones and co-workers (260)have compared AAS and the ICP in the determination of trace elements in brine. AAS was not satisfactory due to lack of sensitivity and to severe matrix problems. Dellefield and Martin (140)have reported on the analysis of wastewater for seven priority pollutant elements. Linearity, detection limits, and stray light effects were reported for each element. Winefordner and co-workers (250)have examined the use of an exponential dilution flask for automated Calibration curve preparation and detection limit determinations. Linearity of the log concentration vs. time plot approached 5 orders of magnitude. Long and Winefordner (300)have recently discussed detection limits and closely examined the IUPAC definition. Klockenkamper and Bubert (270)have developed a scheme where a suitable calibration function can be found for five analytical examples. Maessen and Balke (310)have examined the analytical significance of extended linear working ranges with an ICP and Olsen and co-workers (400)have examined the effect of sintering on the mineralogy of a synthetic heavy metal concentrate. The concentrate was used to calibrate a dc arc emission spectrometer. X-ray diffraction and electron microscopy were used to study the matrices. In a related paper, Bubert and Klockenkiimper (60) have derived calibration and analytical functions for the general case where precision is not constant but is, instead, a function of the measuring quantity. Zhiglinsky and coI
workers (520)have commented on the use of correlations to improve the precision and accuracy of emission spectral analysis. Goldberg and Sacks (190)have reported the direct determination of metallic elements in solid samples by using an electrically vaporized thin film atomic emission technique. The method was evaluated with NBS SRMs. Detection limits were reported in the low- to sub-part-per-million range for a variety of elements. Crock and Lichte (130)have determined trace levels of the rare earth elements in U.S. Geological Survey coals, soils, and rocks. Nygaard, Chase, and Leighty (390)have determined trace elements in water near the detection limit with a sequential scanning spectrometer-ICP. Korte and co-workers (280)have determined Zr:Hf ratios in the mineral zircon. In a particularly well-written review article, Hieftje (230) has commented on approaching the limit in atomic spectrochemical analysis. He stated that the two principal goals in chemical analysis are improved selectivity and improved sensitivity. Basic atomic emission, absorption, and fluorescence monitoring techniques are reviewed. Several papers have discussed hydride generation atomic emission spectrometry as a means of obtaining lower detection limits and reduced interferences. Caruso and co-workers (160) have used a sequential slew-scanning monochromator as a plasma emission chromatographic detection for the determination of volatile hydrides. The detector monitored each chromatographic peak at a different atomic emission wavelength. Detection limits ranged from 0.004 to 0.5 pg. Hahn, Wolnick, and Fricke (200)have commented on the use of a hydride generation/condensationsystem for the determination of arsenic, bismuth, germanium, antimony, selenium, and tin in foods. Nakahara has determined tin in NRS SRMs by a volatile hydride method. Pruszkowska et al. (410)have described a continuous flow hydride system interfaced to a sequential ICP. Chiba et al. (120)have developed a method for the determination of ultratrace levels of fluorine in water and urine using a GC/atomspheric pressure helium (Beenakker type cavity) MIP. In a related paper, Chiba and Haraguchi (110)have determined halogenated organic compounds in water. Han et al. (210)have described an interesting combustion apparatus that allows the quantitative liberation of cadmium, thallium, lead, and bismuth from rocks and soils. A stream of pure oxygen is used. Recovery rates were reported over 95% for all matrices studied and good agreement was found with SRMs. Bratter et al. (50)have used SRMs in the simultaneous multielement analysis of biological materials. By use of multielement SRMs to match approximately the matrix of some biological samples, improved performance is obtained if a chemical digestion of the standards and samples is employed. The procedure provides a constant acid concentration and solids content. In a very interesting paper entitled “Analytical Range”, Butler (70)reviews methods for testing analytical methods. He proposes that “analytical range” be defined in terms of the “best” precision of measurement obtained over a concentration range multiplied by a factor acceptable to the analyst. The factors causing a decrease in precision of measurement at lower and higher concentration ranges are discussed with respect to AAS and atomic emission using an ICP. deKreuk et al. (150)have recently discussed risks associated with automatic data compiling and processing in spectroscopic routine analysis. Three specific examples are given along with some rules to reduce the chance that such errors may occur. Howard and co-workers (240)have tabulated intensities for some spectral lines from hollow cathode lamp discharges. Barbara Cassatt (100)of the AnalyticaZ Chemistry staff has compiled a short but useful bibliography of rCTPAC reports on analytical nomenclature that appeared in Pure and Applied Chemistry during the years 1978-1981.
EXCITATION SOURCES This section considers papers where the primary emphasis is on the source. A total of 266 papers are cited and the breakdown is as follows: arc discharges, 23 citations; DCP, 17 citations; GDL, 14 citations; HCD, 12 citations; ICP, 123 citations; microwave discharges, 29 citations; spark discharges, 14 citations; other excitation papers, 34 citations including 9 MECA citations. This breakdown gives some indication as to the relative popularity of the various sources (at least with ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
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respect to research) at this point in time, Arc Discharges. Much important work in this area continues to come from Yugoslavia. Radic-Peric (220E,221E) has recently calculated the optimum temperatures for the emission of the atomic and ionic spectral lines of calcium and of CaO, CaF, and CaF, electronic bands in the presence and absence of fluorine. It was assumed that the plasma composition, radial temperature distribution, and radial distribution of total calcium can be changed due to the presence of fluorine. Holclajtner-Antunovicand cc-workers (University of Belgrade) have presented (127E)a theoretical model of the spatial particle density distribution of traces in a DC arc plasma. The basic model is grounded on realistic estimations of transport velocities which indirectly include the influence of cathode layer phenomena on the particle distribution. In 129E)have related work, Holclajtner-Antunovic et al. (128E, calculated the spatial particle density distributions in a DC arc plasma according to various theoretical models. The obtained theoretical results were compared with experimental measurements and reasonably good agreement was found particularly for indium, an element with a relatively low ionization potential. Eid et al. (79E)have used a wall stabilized DC arc for the determination of rare-earth elements. At the optimal excitation conditions, the spectrum of the arc has a very low background and contains no molecular bands in the visible region. Analytical curves and limits of detection for 14 rare earths were determined and the matrix effects were studied. Radermacher and Beske (219E)have recently studied the relation between the neutral particle fraction and the charge distribution of the ions in a vacuum arc discharge. The resulta showed that is is not possible to extrapolate the parabolic charge distribution of the ions to the neutral particle fraction. A method was demonstrated, however, to show that the neutral particle fraction can be inferred from the charge distribution of the ions. Hanzsche has commented (117E)on the thermofield emission of electrons in arc discharges and Ecker (75E)has described arc discharge electrode phenomena. Dalvi et al. (60E)have determined thorium and zirconium in uranium by DC arc emission spectrography. Dittrich and co-workers (71E)have investigated the influence of NaCl and Ba(N03)2on the intensities of atomic lines of aluminum, tin, and beryllium and on the axial particle distribution of these elements in a DC arc plasma. NaCl and Ba(N0 )z were found to reduce the temperature of the plasma. The enkancement of the intensities was best in the presence of very large amounts of Ba(N03)2. Eroshenko and Dem’yanchuk (81E)have recently characterized an AC arc used for the spectral analysis of metals and Meubus and Elayoubi (191E)have described the theoretical behavior of a solid article in an arc discharge during transient cooling conditions. kiljevic (193E)has performed a spectroscopic study of a DC gas magnetron discharge and his results indicated a nonequilibrium system. Novak and Shoucri (207E)have simulated high-voltage breakdown in the postarc column and Romanov et al. (2263)have discussed the optical properties of a high-temperature aluminum plasma. In a very important publication, Paksy and Lakatos (214E) have described the axial injection of argon into a conventional arc source through a hole drilled in the upper electrode. In spite of a simple electrode arrangement, the argon produces unexpected and significant changes in emission phenomena. Self-reversalis practically eliminated. Intensity enhancements were studied as a function of line character, excitation potential, electrode type, concentration of analytes and concomitants, the presence of organic materials (solvents and solutes), and the argon purity. It was observed that the intensit enhancement deteriorated if the concentration of excitaile particles (atoms, molecules, free-radicals,etc.) in the plasma increased. Similar results were obtained when the argon was replaced by krypton. Impurities in the argon did not affect results UNLESS the argon contained organic impurities such as methane, propane, etc. The Paksy and Lakatos paper was stated to be the f i s t in a series and it is hoped that there will soon be more papers in the series. Krasnobaeva et al. (166E)have described optimum conditions for DC arc analysis of NH4A1(S04)2.12H20and A1203and the detection limits for impurities were determined. These same workers also considered the applicability of laser spectral microanalysis for monitoring the distribution of neodymium in single 142R ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
crystals. Huczko and Szymanski (132E)have studied the decomposition of carbon dioxide in an arc plasma discharge and Martynov (186E)has discussed improvements in arc discharge excitation with specific reference to spectral analysis of mineral raw materials. Teraoka (240E)has developed a simultaneous method for more than 20 elements in biological tissues using DC arc spectrography. Marode (184E)has published a detailed (47 page) paper discussing the glow-to-arc transition and Ushio (247E)has given a general report on arc-cathode phenomena. Direct Current Plasmas (DCP). As noted previously, Zander has recently written an excellent two-part review (154A,155A)of the DCP and its relationship to the echelle spectrometer. Resolution aspects are discussed in detail in the second (155A)paper. Keliher and Boyko (152E)have discussed problems associated with the introduction of organic solvents into the DCP. Some modification of the sample introduction system of the three-electrode DCP is necessary. The conventional tubing is replaced by silicone rubber tubing and the sample delivery tip geometry is modified. With the modified tip, it is possible to deliver an organic aerosol into the plasma for up to 12 h without a trace of carbon formation on the anode sleeves. In a related publication, Gilbert and Penny (I04E)have alsu modified the sample introduction system to the commercially available (Beckman/SpectraMetrics) DCP. They were able to easily determine trace elements in five organic solvents: hexane, dichloro-, trichloro-, and tetrachloromethane, and 4-methyl-2-pentanone. The solvents were reported to be extensively vaporized in the nebulization system, resulting in improved sample delivery to the plasma and enhanced sensitivity. The technique was used to analyze silicone fluid in the bond paper employed in photocopies and to determine trace elements in seawater following solvent extraction. I n a n important paper, Eastwood and co-workers (73E) have measured sodium-induced emission enhancement of transition-metal resonance lines in a DCP for wavelengths from 210 to 395 nm. Systematic differences in enhancement were observed within individual spectra (Fe I, Ni I, Sc 11)and the enhancement and the excitation potential of a line was found to be linearly related. Electron density and apparent temperature data led to an interpretation of this energy dependence within the context of a recombining plasma in partial thermodynamic equilibrium. Dittrich and co-workers (70E)have studied the influence of different amounts of Ba(N03)2on the distribution of the intensities of manganese, thallium, lead, and mercury in a DCP. It was found that with increasing amounts of barium the plasma temperature decreased and the electron pressures increased. Fujishiro et al. (99E)have used a low-power DCP to estimate the analytical characteristics of an argon-nitrogen plasma as compared to an argon plasma. The optimum plasma was reported to be an argon-O.23% nitrogen plasma. Better precision and lower detection limits were attained for aluminum and cadmium with the argon-0.23% nitrogen plasma than with the pure argon plasma. Boyko and Keliher (35E)have described the construction of a simple drop generator for introducing small (ca. 20-50 NL)repetitive samples to the three-electrode DCP. An individual drop size delivery precision of 5% relative standard deviation or better was obtained for the smallest drop size used (16 pL). Larger drop sizes gave better delivery precision. The magnitude of the emission intensity pulses for the 18-pL drop size was found to be 77% of the continuous sampling level. For larger drop sizes there was an approximate linear relationshi between the emission intensity and drop size. A 27-pL irop gave 97% of the continuous sampling emission intensity whereas a 48-pL drop size gave 104% of the continuous level. Signal linearities for both continuous introduction and discrete sampling modes were presented in the paper and the advantages of discrete sampling were discussed. Griffin and Savolainen (lib!?)have used a DCP-echelle spectrometer in a round-robin determination of niobium in a reference ore. Excellent corroboration was obtained. A quantitative dissolution technique was developed for niobium-bearing alloys and synthetic standards, approximating the solution matrices, were used to analyze both the ores and the alloys. Frank and Petersson (98E)have used a DCP-echelle spectrometer for the simultaneous determination of 14 metals in animal tissues. The analytical emission lines were chosen
EMISSION SPECTROMETRY
after considering the absence of more important interfering emission lines from elements present in the matrix and taking into account their intensity, background, range of linearity, and working range. Ji et al. (138E) have used a DCP for the determination of 19 elements in the hair of cows suffering from chronic lymphocytosis and Lohau and co-workers (175E) have used a DCP for the analysis of various metals in iron and steel products. Mohan et al. (197E) have used a helium DCP for the determination of arsenic in herbicide-treated soils and Johnson and Sisneros (139E) have used a DCP-echelle spectrometer for the determination of various rare earths in ore samples. Natansohn and Czupryna (202E) have used a DCP-echelle spectrometer to determine impurities in two solid materials, ammonium peratungstate and silicon nitride. After sample dissolution, careful matrix matching is essential for the quantitative determination of trace impurities but the technique itself is reported to be rapid and reliable. Grogan (11IE) at Heriot-Watt University in Scotland has used a DCP-echelle spectrometer to determine several trace elements in samples collected from the North Sea during marine monitoring surveys. Analysis of SRMs indicated that the DCP system yields results comparable to other analytical methods such as AAS. I n a particularly interesting paper, Wirz and co-workers (259E) have used a DCP as an atomizer for a Zeeman AAS system. It was reported that the high plasma temperature in connection with the Zeeman technique resulted in analyses that are less prone to matrix effects. It was stated that the radiation from the plasma does have a high intensity (compared to that from a graphite furnace) but the high intensity can be compensated for by modulating the light beam from the source and using a band-pass filter. It was possible to directly determine trace elements in solids such as sewer sludge with the technique. Finally, two recent Ph.D. theses should be mentioned. M e n (6E) has written an in-depth thesis describing his recent research a t the University of Georgia on the subject of sample introduction into the DCP and Hara (118E)at Arizona State University has developed and evaluated a rotating arc DCP as a spectroscopic excitation source. Both of these theses provide detailed information. Glow Discharge Lamps (GDL). Much important work in this area continues to come from the National Physical Research Laboratory of the CSIR in South Africa. Ferreira, Strauss, and Human (NE)have reviewed development work on GDLs at the CSIR and described some recent developments, e.g., the use of a fluorescent atomic vapor as spectral line isolator and the use of a microwave auxiliary discharge to augment excitation of sputtered material. The microwave auxiliary discharge was reported to considerably enhance sensitivities and to lessen self-absorption in the source. In a related paper, the same authors (89E)discuss the absorbance by metastable argon atoms of the Ar 696.54-nm line in a modified Grimm-type GDL. Their preliminary research confirms the findings of other workers that metastable atoms play an important role in excitation and ionization in spectroscopic sources. The authors state, however, that more detailed investigations should be conducted in order to arrive at more quantitative conclusions. Brackett and Vickers (36E) have recently described a unique GDL desi ned specifically for solution analysis. The detection limits ottained were stated to be comparable with demountable-HCL sources but with better precision. Rotational and excitation temperatures were examined as functions of fill gas pressure and discharge current. A sputtering constant was presented and the technique for measuring this parameter was described. The authors stated that their device should be extremely useful in determinations where the amount of available sample is limited. Winefordner and coworkers (2493)have constructed a demountable GDL and have studied the various processes taking place in the discharge. Continuous wave laser excited fluorescence was used to study the spatial distribution of sodium atoms which were sputtered off the cathode. Their results (obtained by using combined laser and classical diagnostics) showed that there exists a region between the electrodes where the intensity of the lines from transitions of the fill gas is low but that this region contains an appreciable amount of atoms sputtered from the sample. Nestor (203E) has commented on the op-
togalvanic spectra of neon and argon in GDLs and Laqua and co-workers (217E)have used a GDL for emission spectrometric surface analysis. Kretschmer et al. (267E) have stated that it is possible to measure several layers of material composition at a surface with a GDL. I n an important publication, McDonald (19OE)has measured temperatures, electron densities, and degrees of ionization in a boosted GDL. The intensities of Fe I and Fe 11 spectral lines emitted by the source were measured over a range of typical lamp operating conditions. It was found that when sufficient booster current was applied, the Fe I and Fe I1 temperatures were comparable (ca. 4000 K) and reasonably independent of discharge parameters. An equation which allows the calculation of the degree of ionization for an element in t ical discharge conditions was formulated an the expected g r e e of ionization was calculated for 15 elements. In another publication, McDonald (189E) used AAS for the study of agglomeration of atoms in a GDL. It was estimated that the fraction of sputtered atoms contained in clusters was about 30%. Loving and Harrison (I 78E)have recently published a very interesting paper whereby they simultaneously use AAS and MS in conjunction with an abnormal GDL. By combining these two analytical methods, they gained useful information concerning the effects of discharge parameters, source design, and electrode positioning in the GDL. Brandt (38E) has discussed arc prevention in a GDL and Lomdahl et al. (176E) have reported on the determination of nonconducting materials with a boosted output GDL. Demyshev and Merkushkin (65E) have described parameters of neon-filled GDLs and Demeny (63E) has studied GDL emission sources with planar cathodes. Hollow Cathode Discharges (HCD). Much important work in this area comes from Caroli and his research associates in Rome, Italy. For a summary of recent work in this area, we once again suggest Caroli's very recent review (28A). Caroli, Alimonti, and Zimmer (51E) have used a HCD for the determination of trace elements in mineral residues from the ashing of biological materials. The precision of the measurements and the detection limits were stated to be entirely satisfactory. In a related publication, Caroli, Senofonte, and Femmine (53E) have performed a comparative study of matrix effects by using an HCD for the determination of trace elements in biological materials. The source was found to be not significantly prone to matrix effects. Caroli, Alimonti, and Petrucci (50E) have coupled a microwave discharge with a HCD. The intensity of spectra emitted by the discharge with and without the superimposition of 2450-MHz microwaves was studied under different operating conditions with argon as the filler gas. The intensities of copper spectral lines were higher in the presence of microwaves whereas the argon lines were reported to be weaker. In a related publication, the same authors (52E) use the microwave-coupled HCD discharge for the determination of trace elements in steel. Farnsworth and Walters (86E)have used time and space resolved emission spectrometry to examine the excitation processes in rf boosted pulsed hollow cathode lamps (HCLs). Sealed commercial HCLs with copper cathodes and neon or argon buffer gases were driven with temporally spaced unidirectional current pulses and rf burst. Three excitation periods were considered: the current pulse, the rf burst, and the afterglow. Each of these periods was marked by a unique set of emission characteristics that suggested different combinations of excitation processes. Excitation during the current pulse appears to be a combination electron impact and charge exchange. In a related paper, the same authors (85E) have used an echelle grating monochromator (McPherson) to monitor atomic line profiles in a HCD. Temporal resolution of 11 s was provided by a gated photon counter. The echelle grating was used in their system without a cross dispersive device. Hasegawa, Haraguchi, and Fuwa (119E) have measured spectral line profiles from HCDs (as well as from ICPs) by using a wavelength modulated echelle spectrometer and Fogs and co-workers (97E) have determined trace elements in aqueous media by using a cryogenic HCD ion source. Kaiyi (147E) has described an automatic HCD device for emission spectrochemical analysis and Gao et al. (1013)have developed a direct method for spectrographic determination of harmful impurities in high-temperature alloys by using an HCD discharge. Ape1 and co-workers (9E)
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have described optogalvanic effects in HCDs with nonlaser sources and Berglund and Thelin (22E) have used a demountable double-chamber HCD for the determination of trace elements in steel. Inductively Coupled Plasmas (ICP). ICP papers continue to proliferate at an amazing rate. Many fundamental and applied papers have appeared during the past 2 years. Because the ICP is expensive (both to purchase and to operate), some workers have considered ways to reduce both the rf power and coolant argon required to sustain the discharge. Hieftje (126E)has considered various approaches to accomplish this, e.g., reducing the size of the ICP, modifying the torch used to support the discharge, alternative torch cooling schemes using water or high air flows as coolants. Hieftje’s article considers some future torch modifications and low-flow, low-power ICP instrumentation that is becoming available. On this subject, deGalan and co-workers (2253) have described an ICP with a total argon consumption of 0.85 L/min. A novel coil construction was used along with a two-tube plasma torch. External cooling is provided by pressurized air, which is blown against the exterior of the torch, thus realizing adequate cooling without losin high coupling efficiency. In a related paper, Ripson and de alan (22423)have used an experimental approach to establish the power balance for three ICPs: (a) a conventional ICP operating on 23 L/min of argon; (b) an air-cooled ICP requiring only 1L/min of argon; (c) a watercooled ICP requiring only 1L/min of argon. The air-cooled plasma was reported to use a much lower incident power of 300 W most efficiently. Kawaguchi and co-workers (151E) have constructed a new type of water-cooled torch made by modifying a conventional three-tube torch. Interference effects of sodium, aluminum, and phosphate ions, and detection limits for many elements were comparable to those in the conventional ICP. Blades and Hieftje (27E) have discussed the significance of radiation trapping in the ICP. In a related paper, Blades (268)has stated that the measured density of electrons in the ICP cannot be explained on the basis of a pure local thermodynamic equilibrium (LTE) calculation. Blades offers a mechanism which involves radiation trapping and the transfer of excitation ener y from the annular regions of the ICP to the aerosol channe . The mechanism is referred to as “assisted ionization” and it is stated that this leads to a more accurate prediction of electron density at a particular temperature. Assisted ionization is stated to be the result of the coupling of high-energy resonance radiation from Ar I in the annular regions of the ICP into the analyte channel. Blades (%E) has also very recently used a photodiode array based spatial emission profiling system for performing an Abel inversion on an ICP. Horlick and his research associates a t the University of Alberta in Canada are continuing their fundamental studies of ICPs. Belchamber and Horlick (17E) have measured noise power spectra of emission signals from an ICP discharge. Below 5 Hz the noise power spectra showed a marked dependence on the type of nebulizer used. Above 5 Hz the noise power spectra were relatively independent of the nebulizer. Distinct peaks were observed in the noise power spectra in the 200-400 Hz region. The exact position and intensity of these peaks were dependent upon rf power, coolant gas flow rate, and torch design. Furuta and Horlick (IOOE)have measured vertical, lateral, and radial profiles of analyte emission in an ICP and Belchamber and Horlick (18E)have commented on the effect of signal integration period on measurement precision with an ICP. In another publication, the same authors (19E)have correlated fluctuations in emission signals from an ICP with fluctuations in the nebulizer spray chamber pressure. Horlick and Furuta (131E) have published a paper showing many spatial photographs that have influenced their formulation of an overall spatial picture of anal@ emission in the ICP. Their paper shows clearly that a picture can be worth a thousand words! Myers and co-workers (2443) have found that electrostatic fields created by the charge on the spray in the pneumatic nebulizer are found to be an intermittent source of several types of ICP emission instability. The electrostatic effects act to reduce the sample aerosol density leaving the spray chamber. Simple diagnostics, however, allow unambiguous conformation of the presence of electrostatic signal depression and suggest techniques for its control. Tracy and Myers
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(243E) have measured the spectral radiance of the plasma continuum of a 27-MHz argon ICP for two sets of operating conditions in the wavelength range from 192 to 600 nm. For wavelengths below 400 nm, the absolute plasma emission spectrum was found to be represented by a graybody function with a temperature of 5480 K and an emissivity of 4 X Boumans and co-workers (218E)have presented a detailed theoretical and experimental investigation of non-LTE phenomena in an ICP and Boumans (33E) has commented on excitation mechanisms in the ICP. Boumans and Lux-Steiner (34E)have modified and optimized a 50-MHz argon ICP with special reference to analysis with organic solvents. Kornblum and Smeyers-Verbeke (161E) have commented on the behavior of the excitation temperature in the ICP and Liu and co-workers (174E) have determined radial temperature distribution in an ICP. Lovett (177E) has presented a well thought out model which explicity considers the various rates of excitation, deexcitation, ionization, and recombination for analyte species in an ICP of defined electron density and temperature. The model reveals that radiative decay, radiative recombination, and radiative absorption affect the level populations of a fundamentally collisionally dominated plasma. In addition, Penning ionization is shown to have a negligible effect on spectrally derived temperatures except for eIements of high second ionization potential. Maessen et al. (180E)have studied separate and combined matrix effects on 13 ICP analysis lines and Botto (32E) has devised a dual spectrometer system for reducing spectral interferences in multielement ICP-AES. In a related paper, Botto (31E) has commented on the long-term stability of spectral interference calibrations for the ICP. In a n important paper, Fuwa and his research associates at the University of Tokyo (206E)have observed spatial distributions of calcium atom and ion lines in an ICP. The number densities of metastable argon and ground-state calcium atom and ion lines in an ICP are estimated from the results. Excitation mechanisms are also discussed in the paper. Gunter et al. (112E)have considered some aspects of matrix interference caused by elements of low ionization potential in the ICP and Gunter et al. (113E) have also measured radial excitation temperatures and electron number densities in 9-, 27-, and 50-MHz ICPs. Kawaguchi et al. (150E)have performed interferometric measurements of spectral line widths emitted by an ICP and Eckert and Danielsson (76E) have described an equilibrium model for the radial intensity distribution of analyte lines in an ICP discharge. Fischer and co-workers (91E)have used a 10-channel grating polychromator for plasma emission diagnostics. Mermet and his research associates at the SCA-CNRS in France are continuing their fundamental studies. Batal and Mermet (15E)have given a tentative classification of energy of analytical lines in an ICP according to possible excitation mechanisms. The charge transfer from the argon ion is emphasized but other possible mechanisms are also described. Abdallah and Mermet (2E)have compared temperature measurements in an ICP and an MIP with argon and with helium as plasma gases. Batal, Jarosz, and Mermet (14E)are continuing their spectrometric studies of a 40-MHz ICP; in their latest paper the continuum of the argon-hydrogen plasma is determined both theoretically and experimentally. In another important paper from France, Borsier and Garcia (30E) discuss methods for high sample rate analysis of geological samples with an ICP. It is well known that echelle spectrometers are commonly used with DCPs but are less likely to be used with ICPs. For that reason, Fernando’s recent paper (88E)describing an ICP-echelle spectrometer combination is particularly important. The need for high spectral resolution for the accurate analysis of complex samples by ICP-AES has become increasingly evident with the realization that spectral interferences can be significant in an ICP. Fernando has presented ”figures of merit” for an ICP-echelle spectrometer for 55 elements. The analytical importance of each figure of merit is discussed. The analytical results obtained with the ICPechelle system were stated to compare well with previously published figures for ICP studies. Fernando concludes his paper by stating “The echelle grating spectrometer featuring high resolution, good analytical characteristics, and flexible direct reader capabiFty is an excellent choice for high performance ICP-AES.
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Benetti and co-workers (21E)have recently studied the noise properties of an ICP. A fast Fourier transform spectrum analyzer was directly coupled with the PMTs of an ICP system. Aeschbach (3E)has studied electron density in argon ICP discharges and Xi-en and Qi-lan (2643)have noted that small amounts of phosphoric acid even down to 0.1% in a sample solution will appreciably reduce the line intensities of analytes in the ICP. The phenomenon was reported to be due chiefly to insufficient desolvation of the aerosols. Hayakawa and co-workers (120E)have determined several nonmetals in an ICP using lines in the vacuum-UV and Kempster and co-workers (153E)have determined interference correction coefficients in an ICP. Walters et al. (2523)have described the influence of dispersion and stray light on the analysis of geological samples using an ICP and Seeverens et al. (2333) have performed a critical evaluation of the performance of triphenylphosphine and N,N’-diphenylthiourea in solvent extraction into an ICP. Caruso and co-workers (188E)have determined several elements in an ICP for complex samples and, in a related paper, Ng and Caruso (204E)have used a microliter sample introduction system (electrothermal carbon cup vaporization) into an ICP. Sugimae and Mizoguchi (2373) have determined airborne particles by direct nebulization of suspensions into an ICP. He (121E)has studied the excitation characteristics of various lines in an ICP and Degner (62E) has determined various spectral interferences with an ICP using iron, chromium, and copper as matrix elements. An important “ICP Center” continues to be Atlanta, GA, where Browner and his associates are continuing their studies on the ICP with an emphasis on sample introduction and fundamental aerosol studies. In addition to the papers already cited (15C,103C, IllC),Boorn and Browner (29E)have studied the effects of organic solvents in an ICP. The tolerance of a lower power (1.75 kW) ICP for 30 common organic solvents was reported in terms of their limiting aspiration rates. It was found that solvent vapor loading is the major factor influencing plasma stability with organic solvent introduction. Signal magnitudes were compared for both aqueous and organic solutions of several elements. Leary and co-workers (173E)have performed an objective function for optimization techniques for simultaneous ICP and Wichman, Fry, and Kohamed (2563)have developed a Teflon version of the Babington slurry nebulizer. The updated design was stated to be free of contamination and easier to construct and repair than previous designs. In a related paper, Wolcott and Sobel (260E)have described a unique Babington-type nebulizer. It was stated that the nebulizer could be used for the analysis of clear dilute solutions, solutions with suspended solids, and solutions containing high percentages of dissolved solids. Ramsey et al. (2233)have modified a concentric glass nebulizer in order to reduce memory effects in an ICP and Nygaard and Lowry (208E)have developed a sample digestion procedure for the simultaneous determination of arsenic, antimon , and selenium that uses hydride generation into an ICP. 8ustavsson (114E) has developed an interesting mathematical model for concentric nebulizer systems and Zagatto et al. (153A)have used FIA in conjunction with the ICP. Smythe (2343)has described a liquid microsampling technique for ICP-AES and Wallace and co-workers (250E) have described a HF acid resistant sample introduction system for the ICP. Kirkbright and co-workers (13E,1553,156E) have commented on the advantages of combining the ICP with graphite furnace (and other related) techniques. Other papers from Kirkbright’s laboratory describing these important interfaces have been cited previously (24C,69C,70C,71C,76C). In a particularly interesting paper, Downey and Hieftje (72E)have significantly reduced spectral interferences in an ICP through the use of selective spectral-line modulation. In this method, a mirrored, rotating chopper directs the emission from the ICP alternately through and past a flame; selective modulation is achieved when the flame contains absorbing atoms identical with emitting atoms in the ICP. The authors clearly demonstrate the ability of selective spectral-line modulation to minimize broad band, narrow line, and scattered light spectral interferences. Golloch and co-workers (1063)have used optical quartz fibers for a polychromator ICP system and Krull et al. (1683)have speciated Cr(II1) and Cr(V1) by using reversed-phase HPLC in conjunction with an ICP.
Papers cited up until this point have used only one ICP (at least only one at a time) but Kosinski, Uchida, and Winefordner (163E)have bravely used two ICPs in an AFS system. One ICP is used as the excitation source and the second ICP is used as the atomization cell. The authors have obtained emission, excitation, and fluorescence analytical curves of growth and verticial distributions for zinc atomic and calcium ionic fluorescence intensities were also obtained. The paper concludes with a discussion of interelement effects, spectral interferences, and noise sources. This technique should probably be referred to as (ICP)*. In related work, Kosinski, Uchida, and Winefordner (164E)have evaluated an ICP with an extended sleeve torch as an atomization cell for laser-excited AFS and Uchida, Kosinki, and Winefordner (246E)have studied the characteristics of atomic and ionic fluorescence excited by a pulsed dye laser in an ICP from the point of view of plasma diagnostics. Kosinki’s recent Ph.D. thesis (162E) (University of Florida) contains detailed fundamental information regarding plasma diagnostic studies. At this point in time, one commercial firm (Baird Corp.) has introduced an ICP-AFS system. The ICP is used as the atomization cell and HCLs are used in the multielement system. Two recent review articles (643,1723)describe the Baird system in some detail. Prack and Bastiaans (215E)have recently described an evolved gas/emission spectrometer system capable of speciating inorganic compounds in solid samples. Samples are gradually heated to 2300 “C in a graphite sample probe that is moved in a controlled manner into an ICP. As the sample is heated, its components vaporize at characteristic temperatures into the supporting argon of the ICP which acts, of course, as the emission source. Identification of a given compound is based upon the position of the sample at the time of evolution of the metal. This is an interesting approach. It is stated, however, that problems which can complicate identification and speciation include chemical reactions in the sample and between the sample and ita surroundings. Further studies may solve some of these problems. Many papers published during the past 2 years have described new ICP methods for the determination of elements in various materials such as agricultural products, marine samples, sludge, etc. Our 1984 award for the most interesting material, however, goes to Parsons and co-workers at Arizona State University (&E) who have used an ICP for the analysis of elements in “pink bollworm” (PBW). One might wonder why one would be interested in determining elements in PBW. It turns out that PBW is one of the major pests in the cotton industry in Arizona. One of the areas of investigation in agricultural research has been the search for an element which can be physiologically incorporated within PBW when reared on an artificial diet. By observing the higher levels of elemental uptake with the PBW moth, the discrimination of mass-reared (sterile) PBW from native PBW can be made. This paper is certainly a very practical example of the utility of the ICP in the analysis of genuine in real life samples. In addition to PBW, the ICP has been used in the analysis of agricultural products (136E,169E),alloys (39E,40E,84E, 92E,2663),amino acids (265E),animal diets (93E),bauxite (12E),biological tissue (61E,2303,231E),blood (1553),bone (155E,183E),chromates (255E),coal (182E,216E),fatty acids (11E), feces (93E),fertilizers (140E),foodstuffs (83E),geological materials (28E,54E,1983,211E),graphite (181E), lake sediments (55E),lanthanum oxide (]%E), liver (155E),marine samples (66E),milk (13E,47E,1553),muscle (155E),nuclear material (24E,56E,87E,95E,2123,213E),petroleum products (41E),plant material (141E,179E),serum (1253,1553), sludge, soils, and rocks (1543,2323),steel (80E,241E),urine (IOE,96E,192E,194E),water (74E,153E,1953,196E,242E), yttrium oxide (205E),and zirconium oxide (134E).The above papers have been cited in this section of the review since some ICP development work has been required to do the analyses. Microwave Discharges. Two categories of microwave plasma are generally used in analytical chemistry (a) the capacitively coupled plasma (CMP) where a magnetron generates microwaves which are conducted through a coaxial waveguide to the tip of an electrode and (b) the microwave induced plasma (MIP) where the energy is applied with an external cavity (Broida, Beenakker, etc.) or antenna. The MIP is more commonly used. Recent work has focused on (a) fundamental studies and direct sample introduction into MIPS and (b) use of MIPS as chromatographic detectors. ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
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I n an important publication, Tanabe, Haraguchi, and Fuwa (2383) have characterized an atmospheric pressure helium MIP and discussed excitation mechanisms in the MIP. Comparisons were made with argon and mixed gas (argon/ helium) MIPs. Kollotzek, Tschopel, and Tolg (159E) have found it possible to generate different forms of an argon MIP in a cylindrical TM (Beenakker type) cavity if special mountings for the Ascharge tubes were used. A stable three-filament MIP proved very suitable for the analysis of nebulized solutions. The optimum observation zone for each plasma form was determined by radial profiles of the signal and background intensities. Goode and Baughman (108E)have developed a novel method for monitoring the atomization processes in a reducedpressure MIP. The method utilizes MS detection of atomization fragments. A doubly labeled stable isotope of carbon monoxide was added to the MIP and the relative concentrations of recombination products were used as an index of the degree of atomization. Response-data methodology, including analysis of the data by multifactor least-squares methods, was used to present the data in more easily viewed form. The authors demonstrated the dependence of atomization on the support-gas pressure, analyte concentration, and microwave power. In somewhat related work, Gonzalez-Flesca et al. (107E)have studied the production of 0 (5S) metastable oxygen atoms in an MIP. The density of metastable atoms was measured by AAS in the pressure range of 0.2-15 torr. A qualitative analysis of the results showed that the electron temperature plays a more important role in the 0 (%) formation rate than the electron density does. Brake et al. (378) have commented on the dissociation and recombination of oxygen atoms in a microwave discharge and Bauer and Skogerboe (16E) have determined which nonmetal emission wavelengths are excited in MIPs operated in argon, helium, and neon. Of the three proposed mechanisms which may induce excitation of nonmetal species, only sequential ionization and excitation are consistent with the spectral data obtained in argon, helium, and neon. Haas, Carnahan, and Caruso (115E) have recently constructed an internally tuned TWlo(Beenakker type) resonant cavity for moderate power (200-500 W) MIPS. Direct solution nebulization was readily accomplished with this cavity and preliminary studies indicated that detection limits might approach ICP detection limits. Both argon and helium were used as support gases. Holman and Vickers (130E)have used a sealed microtube MIP to determine several elements. Detection limits were reported as about 4 ng for sulfur, chlorine, and bromine and 100 ng for cadmium and tin in 30-pL samples. Both gaseous and liquid samples could be analyzed with the sealed system. Dingjan and deJong (68E) have studied atomic emission spectra from halogen- and sulfur-containing compounds in order to obtain ratio formulas for organic compounds. Results indicated a reasonably good agreement with theoretical values; however, results became worse with increasing number of atoms per molecule. Detection limits ranging from 10 to 200 pg per element were routinely obtained. VanDalen, Kwee, and deGalan (2483) have selectively determined halogens and sulfur in solution by atmospheric pressure helium-MIP coupled with an electrothermal system. Winefordner and co-workers (116E) have speciated inorganic and organometallic compounds in solid biological samples by using thermal vaporization in conjunction with a high-power (ca. 500 W) microwave plasma torch. The plasma temperature was reported to be about 5500 K. The system was used to measure carbon, hydrogen, nitrogen, oxygen, and mercury in orchard leaves and in tuna. Kumamaru Riordan, and Vallee (170E)have described a low-pressure MIP for the determination of zinc in biological samples. The system uses a tungsten filament vaporization device. Wuensch and co-workers (263E) have determined tunsten with a CMP and optimized the CMP by using fadorial design and simplex procedures. Disam et al. (69E)have used a mantle gas stabilized CMP for the determination of various elements in aqueous solutions. Another way to generate a microwave plasma is to use a length of a coaxial transmission line terminated at one end by a short circuit and a t the other end by a capacitive gap. The plasma is obtained by surface wave propagation and has been referred to as a “surfatron”. I n a most important publication, Mermet and co-workers ( I E ) have described a 146R
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helium “surfatron” adapted to the analysis of elements in solution. The aerosol is injected into the plasma by means of an ultrasonic nebulizer with a desolvation system. This paper assesses the analytical performance in terms of detection limits, calibrations, and interferences. Further research with “surfatrons” is clearly indicated but these systems may be quite important in the future. Of related interest, Kat0 et al. (149E) have analyzed radial distribution of plasma parameters in a coaxial-line microwave discharge tube. There is continued interest in interfacing the MIP with chromatographic systems. In addition to the citations in section C of this review, several other reports use chromatography where the primary interest is in the microwave discharge. Chiba et al. (58E)have determined alkylmercury in seawater at extremely low levels with GC-MIP and Chevrier et al. (57E)have developed a novel MIP detector system for chromatography. Genna, McAninch, and Reich (102E)have used a GC-MIP for the analysis of low molecular weight sulfur gases and Huf and Jansen (133E)have designed a helium-MIP generated at atmospheric pressure between electrodes. The design eliminates the need for a silica discharge tube in order to avoid undesirable reactions with the silica wall. Coupling of this MIP with chromatographic systems can easily be accomplished since the capillary inner electrode of the system cannot be considered as a prolongation of the chromatographic column. Jordan and co-workers (142E)have described an all glass-lined, open split, solvent-venting interface for GC-MIP and, in a related publication, Jordan, Krull, and Smith (143E) used their system for determination of catechol derivatives. Heppner (124E) has developed a fascinating system that uses a low-pressure MIP for selective elemental detection in a COMBINED GC-MS system. With this technique, complex organic molecules are converted into a few simple neutral species by passage through the MIP unit. The elements present in the original molecules determine which species will be formed in the MIP. In a hydrogen-rich plasma, oxygen forms CO and HzO, sulfur forms CS2,nitrogen forms HCN, chlorine forms HC1, and carbon forms various hydrocarbons. Identification and quantification of these simple neutral species enable elemental composition information for the ORIGINAL molecules to be determined. The author concludes his paper by stating that the MIP/GC-MS system has not as yet been optimized but that future refinement should considerably improve its operation. This seems (to the authors of this review) a very promising direction for future research. Carnahan and Caruso (49E)have determined bromine and chlorine in high molecular weight halogenated organic compounds. The analyte is desolvated, electrothermally vaporized, and swept into the helium MIP to produce emission from the halogen. The bromine 478.6-nm and the chlorine 479.5-nm lines were used and the method was applied to the determination of bromine in the fire-retardant tris(2,3-dibromopropyl) phosphate. In a related publication, Eckhoff, Ridgway, and Caruso (77E)have developed a polychromator system for multielement determinations by GC with MIP spectrometric detection. Recognizing that the purity of the helium is very important in an atmospheric pressure GC-MIP system, Koirtyohann (157E) has commented on the deleterious effects of impurities such as nitrogen in the helium. Koirtyohann states that even small leaks in the chromatographic system may lead to intolerable impurity levels in the helium. A simple diagnostic test is plasma color: 0.1% nitrogen gives a blue discharge instead of the yellow of pure helium. Molecular structure in the background emission near lines is another indication of a problem. Finally, three recent Ph.D. theses should be mentioned. All of these provide detailed information on interfacing chromatography with the MIP. Carnahan (48E) and Mulligan (199E) (both at the University of Cincinnati) and Estes (82E) (at the University of Massachusetts) have contributed a great deal to this area during their time of study. Spark Discharges. In an important paper, Washburn and Walters (2543) have used high-power positionally stabilized sparks to sample several types of ferrous alloys. The power was increased by sparking at repetition rates up to 1920 sparks/s and peak discharge currents up to 800 A. The signal/background ratios of several spectral lines were measured while the power was varied and the number of coulombs held constant. With this system, it was found possible to decrease analysis time by a factor of 16 while the signal/background
E M I S S I O N SPECTROMETRY
ratio for sample s ectral lines decreased only by a factor of 2.5. This small oss could be easily recovered by spatial masking and gated integration. Walters and Eaton (251E) have an adjustable wave form spark source and argon flow jet to produce a positionally stable spark train. Background, plasma, and ionized electrode emissions are minimized by positioning the mask in front of the central core of the discharge, leaving simpler spectra with less noise to enter the spectrometer. Three- to ten-fold improvementsin signal/noise are reported for common impurities in commercial aluminum alloys. It is also shown that the lost signal due to masking can be recovered by rotating the disk sample and increasing the repetition rate of the source. In a related publication, Olesik and Walters (209E) obtained statistical emission maps of ferrous alloy samples by using stable spark discharge trains for improved sampling resolution. Scheeline and Tran (2293) have recently performed some interesting experiments simulating gap breakdown and dynamic impedance effects in high-voltage spark sources. The importance of diode shunt capacitance in determining gap breakdown behavior is shown. Ageev and co-workers (4E) have studied the temporal development of an electrical discharge and Belyi and co-workers (20E) have provided an analytical description of electric-dischargesintering of metallic powders. Eroshenko and Dem’yanchuk (81E)have studied high-frequency spark discharges used in the spectral analysis of metals and alloys in air and argon and Jurenka (144E)has described the existence of an electron shock structure in the electrical breakdown of nitrogen. Gilbert and co-workers (103E)have performed a detailed Schlieren study of the transition to spark of a discharge in air and in sulfur hexafluoride and Calkin’s thesis (45E) provides useful information on the use of a high-voltage spark emission detector for chromatography. Ehrlich, Stahlberg, and Scholze (78E) have compared atomic emission and spark source MS for the analysis of nonconducting owders. Spark source MS was considered to be more suita le. Kurochkin (I71E) has discussed certain aspects of the effect of the material of the reference electrode on the intensity of lines in a spark discharge. For many years, John P. Walters of the University of Wisconsin has been continuing his pioneering work on s ark discharges. With the departure of Professor Walters rom Wisconsin, it would seem that an era is over. It seems appropriate, therefore, to conclude the spark portion of this review by citing three important Ph.D. theses that have recently come out of Professor Walters’ laboratory. Helmer (122E) has characterized the effluent from a spark discharge, Mathews (187E) has performed a Schlieren study of the postdischarge environment in a high-voltage spark discharge, and Washburn (253E) has investigated high-power spark trains for spectrochemical analysis. These theses are “state of the art” with respect to current spark discharge research. Other Excitation Papers. I n an important publication, Hanle and co-workers (258E)in Germany have used forward scattering spectroscopy (FSS) in a transverse magnetic field for the detection of low concentrations of elements. The basic principle of FSS is as follows: A spectral line source or continuum lamp produces a beam that passes successively through a linear polarizer, a sample cell containing the analyte atoms, and again a linear analyzer. The intensity of the radiation passing through the analyzer in the forward direction (and eventually a spectral selector) is measured with a photodetector. This is discussed in more detail in Alkemade’s recent article (5E). In the FSS system used by Hanle and co-workers (258E), a continuous light source (xenon high-pressure lamp) and a vidicon camera detector system are used. In contrast to emission spectroscopy, the spectra obtained in the FSS system are easy to identify because they only consist of a few resonance lines. Since the sensitivity of the vidicon was very low below 260 nm, the authors confined their measurements to the 260-335 nm region. The authors conclude their paper by stating what needs to be done next to make FSS a viable technique. Strauss, Ferreira, and Human (236E) have investigated the role of metastable argon atoms in the after low plasma of a low-pressure discharge. Results obtained y! time-resolved emission and absorption measurements of several argon and copper spectral lines indicated that low-energy electrons in the afterglow are converted to high-energy electrons via the
P
E
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recombination of electrons with argon ions and the subsequent collisions of pairs of metastable argon atoms. The high-energy electrons excite the sputtered metal atoms to give rise to a slow decaying emission tail in the afterglow. In a related paper, Taylor et al. (2393) have determined moisture and trace impurities in helium by the helium (z3s) flowing afterglow. The afterglow method utilizes the energy transfer reactions of electronically metastable, rare gas atoms to produce light emissions from impurity atoms and molecules in the rare as medium. Wrembel(261E) has used a low-pressure ring-cfischarge for the determination of mercury in several different water and air samples. In a related paper, the same author (2623) has used the low-pressurering-dischargein conjunction with electrodeposition to determine mercury in a variety of water samples. Nakajima et al. (201E)have used shock tube excitation to determine trace metals in copper oxide and Na and Niemczyk (200E) have developed an emission technique based on excitation of atomic species by an energy transfer process from an active nitrogen plasma. The main excitation pathway appears to be a collisional energy transfer from the N2(A32,+)species in the active nitrogen plasma to the atomic species of interest. The authors state that the technique shows an immunity to interferences and has potential for multielement analysis. Radziemski, Cremers, and Loree (222E) have reported on the analytical utility of laser-induced-breakdown spectroscopy (LIBS) for the determination of beryllium in air at extremely low (0.5 ng/g) levels. Approximately linear working curves were obtained over the concentration range 0.5 to 2 X IO4ng/g. Kagawa and Yokoi (146E) have applied a N2 laser to the spectrochemical analysis of microareas. It was found that when the pressure of the surrounding gas is reduced to about 1torr, the plasma induced by the bombardment of N2 laser light yields sharp atomic line spectra with a negligibly low background signal, facilitating quantitative analysis with reasonable precision. Although carbon furnace (CF) devices are normally used in AAS, some workers are using CF-AES for elemental determinations. Gregoire and Chakrabarti (109E)have studied the effect of inserting a pyrolytic raphite platform into a heated graphite atomizer (PE H8A-2100) on the atomic emission of several elements. A comparison of calibration curves obtained with and without the use of the platform showed that although the linear dynamic range is diminished by the use of the platform, atomic emission intensities are increased by as much as 24 times in the most favorable case (aluminum) studied. Ottaway and co-workers are continuing their research in this area. A simultaneous multielement CF-AES system has recently been described (185E)in some detail. Ottaway and co-workers (105E) have also considered the graphite probe and, in a very pragmatic paper, Ottaway and Marshall have used CF-AES for the determination of copper in urine (210E). Jenke and Woodriff (137E) have used CF-AES with a constant-temperature atomizer. Stephens (2353)has derived general formulas to describe the formation of linear magnetooptic signals and Kankare and Stephens (148E)have derived formulas for the signal-to-noise ratio observed when the Voigt effect is used for the detection of atomic species. Comparison of the signal-to-noise ratio given by the Voigt effect with that of the corresponding AAS signal is generally found to favor the latter. Savoie and Pigeon-Gosselin (2283) have used argon and neon spectra for the direct calibration of Raman spectrometers and Winter (2573) has developed an improved monochromator spectral calibration using a tungsten strip lamp. devilliers (67E) has developed a suitable cut film for spectrographic analysis and Burgudjiev and Apostolova (42E) have compared experimental and computed blackening curves of some spectrographic plates used in emission analysis. Of related interest, Kabiel et al. (145E)have described some investigationsbased on theoretical assumptions and experimental results for using the line width as a concentration index in spectrographic analysis of complex materials. Florian and Zimmer (94E) have studied fragments of archeological pearl findings by means of an optimized spectrographic method. By use of statistical tests, the analytical results led to a classification of the pearls into eight color groups. The dominant coloring elements of each group were identified. Berndt and Messerschmidt (23E)have developed an interesting loop method for the determination of various ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
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elements in biological materials. It would seem that this could be used with various plasma devices. Kojima and Iida (158E) have determined metals by automatically triggered digital flame emission spectrometry. Samples (100 pL) were injected into a Teflon funnel connected to the nebulizer. This could be modified for usage with DCPs and ICPs. Townshend and his research associates (now at the University of Hull in England) are continuing their Molecular Emission Cavity Analysis (MECA) studies. MECA Part 22 (2273)discusses the determination of selenium and tellurium bydirect injection into the cavity; MECA Part 23 (8E) describes the determination of nitrate and nitrite after conversion to NO; and MECA Part 24 (7E) is concerned with the determination of germanium, gallium, and thallium. Kouimtzis (165E) has used MECA for the determination of sulfur in selenium and Henden (123E) has attempted to eliminate interferences in the determination of arsenic, antimony, tin, and germanium by using hydride generation techniques with MECA. Burguera et al. (43E) have used MECA to determine organic chlorine containing compounds and Calokerinos and Hadjiioannou (46E) have studied the effect of various experimental parameters on the slope and the deviations from linearity of the S2 calibration curve for thiourea. Cope and Townshend (59E) have developed a phosphorus-sensitive MECA detector for HPLC. The detector consisted of a water-cooled duralumin disk with 40 cavities drilled into its circumference. By changing the wavelength from the HPO 528-nm band to the S2 384-nm sulfur band, the device could also be used as a sulfur detector. Finally, Tzeng and Fernando (2453) have compared two types of flames, the nitrogen-cooled and the argon-cooled hydrogen flame, for the determination of sulfur-containing species in solids by MECA. It was stated that the argon-cooled flame has a much greater sensitivity than the nitrogen-cooled flame for the determination of Sod2-.The nitrogen-cooled flame was found useful in special cases such as the determination of the components of a mixture of S8 and S032-present in a solid matrix.
SELECTED APPLICATIONS Because of space considerations, we have chosen only a few typical applications of emission spectrometry for this section. As indicated previously, reviews and compilations of practical emission spectrochemical applications can be found in recent issues of ARAAS (38A, 49A) and in the Application Reviews of this Journal (3A). Broekaert (IF)has recently published an article considering some applications of the ICP to industrial analytical problems. Garbarino and Taylor ( 1 0 0 have described an automated standardization technique useful for industrial sample analysis and Sabina Slavin and co-workers (36F) have considered the ICP for environmental samples. In an interesting paper, Chandola and Lordello (3F) have used a DC arc spectrographic method to determine various elements in horse hairs. A knowledge of horse hair elemental distribution was stated to be important from the point of view of their production, feeding, and health requirements. Uchida and co-workers (45F) have used a DC arc method for the spectrochemical determination of boron and tungsten in a mineral matrix. The oxidizing influence of CuO buffer was utilized to prevent carbide formation and to increase the volatilization rate of the analysis elements. Two applications of laser-induced breakdown spectroscopy (LIBS) (2233) have recently been reported. Radziemski et al. (34F) have detected beryllium in air at very low concentrations and have also established limits of detection for sodium, phosphorus, arsenic, and mercury in air. In a related paper, Cremers and Radziemski (6F)detected chlorine and fluorine in air by using LIDS. Minimum detectable concentrations of chlorine and fluorine were 8 and 38 ppm (w/w). The precision for replicate sample analysis was reported to be 8% RSD. Ebdon and Cave (48A,8F)have studied different nebulization systems for the ICP and reported analysis results and Headridge (13F)has described ultratrace element detection in nickel alloys. Mainka et al. (24F) have bravely determined plutonium in radioactive products by using an ICP and Pyy et al. (33F) have determined vanadium in workplace air by using a DCP. Norman et al. (31F) have determined uranium in phosphatic materials and Bonner Denton and co-workers (14F) have used an LC-ICP system to determine nucleotides. P I emissions are observed at 213.6 nm and a 148R
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Babington nebulizer is used to aspirate the high percentage salt solutions with 6% efficiency. Maksimov and Rudnevskii (25F) have used a HCD for the spectral analysis of high-pwity substances and Matynov (26F) has described an improved arc discharge excitation system in the spectral analysis of mineral raw materials. Kim and co-workers (208‘) have studied the complexation characteristics of poly(acry1amidoxime) chelating resins by using an ICP and Korte et al. (21F)have determined uranium, thorium, yttrium, zirconium, and hafnium in zincon. Lee (22F) has studied calcium matrix effects in multielement analysis of animal bone by using an ICP and Mazzucotelli et al. (27F) have determined lanthanides in silicates by using an ICP. In addition, plasma emission techniques (usually ICP) have been applied to the analysis of the following materials: alloys (16F, 46F, 48F), autopsy samples (40F),biological materials (41F),cesium chloride (4F), clays (38F), coal (18F),drinking water (39F),fertilizers (17F),fluid inclusions (5F),geological materials UlF, 30F), magnetic bubble garnet films ( 2 3 9 , noble metals (9F),oil refinery products (49F),organic solvents (7F), petroleum products (152A),plant samples (ZF), pond sediment (32F),pottery (12F),sludge, soils, and rocks (15F, 44F, 47F), tea (42F,43F), water (19F, 28F, 29F, 35F). The above papers have been cited in this section of the review since they are primarily application oriented.
MEETIN GS We continue our tradition (18A, 19A) of concluding our review by making some general. comments about important meetings that have been held during the past 2 years and that will be held in the future. Trends and events of importance can certainly be gleaned from meetings. The most important meeting of the past 2 years was certainly the recently held Colloquium Spectroscopicum Internationale-International Conference on Atomic Spectroscopy (CSI/ICAS). The 23rd CSI 10th ICAS joint meeting was held in Amsterdam, Holland from June 26 through July 1,1983. Professor Leo deGalan (Technisiche Hogeschool, Delft) i s to be congratulated for utting together such an impressive program. As previou& mentioned, the abstracts for the meeting have been published in Spectrochimica Acta, Part B (132A) and the same journal has recently published several of the invited talks in a special issue (135A). Of special interest are two talks with fascinating titles: “AtomicPhysics and Atomic Spectroscopy: Mother and Daughter?” by Alkemade (5E) and “Mini, Micro, and High-Efficiency Torches for the ICP-Toys or Tools” by Hieftje (126E). Alkemade’s paper is not exactly a review but rather a speculative look into the future and is certainly highly recommended reading. Hieftje’s paper describes recent work on improving ICP sources. The next CSI/ICAS meeting will be held in Garmisch-Partenkirchen, Germany (south of Munich near the Austrian border) from September 15 through 21, 1985. Information on this meeting may be obtained by writing to CSI XXIV Or anisationsburo, Institut fur Spektrochemie und angewanfte Spektroskopie, Postfach 778, D 4600 Dortmund, West Germany. The 1987 CSI/ICAS meeting is scheduled to be held in Toronto, Canada. Recent American Chemical Society meetings have been held in Las Vegas, NV, Seattle, WA, and Washington, DC. The 1984 meetings are scheduled for St. Louis, MO, and Philadelphia, PA. In addition, the International Congress of Pacific Basin Societies will be held from December 16 through 21 in Honolulu, HI, and will be cosponsored by the ACS. The 1985 ACS meetings are scheduled to be held in Miami Beach, FL, and in Chicago, IL. Recent Pittsburgh Conferences have been held in Atlantic City, NJ, but in 1985 the Pittsburgh Conference moves southwestward to New Orleans, LA. The meeting will be held from February 25 through March 1. In 1986, the Pittsburgh Conference is scheduled to “leap back” to the East Coast and the meeting has been tentatively (we repeat “tentatively”) scheduled for New York City from March 4 through 11. This meeting has become the major analytical trade show in the United States and it is interesting to speculate on where it might (or might not) be meeting during the next few years. The Federation of Analytical Chemistry and Spectroscopy Societies (FACSS) meetings have developed into highly regarded North American scientific meetings held annually in the autumn. FACSS is a consortium of the Association of Analytical Chemists, Chromatography Forum of the Delware
EM I SS I O N SPECTROMETRY
Valley, Division of Analytical Chemistry (ACS), Instrument Society of America Analysis Instrumentation Division, and the Society for Applied Spectroscopy. Beginning in 1984, the Coblentz Society becomes an Associate member of FACSS. The 1984 meeting is scheduled to be held at the Philadelphia Marriott Hotel from September 16 through 21. Further information on the upcoming FACSS meeting can be obtained by writing to one of the authors (P.N.K.) of this review. A limited number of 1983 FACSS Program Booklets are available upon request. The 31st Annual Conference of the Spectroscopy Society of Canada will also be held in the autumn in the Laurentian Mountains (ca. 75 miles or 125 km northwest of Montreal) from October 1through 3,1984. Information on this meeting may be obtained from Dr. James McLaren or Dr. Ralph Sturgeon, National Research Council of Canada, Division of Chemistry, Ottawa K1A OR6, Canada. The 1982 Winter Conference on Plasma Spectrochemistry was held in Orlando, FL, and many important papers from that conference have been published in a special issue of Spectrochimica Acta, Part B (133A). The 1984 Winter Conference was recently held (January 2-6) in San Diego, CA. This was an extremely successful meeting and attracted over 300 conferees. The conference organizer, Professor Ramon L. Barnes, did an excellent job in arranging sessions including several interesting panel sessions held in the evenings. Further winter conferences are planned. The 1985 Winter Conference will shift to Europe and has been scheduled to be held January 7-11 in Leysin, Switzerland. The 1986 Winter Conference will be held from January 3 to 10 (this is a Friday-to-Friday format) on the delightful island of Maui in the Hawaiian Islands. Major sessions on ICP-MS, ICP-AFS, plasma instrumentation and plasma processes are planned. Although these winter conferences are certainly held in superb locations, they are truly hard working conferences with much scientific content. There is a great deal of “up to the minute” scientific information exchanged and it is certainly recommended that those who have an opportunity to attend do so. Information on future winter conferences may be obtained by writing to Professor Ramon M. Barnes, Chemistry Department, University of Massachusetts, Amherst, MA 01003. European readers may obtain information on the 1985 Leysin conference by writing to Dr. J. M. Mermet, SCA-CNRS, BP 22, Vernaison 69390, France. The National Conference on Spectrochemical Excitation and Analysis continues to be held on the island of Martha’s Vineyard (off the coast of Cape Cod, MA) in September. This meeting is a “club type” conference where most of the attendees are actively working with various sorts of plasmas and the papers presented are largely of a very pragmatic nature. Some fundamental papers are presented but commercial type presentations are strongly discouraged. The next meeting for this conference is scheduled for September 4-7,1984. Further information on this meeting can be obtained from Mr. Hank Griffin, Texas Instruments, MS-10-16, 39 Forest Street, Attleboro, MA 02703. The 22nd (1983) Eastern Analytical Symposium (EAS) was held in mid-November a t the Hotel Penta in New York City and was highly successful. The conference chairman, Concetta M. Paralusz, did a magnificent job with all aspects of this meeting. In 1984, the EAS expands to 4 days and will, once again, be held a t the New York Penta Hotel. Meeting dates are November 13-16. Information concerning the 1984 EAS can be obtained from Mr. John D. Johnson, Spectrogram Corp., 385 State Street, North Haven, CT 06473. SAC 83: an international conference and exhibit organized by the Analytical Division of the Royal Society of Chemistry was held in Edinburgh, Scotland, from July 17 to 23, 1983. The June 1983 issue of Analytical Proceedings (published by the Division) contains abstracts of all the papers presented at the meeting. As noted in our previous review, a new British meeting, the Biennial National Atomic Spectroscopy Symposium, has been started. The first meetin was held in Sheffield in 1982 and the second meeting is scieduled to be held in Leeds from July 10 to 13, 1984. Information on this meeting can be obtained from Dr. F. Buckley, Department of Earth Sciences, University of Leeds, West Yorkshire LS2, 9JT, England. Analyticon 84 is a conference sponsored by the Scientific Manufacturers’ Association of Great Britain (SIMA-GB) in association with the Royal Society of Chemistry, the next meeting is scheduled for September 4-6 in
London. Information from Mr. G. C. Young, SIMA-GB, Leicester House, 8 Leicester Street, London Wc2H 7BN, UK. The Annual Symposium on the Analytical Chemistry of Pollutants continues to alternate between the United States and Europe. American meetings are always in Jekyll Island, GA, but the European meetings can be anywhere in Europe. The 14th Annual Symposium on the Analytical Chemistry of Pollutants (joint with the 3rd International Congress on Analytical Techniques in Environmental Chemistry) will be held in Barcelona, Spain, from November 21 to 23, 1984. Meeting information can be obtained from Dr. J. Albaiges, Expoquimia, Avenida Reina Maria Cristana, Barcelona 4, Spain. The 15th Annual Symposium will be held in Jekyll Island, GA, from May 22 to 24, 1985. Another important European meeting is Euroanalysis and the 5th meeting will be held in Cracow, Poland, from August 26 to 31, 1984. It should be noted, in concluding this review, that the Annual Reports on Analytical Atomic Spectroscopy (38A, 49A) lists papers presented at all of the major meetings in a given year. Full author addresses are given allowing interested persons to directly contact the author(s) for more information. This provides a most useful service!
ACKNOWLEDGMENT The following all helped, in various ways, in the preparation of this review and we wish to thank them here: Fred Albright, Ramon M. Barnes, Jan H. Busch, Malcolm S. Cresser, Jose De La Vega, Bernard J. Downey, John R. Edwards, Mary L. Finley, Richard A. Furman, Lawrence C. Gallen, William L. Greene, Jr., Hank Griffin, Howard A. Harner 111, Donna Hershey, Bonnie M. Keliher, Mark Keliher, Claire Keliher, Bonzo Keliher, Dana Keliher, Gordon F. Kirkbright, Oliver G. Ludwig, James J. Markham, Susan B. Markley, Joseph S. McDonnell, Felor Moran, Lydia Moccero, George Norwitz, Ritchard C. Parry, Donna Faust Patterson, Barry L. Sharp, Saul I. Shupack, and Andrew T. Zander. LITERATURE CITED BOOKS AND REVIEWS
(1A) Albaiges, J., Ed. “Analytical Techniques in Environmental Chemistry-2”; Proceedings of the Second International Congress, Barcelona, Spain, November 1981; Pergamon Press: New York, 1982. (2A) Alkemade, C. Th. J.; Hollander, T. J.; Snelleman, W.; Zeegers, P. J. Th. “Metal Vapors in Flames”; Pergamon Press: New York, 1982. (3A) Applicatlon Reviews Anal. Chem. 1983, 55, 1R-313R. (4A) Atomlc Absorption and Emission Spectrometry Abstracts; PRM Science and Technology Agency, Ltd.: London, United Kingdom. (5A) Atkins, P. W. Chem. Brit. 1983, 19, 122-123. (6A) Barker, P. G. “Computers in Analytical Chemistry”; Pergamon Press: New York, 1983. (7A) Barnes, R. M. Philos. Trans. R . SOC., London, Ser. A 1982, 305, 499-508. (8A) Barnes, R. M., Ed. “Developments in Atomic Plasma Spectrochemical Analysis”; Wiley: New York, 1982. (9A) Barnes, R. M. ICP Inf. Newsl. 1983, 8 , 171-172. (10A) Barnes, R. M. ICP I n f . Newsl. 1983, 9 , 1-2. (11A) Bastien, F. NATOAdv. Sci. Inst. Ser., Ser. 8 1983, 89, 267-291. (12A) Benll, H. ICP I n f . News/. 1982, 8 , 315-316. (13A) Benli, H. Spectrochlm. Acta, Part8 1983, 38, 81-91. (14A) Bezur, L.; Marshall, J.; Ottaway, J. M.; Fakhrul-Aldeen, R. Analyst (London) 1983, 108, 553-572. (15A) Boksenberg, A. fhllos. Trans. R . SOC.London, Ser. A 1982, 307, 531-548. (16A) Borman, S. A., Ed. “Instrumentation in Analytical Chemistry”; ACS: Washington, DC 1982. (17A) Boumans, P. W. J. M. Spectrochlm.Acta, Part8 1983, 38, 665-668. (18A) Boyko, W. J.; Keliher, P. N.; Malloy, J. M. Anal. Chem. 1980, 52, 53R-69R. (lgA) Boyko, W. J.; Keliher, P. N.; Patterson, J. M., I11 Anal. Chem. 1982, 54, 188R-203R. (20A) Broekaert, J. A. C. ICP I n f . Newsl. 1983, 9 , 413-415. (21A) Broekaert, J. A. C. Spectrochlm. Acta, Part 8 1982, 37, 359-369. (22A) Broekaert, J. A. C. Spectrochim. Acta, Part 8 1982, 3 7 , 727-732. (23A) Brown, R. D.”Introduction to Chemlcal Analysis”; McGraw-Hill: New York, 1982. (24A) Browner, R. F. Trends Anal. Chem. 1983, 2 , 121-124. (25A) Busch, K. W.; Benton, L. D. Anal. Chem. 1983, 55, 445A-460A. (26A) Calokerlnos, A. C.; Townshend, A. frog. Anal. A t . Spectrosc. 1982, 5,63-77. (27A) Cantle, J. E., Ed. “Atomic Absorptlon Spectroscopy”; Elsevier Scientific Publlshlng Company: New York, 1982. (28A) Caroli, S. frog. Anal. At. Spectrosc. 1983, 6 , 253-292. (29A) Caroli, S.; Delle Femmlne, P.; Aiimonte, A,; Petrucci, F.; Vlolante, N. Spectrosc. Lett. 1982, 15, 303-312. (30A) Caulcutt, R.; Boddy, R. ”Statlstics for Analytical Chemists”; Chapman and Hall: London, 1983. ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
149R
EMISSION SPECTROMETRY (31A) Chakrabartl, C. L. "Progress in Analytical Atomlc Spectroscopy, Volume 4"; Pergamon Press: New York, 1982. (32A) Chakrabarti, C. L. "Progress In Analytical Atomic Spectroscopy, Volume 5";Pergamon Press: New York. 1983. (33A) Chalmers, R. A. "Gains and Losses"; Pergamon Press: New York, 1983 (Talanta 1982, 29, 963-1055). (34A) Cooper, J. "The Minlcomputer In the Laboratory, 2nd Edltlon"; Wiley: New York, 1982. (35A) Cope, M. J.; Klrkbright, G. F. J . Phys. E 1983, 76, 581-590. (36A) Corney, A. Philos. Trans. R. SOC. London, Ser. A 1982, 307, 573-590. (37A) Cresser, M. S. Prcg. Anal. A t . Spectrosc. 1982, 5, 35-62. (38A) Cresser, M. S.,Sharp, B. L., Eds. "Annual Reports on Analytical Atomic Spectroscopy" (Reviewing 1961); The Royal Society of Chemistry: London, 1982; Vol. 11. (39A) Date, A. R.; Gray, A. L. Spectrochlm. Acta, Part8 1983, 38, 29-37. (40A) Date, A. R. Trends Anal. Chern. 1983, 2 , 225-230. (41A) Denney, R. C. Chem. Brit. 1983, 19, 298-301. (42A) Denney, R. C. "A Dlctlonary of Spectroscopy"; Macmillan, New York, 1982. (43A) DeVilllers, D. B. Spectrochlm. Acta, Part 8 1983, 38, 881-884. (44A) Duiey, W. W. "Laser Processing and Analysis of Materials"; Plenum Press: New York, 1983. (45A) Dumke, J.; Niemann, E. G. Rev. Scl. Insfrum. f982, 53, 194-196. (48A) Duursma, R. P. J.; Steigstra, H.; Logchies, R. G.; Smit, H. C. Anal. Chlm. Acta 1982, 144, 13-23. (47A) Ebdon, L. "An Introduction to Atomic Absorptlon Spectroscopy-A Self Teaching Approach"; Heyden and Sons: London ana Philadelphia, 1982. (48A) Ebdon, L.; Cave, M. R. Ana/yst (London) 1982, 107, 172-178. (49A) Ebdon, L., Jackson, K. W., Ed. "Annual Reports on Analytlcal Atomic Spectroscopy" (Reviewlng 1982); The Royal Society of Chemistry: London, 1983; Vol. 12. (50A) "Elemental Analysis System is Useful Hybrid Techniaue" (non-authored report) Chem. Eng. News 1983, (March 21), 40. (51A) Evans, T. R. "Applicatlon of Lasers to Chemical Problems"; Wiley: New York, 1982. (528) Facchetti, S.,Ed. "Analytlcai Techniques for Heavy Metals in Biological Fluids"; Elsevler Science Publishing Company: New York, 1983. (53A) Falk, H. Prog. Anal. At. Spectrosc. 1982, 5 , 205-241. (54A) Farago, P. J. Chem. Brit. 1982, 78, 40-43. (55A) Fassel, V. A. Recent Adv. Anal. Spectrosc., Proc. Int. Conf. At. Spectroscopy, K. Fuwa, Ed. 1982, 1-14 (see ref 57A). (56A) Fassel, V. A. ICP Inf. News/. 1982, 8 , 69-75. (57A) Fuwa, K. "Recent Advances In Analytlcal Spectroscopy-Proceedings of the 9th International Conference on Atomic Spectroscopy and the 22nd Colloquium Spectroscopicum Internatlonale" (Held in Tokyo, Japan from September 4-8, 1981), Pergamon Press: New York, 1982. (58A) Garetz, B. A.; Lombardl, J. R. "Advances In Laser Spectroscopy"; Wiley-Heyden: New York, 1982. (59A) Gegus, E.; Zlmmer, K. ICP I n f . Newsl. 1983, 9 , 299. Brenner, I.B. ICP. Inf. News/. 1983, 8 , 566-572. (60A) Goldbart, 2. I.; (61A) Grasshoff, K.; Ehrardt, M.; Kremilng, K. "Methods of Seawater Analysis"; Verlar Chemie International Inc.: Deerfleld Beach, FL, 1983. (62A) Gray, A. L.; Date, A. R. Inl. J . Mass Spectrom. Ion Phys. 1983, 46, 7-10. (63A) Greenfield, S. ICP I n f . News/. 1983, 9 , 303-306. (64A) Gustavsson, A. ICP Inf. News/. 1983, 9 , 283-288. (65A) Haraguchi, H. ICP Inf. News/. 1982, 8 , 91-98. (66A) Heller, S. R., Potenzone, R., Jr., Eds. "Computer Applicatlons in Chemistry"; Elsevier Science Publishing Company: New York, 1983. (67A) Horlick, G.; Hall, R. H.; Yuen, W. K. Fourier Transform Infrared SpectroSC. 1982, 3 , 37-81. (68A) Houk, R. S.;Fassel, V. A,; Flesch, G. D.; Svec, H. J.; Gray, A. L.; Taylor, C. E. Anal. Chem. 1980, 52, 2283-2289. (69A) Hughes, H. Analyst (London) 1983, 108, 286-292. (70A) Hutley, M. C. "Dlffraction Gratings"; Academlc Press: New York, 1982. (71A) "ICP Hyphenated Technlques for Elemental Detection" (non-authored report) Anal. Chem. 1983, 55, 611A-612A. (72A) Imal. S. ICP I n f . News/. 1982, 8 , 85-91. (73A) Isenhour, T. L. Anal. Chem. 1983, 55, 824A-834A. (74A) James, E. B. Chem. in Brit. 1982, 18, 620-624. (75A) Johnson, R. E. "An Introduction to Atomic and Molecular Coilislons"; Plenum Press: New York, 1982. (76A) Kahn, H. L. Ind. Res. Dev. 1982, 24 (2), 156-160. (77A) Kahn, H. L. Ind. Res. Dev. 1982, 24 (3), 150-153. (78A) Kahn, H. L.; Chase, D. S. Am. Lab. 1983, 15 (e), 46-55 ("Tomorrow's fish is wrapped In the paper which contains today's wlsdom", Translated by Margaret Fernald, Weston High School, Weston, MA). ( 7 9 4 Katz, S. A.; Jenniss, S. W. "Regulatory Compliance Monltoring by Atomic Absorption Spectroscopy"; Verlag Chemle International Inc.: Deerfield Beach, FL, 1983. (80A) Kawaguchi, H. ICP Inf. Newsl. 1983, 9, 299-303. (81A) Keliher, P. N. ICP Inf. News. 1982, 8 , 167-171. (82A) Kirkbright, G. F. Pure Appl. Chem. 1982, 54, 769-788. (83A) Kolbe, W. F.; Leskovar, 6. Rev. Scl. Instrum. 1982, 53, 769-775. (84A) Kopanica, M.; Stara, V. I n "Comprehenslve Analytical Chemistry, Volume XVI 1"; Svehla, G., Ed.; Elsevier Science Publishing Company: New York, 1983. (85A) Kubota, M. Bunsekl 1983, 5, 345-352. (86A) Kubota, M. ICP Inf. News/. 1982, 8 . 76-85. (87A) Kuehn, D. G.; Smulders. J.; Chanln, L. M. Rev. Scl. Instrum. 1982, 53, 102. (88A) Learner, R. L. M. J. Phys. 8 1982, 15, L891-L895.
159R
ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
(89A) Leyden, D. E.; Cronln, J. T.; Ellls, A. T. Int. J . Envlron. Anal. Chem. 1982, 7 1 , 105-115. (9OA) Loveil, D. J. "Optical Anecdotes"; SPIE Bellingham, WA, 1981. (91A) Lowe, R. M.; Wiilis, J. 8. ICP f n f . News/. 1982, 8 , 313-314. (92A) Lowdln, P. O., Ohm, Y., Eds. "Proceedings of the International Symposium on Atomic, Molecular, and Solid-state Theory, Collision Phenomena and Computational Quantum Chemistry"; Wlley: New York, 1982. (93A) Magyar, B. "Guide-Lines to Planning Atomic Spectrometric Analysis"; Elsevier Science Publlshing Company: New York, 1982. (94A) Marcuse, D. "Light Transmission Optlcs-2nd Edition"; Van Nostrand Relnhold Company: New York, 1982. (95A) Marr, I.L.; Cresser, M. S."Environmental Chemical Analysis"; Blackie and Son: Glasgow, Scotland, United Kingdom, 1962. (96A) Marshall, A. G., Ed. "Fourier, Hadamard and Gilbert Transforms in Chemlstry"; Plenum Press: New York, 1982. (97A) McCrory-Joy, C.; Joy, D. C. Talanta 1983, 30, 299-315. (98A) MacDonald, J. C. Am. Lab. 1983, 15(9), 90-98. (99A) McLaren, J. ICP I n f . Newsl. 1983, 9 , 416-418. (100A) McGeorge, S.W.; Saiin, E. D. Can. J. Spectrosc. 1982, 27, 25-36. (10IA) Mermet, J. M. ICP Inf. News/. 1983, 9 , 415-416. (102A) Mermet, J. M.; Hubert, J. Prog. Anal. At. Spectrosc. 1982, 5 , 1-33. (103A) Miller, F. A. Appl. Spectrosc. 1983, 37, 219-225. (104A) Minczewski, J.; Chwastowska, J.; Dybczynski, R. "Separation and Preconcentration Methods in Inorganic Trace Analysis"; Wiley: New York, 1982. (105A) Mlttleman, M. H. "Introductlon to the Theory of Laser-Atom Interactions"; Plenum Press: New York, 1982. (106A) Nakahara, T. Prog. Anal. At. Spectrosc. 1983, 6, 163-223. (107A) Newman, E. J. Lab. Pract. 1983, 32, 37-38. (108A) O'Haver, T. C. J . Pharm. Homed. Anal. 1983, 1 , 3-9. (109A) Ohno, K.; Morokuma, K. "Quantum Chemlstry Literature Data Base"; Elsevier Science Publishlng Company: New York, 1982. (IIOA) Ohtake, Y. Oputoronlkusu 1982, 9 , 11-19. (111A) Ottaway, J. M.; Ure, A. M. "Practical Atomic Absorption Spectroscopy"; Pergamon Press: New York, 1983. (112A) Parsons, M. L.; Major, S.;Forster, A. R. Appl. Spectrosc. 1983, 37, 411-418. (113A) Phelps, F. M., I11 "MIT Wavelength Tables, Volume 2. Wavelengths by Elements"; The MIT Press: Cambridge, MA, 1982. (1 14A) Reif-Lehrer, L. "Writing a Successful Grant Application"; Science Books International, Knc.: Boston, MA, 1982. (115A) Rentzepls, P. M. Science 1982, 218, 1183-1189. (116A) Rev. Anal. Chem. 1983, 7 , 1-192. (117A) Risby, T. H.; Talmi, Y. CRC Crlt. Rev. Anal. Chem. 1983, 14, 231-265. (118A) Robin, J. P. Prog. Anal. At. Spectrosc. 4982, 5 ,79-110. (119A) Robinson, J. W. "Undergraduate Instrumental Analysis"; Marcel Dekker: New York, 1982. (120A) Rossi, G. ICP Inf. News/. 1983, 9 , 345-347. (121A) Ruzicka, J. Anal. Chem. 1983, 55, 1040A-1053A. (122A) Ruzicka, J.; Hansen, E. H. Anal. Chem. Acta 1983, 145, 1-15. (123A) Sacks, R. D.; Goldberg, J. M.; Suh, S.Y. Prog. Anal. At. Spectrosc. 1982, 5 , 111-151. (124A) Sam-Medel, A.; Rora, R. R.; Perez-Conde, C. Analyst (London) 1983, 108, 204-212. (125A) SAVANT (Sloane Audio Visuals for Analysis and Training), Post Office Box 3670, Fullerton, CA 92634. (126A) Sermin, D. F. Laborpraxis 1983, 7 , 696-698. (127A) Shutian, L. Rev. Anal. Chem. 1983, 7 , 153-192. (128A) Skidmore, P. R.; Greetham, S. S. Analyst (London) 1983, 108, 171-177. (129A) Skoog, D.; West, D. "Fundamentals of Analytical Chemistry-4th Edition"; W. B. Saunders Company: Philadelphia, PA, 1982. (130A) Slavin, W. Anal. Chem. 1982, 54, 685A-694A. (131A) Spectrochlm. Acta, Part 8: Special Issue-Spectrochemical Anaiysis in the U.S.S.R. 1981, 36 (no. 12), 1139-1250. (132A) Spectrochim Acta, Part 8: Special Issue-Abstracts of the 23rd CSI/lOth ICAS Meetlng, Amsterdam 1983, Supplement, 1-410. (133A) Spectrochim. Acta, Part 8: Speclal Issue-Plasma Spectrochemistry Proceedings of the 1982 Wlnter Conference on Plasma Spectrochemlstry hew in Orlando, Florida January 4-9, 1982; Ramon M. Barnes, Guest Editor, 1983, 38 (no. 1 and 2), 1-445. (134A) Spectrochlm. Acta, Parf 8: Special Issue-Atomic Spectroscopy in the Netherlands and Countries Historlcally Linked to the Netherlands: Belgium and South Africa 1983, 38 (no. 5 and a), 663-975 (This issue dedicated to Paul W. J. M. Boumans on the occasion of the 23rd CSI and to celebrate his 25th anniversary in atomic spectroscopy). (135A) Spectrochlm . Acta, Part 8: Speclal Issue-Analytical Spectroscopy: A Polychrome Branch of Science 1983, 38 (no. 11 and 12), 1373-1568. (136A) Stewart, K. K. Anal. Chem. 1983, 55, 931A-940A. (137A) Strasheim, A. Spectrochlm. Acta, Part 8 1982, 37, 219-258. (138A) Thompson, M.; Walsh, J. N. "A Handbook of Inductively Coupled Plasma Spectrometry"; Methuen, Inc.: New York 1983 (European Publisher Blackie and Son, Glasgow, Scotland, United Kingdom). (139A) Tolmacher, Y. A. Khlrn. Plazmy 1982, 9 , 80-100. (140A) Travis, J. C.; Turk, 0. C.; Green, R. B. Anal. Chem. 1982, 54, 1006A-1018A. (141A) Tsalev, D. L.; Zaprianov, 2 . K. "Atomic Absorption Spectrometry in Occupatlonai and Environmental Health Practice-Volume I"; CRC Press: Boca Raton, FL, 1983. (142A) Turk, C.; Kirkman, J. "Effective Writing"; Chapman and Hall: London. 1982.
.
EMISSION SPECTROMETRY (143A) Ullman, A. H. Anal. Chem. 1982, 54, 780A-785A. (144A) Valkovlc, V. “Trace Elements In Coal-Volume I”; CRC Press: Boca Raton, FL, 1983. (145A) Valkovlc, V. “Trace Elements in Coal-Volume 11”; CRC Press: Boca Raton, FL, 1983. (146A) Van Grleken, R. Anal. Chim. Acta I982, 143, 3-34. (147A) Van Loon, J. C., Ed. “Chemical Analysis of Inorganic Constituents of Water”; CRC Press: Boca Raton, FL, 1982. (148A) Wather, H. NATO Adv. Scl. Inst. Ser., Ser. B 1983, 94, 293-324. (149A) Watson, A. E. ICf I n f . Newsl. 1983, 9 , 411-413. (150A) Weber, M. J., Ed. “CRC Handbook of Laser Science and Technology, Volume 1: Lasers and Masers”; CRC Press: Boca Raton, FL, 1982. (151A) Weber, M. J., Ed. “CRC Handbook of Laser Science and Technology, Volume 2: Gas Lasers”; CRC Press: Boca Raton, FL, 1982. (152A) Wllllams, R. W.; Mason, P. R. R o c . Inst. Pet., London 1982, 215-226. Krug, F. J.; Rels, 8. F.; Bruns, R. (153A) Zagatto, E. A. G.; Jaclntho, A. 0.; E.; Araujo, M. C. U. Anal. Chlm. Acta 1983, 145, 169-178. (154A) Zander, A. T. Ind. Res. Dev. 1982, 24 (2), 146-150. (155A) Zander, A. T. Ind. Res. Dev. 1982, 24 (3), 142-147. (156A) Zll’bersteln, Kh. I.ICP I n f . Newsl. 1983, 8 , 445-452. (157A) Zlmmer, K.; Hetal, Gy.;Florian, K. frog. Anal. At. Spectrosc. 1982, 5 , 341-467. (158A) Zolotov, Yu. A.; Bodnya, V. A.; Zagruzina, A. N. CRC Crlt. Rev. Anal. Chem. 1982, 14, 93-174.
SPECTRAL DESCRIPTIONS AND CLASSIFICATIONS (18) Ahmad. S. A.; Saksena, G. D. Spectrochim. Acta, Part B 1983, 38, 1065- 1066. (28) Ahmad, S. A.; Venugopalan, A,; Saksena, G. D. Spectrochlm. Acta, Part 8 1982, 37, 837-45. (38) Ahmad, S. A.; Venugopalan, A.; Saksena, G. D. Spectrochim. Acta, Part B 1983, 38. 639-844. (48) Ahmad, S. A.; Venugopalan, A,; Saksena, G. D. Spectrochim. Acta, Part B 1983, 38, 1115-1124. (58) Amln, S. R. J . Opt. SOC.Am. 1983, 73, 862-863. (68) Andrac. H. J. Nucl. Instrum. Methodfhys. Res. 1982, 202, 123-137. (78) Arbuzov, V. A. Opt. At. Flz. (Izd. 2-9, fereab. Dop.) 1983, 218-243. (88) Arbuzov, V. A. Opt. At. Fir. (Izd. 2 - 8 , fereab. Dop.) 1983,423-460. (98) Balrd, K. M. fhilos. Trans. R . SOC. London, Ser. A 1982, 307, 673-683. (108) Bentzen, S. M.; Nielson, U.; Poulsen, 0. J. Opt. SOC.Am. 1982, 72, 1201-1210. (118) Berry, H. G.; Hass, M. Annu. Rev. Nucl. Part. Scl. 1982, 32, 1-34. (128) Blrnbaum. G.; Gulllot, 8.; Bratos, S. A&. Chem. fhys. 1982, 51, 49-112. (138) Blackwell. D. E.; Menon, S. R. L.; Petford, A. D. Mon. Not. R . Astron. SOC.1982, 201, 603-810. (148) Blackwell, D. E.; Menon, S. R. L.; Petford, A. D. Man. Not. R . Astron. SOC.1983,204,883-890. (158) Blackwell, D. E.; Menon, S. R. L.; Petford, A. D.; Shallls, M. J. Mon. Not. R . Astron. SOC.1982. 201, 811-817. (168) Blackwell, D. E.; Petford, A. D.; Shallls, M. J.; Leggett, S. Mon. Not. R . AStrOn. SOC.1982, 199, 21-31. (178) Blackwell, D. E.; Petford, A. D.; Shallis, M. J.; Simmons, G. J. Mon. Not. R . AStrOn. SOC. 1982, 199, 43-51. (188) Blackwell, D. E.; Petford, A. D.; Simmons, G. J. Mon. Not. R . Astron. SOC.1982, 201, 595-802. (198) Boumans, P. W. J. M. Spectrochim. Acta, Part B 1983, 38, 747-776. (208) Chaghtal, M. S. 2.; Ahmad, T. Report INDC(IND)-31/GA, 1982; 81 pp. (218) ChlMs, W. J.; Cok, D. R.; Goodman, L. S. J . Opt. SOC.Am. 1983, 73, 151-155. (228) Chung, S.; Lin, C. C.; Fisher, C. F.; Lee, E. T. P. J . Chem. fhys. 1982, 76, 498-501. (238) Coeizer, F. J.; Koize, P. 8.; Van der Westhulzen, P. Nucl. Intrum. Methods fhys. Res. 1982, 202, 19-23. (248) Coetzer, F . J.; Mostert, F. J.; Van der Westhulzen, P. Spectrochlm. Acta, Part 6 1983, 38, 885-887. (258) Corllss, C.; Sugar, J. J . fhys. Chem. Ref. 1982, 11, 135-241. (288) Cowley, C. R. Mort. Not. R . Astr. SOC.1983, 202, 417-425. (278) Cowley, C. R.; Corliss, C. H. Mont. Not. R . Astr. SOC.1983, 202, 651-659. (288) Czernichowskl, P. A.; Chapelle, J. Acta fhys. Pol. A 1983, A83, 67-75. (298) Dlmtrljevlc, M. S.; Konjevlc, N. J. Quant. Spectrosc. Radiat. Transfer 1983, 30, 45-54. (308) Eicher, C. A.; Allen, L. fhys. Lett. A 1983, 93A, 119-120. (318) Engleman, R., Jr.; Palmer, 8 . A. J. Opt. SOC. Am. 1983, 73, 694-701. (328) Fonseca, V.; Campos, J. J . fhys. B 1982, 15, 2349-2355. (338) Fonseca, V.; Ortlz, M.; Campos, J. J . Opt. SOC. Am. 1983, 73, 1070- 1073. (348) Frank, P.; Krauss, L. Spectrochim. Acta, Part B 1982, 37, 281-291. (358) FuJimoto, T.; Goto, C.; Fukuda, K. fhys. Ser. 1982, 26, 443-450. (368) Ganas, P. S. fhys. Lett. A 1982, 87A. 394-395. (378) Gelfand, J. J. Report N-82-25048, 1982. (388) Goly, A.; Rakotoarijlmy, D.; Wenlger, S. J. Quant. Spectrosc. Radlat. Transfer 1983, 30, 417-431. (398) Goly, A.; Wenlger, S. J. Quant. Spectrosc. Radlat. Transfer 1982, 28. 389-391. (408) Greene, R. L. J. Quant. Spectrosc. Radiat. Transfer 1982, 27, 839-651. (418) Greene, R. L. J. Quant. Spectrosc. Radiat. Transfer 1983, 30, A.-9 -9 - A.i .3- . (428) Halstead, J. A.; Reeves, R. R. J. Quant. Spectrosc. Radiat. Transfer 1982, 28, 289-298.
(438) Harmin, D. A. fhys. Rev. Lett. 1982, 49, 128-131. (448) Hartmetz, P.; Schmoranzer, H. fhys. Lett. A 1983, 93A, 405-408. (458) Helllg, K. Spectrochlm. Acta, Part B 1982, 37, 417-455. (488) Hollander, Tj.; de Leeuw, A.; ter Horst, E. Spectrochim. Acta, Part B 1983, 38, 691-895. (478) Hubeny, I.; Oxenlus, J. J . Quant. Spectrosc. Radlat. Transfer 1983, 2 9 , 477-493. Oxenlus, J. J. Quant. Spectrosc. Radiat. Transfer 1983, (488) Hubeny, I.; 2 9 , 495-506. (498) Humllcek, J. J. Quant. Spectrosc. Radiat. Transfer 1983, 2 9 , 125- 130. (508) Iglesias, C. A. J. Quant. Spectrosc. Radiat. Transfer 1983, 30,
55-60. (518) Inoue, G.; Setser, D. W.; Sadeghi, N. J. Chem. fhys. 1982, 76, 977-983. (528) Jamelot, G.; Jaegle, P.; Carillon, A. Ann. fhys. (Paris) 1982, 7 , 399-416. (538) Joensson, G.; Levlnson, C.; Svanberg, S.; Wahlstroem, C. G. fhys. Lett. A 1983, 93A, 121-123. (548) Julienne, P. S. fhys. Rev. A 1982, 26, 3299-3317. (55B) Kawaguchl, H.; Oshio, Y.; Mlzuike, A. Spectrochim. Acta, Part 6 1982, 37, 809-816. (568)Kelly, R. L. Report ORNL-5922, Order No. DE83002582, 1982; 408 pp. (578) Kleppner, D. “Interact. Laser-Plasma, Les Houches, (Ec. Ete Phys. Theor.), 34th. 1960”; Balln, R., Adam, J.-C., Eds.; North Holland: Amsterdam, 1982; pp 733-734. (588) Knight, R. D. fhys. Rev. Lett. 1982, 48, 792-795. (598) Knystautas, E. J. I€€€, Trans. Nuci. Sci. 1983, NS-30, 987-990. (80B) Kolzuml, H.; Olhsi, K.; Yasuda, K. Appl. fhys. Lett. 1982, 40, 122- 123. (818) Kono, A.; Hattori, S. J . Opt. SOC. Am. 1982, 72, 601-605. (628) Kono, A.; Hattorl, S. J. Quant. Spectrosc. Radiat. Transfer 1982, 28, 383-387. (638) Kotllkov, E. N.; Tokarev, V. I.Opt. Spetrosk. 1982, 53, 806-609. (648) Kwela, J.; Zachara, S. J. Opt. SOC. Am. 1983, 73, 1074-1078. (658) Kwlatkowskl, M.; Mlcall, G.; Werner, K.; Zlmmermann, P. J. fhys. B 1982, 15, 4357-4381. (868) Laklcevlc, I.S.;Puric, J.; Cuk, M. Phys. Lett. A 1982, 19A, 19-21. (678) Le Gouet, J. L. Ann. fhys. (Paris) 1983, 8, 169-174. (888) Llngaard, A,; Mannevlk, S.;Jelenkovic, 8.; Veje, E. Nucl. Instrum. Methods fhys. Res. 1982, 202, 59-65. (698) Magazzu, A.; Plrronello, U.; Strazzuilia, G. J . Quant. Spectrosc. Ra diat. Transfer 1983, 2 9 , 375-378. (708) Martin, W. C.; Zaubas, R. J . fhys. Chem. Ref. Data 1983, 12, 323-380. (718) Martlnsor, I . Nucl. Instrum. Methods fhys. Res. 1982, 202, 1-12. (728) Mlchaud, K.; Mermet, J. M. Spectrochim. Acta, Part B 1982, 37, 145- 184. (738) Mohamed, K. A. J. Quant. Spectrosc. Radiat. Transfer 1983, 80, 225-228. (748) Moscatelll, F. A.; Redi, 0.; Schonberger, P.; Stroke, H. H.; Wiggens, R. L. J . Opt. SOC.Am. 1982, 72, 918-922. (758) Moscatelll, F. A.; Redi, 0.; Schonberger, P.; Stroke, H. H.; Wlggens, R. L. J . Opt. SOC.Am. 1983, 73, 158-159. (768) Murakawa, K. Kaku Yugo Kenkyu, Bessatu 1982, 47, 231-234. (778) Musiol, K.; Jones, D. W.; Wlese, W. L. J. Quant. Spectrosc. Radiat. Transfer 1983, 29, 321-327. (788) Musiol, K.; Stanek, K. Spectrochim. Acta, Part B 1983, 3 8 , 1067- 1070. (798) Pegg, D. J.; Galllard, M. L.; Bingham, C. R.; Carter, H. K.; Mlekodaj, R. L. Nucl. Instrum. Methods fhys. Res. 1982, 202, 153-158. (808) Peterkop, R. fhys. Lett. B 1982, 90A, 182-184. (818) Petersson, S. fhys. Scr. 1982, 26, 296-318. (828) Pinnlngton, E. H.; Bahr, J. L.; Irwin, D. J. G.; Kernahan, J. A. Nucl. Instrum. Methods fhys. Res. 1982, 202, 67-71. (838) Planarosa, P.; Gagne, J. M.; Larln, G.; Saint-Dlzler, J. P. J. Opt. SOC. Am. 1982, 72, 392-394. (848) Prost, M. M. Spectrochim. Acta, Part B 1982, 37, 541-570. (858) Rudolph, J.; Helbig, V. J . fhys. B 1982, 15, L599-L602. (86B) Rudolph, J.; Helblg, V. fhys. Lett. A 1982, 89A, 339-341. (87B) Russo, R. E.; Hleftje, G. M. Appl. Specfrosc. 1982, 36, 92-99. (888) Schmieder, R. W. J . Opt. SOC.Am. 1982, 72, 593-600. (89B) Schnehage, S. E.; Danzamnn, K.; Kunnemeyer, R.; Kock, M. J. Quant. Spectrosc. Radiat. Transfer 1983, 29, 507-516. (908) Schneider, R. T.; Roxey, T. E. Appl. Opt. 1982, 21, 4204-4206. (918) Shlmizu, T. Oyo Butsuri 1982, 51, 435-437. (928) Sulzmann, K. G. P. J. Quant. Spectrosc. Radiat. Transfer 1983, 29, 89-92. (938) Tachlbana, K.; Harlma. H.; Urano, Y. J. Phys. B 1982, 15, 3169-3178. (948) Tang, 2 . Huaxue Tongbao 1982, 697-700. (958) Uchlda, H.; Koslnski, M. A.; Omenetto, N.: Winefordner, J. D. Spectrochim. Acta, Part B 1983, 38, 529-532. (988) Ueda, K.; Karasawa, M.; Fukuda, K. J . fhys. SOC.Jpn. 1982, 51, 2267-2270. (978) Verges, J. Ann. fhys. (Paris) 1983, 8 , 187-198. (988) Verolalnen, Y. F. Usp. Fir. Nauk 1982, 137, 305-338. (99B) Verolalnen, Y. F.; Piekhotkina, G. A.; Privalov, V. I.Opt. Spektrosk. 1982, 53, 981-984. (1008) Waiters, P. E. Spectrochim. Acta, Part B 1983, 38, 889-898. (1018) Wiese, W. L.; Konjevlc, N. J. Quant. Spectrosc. Radiat. Transfer 1982, 2 8 , 185-198. (1028) Wllllams, R. R.; Coleman, G. N. Spectrochim.Acta, Part6 1983, 38, 1171-1 178. ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
151 R
EMISSION SPECTROMETRY (1038) Wujec, T.; Weniger, S. J . Quant. Spectrosc. Radiat. Transfer 1982, 28, 113-129. (1048) Zlmmermann, P. Nuci. Instrum. Methods Phys. Rev. 1982, 202, 167- 169. INSTRUMENTATION
(IC) Alexander, P. W.; Flniayson, R. J.; Smythe, L. E.; Thalib, A. Analyst (London) 1982, 707,1335. (2C) Adams, M. J.; Mitchell, M. C.; Ewen, 0. J. Anal. Chlm. Acta 1983, 749, 101-106. (3C) Anderson, R. D.; Munter, R. C. Spectrochim. Acta, Part B 1983, 38, 15 1-1 55. (4C) Azlz, A.; Broekaert, J. A. C.; Leis, F. Spectrochlm. Acta, Part B 1982, 37,369-379. (5C) Aziz, A.; Broekaert, J. A. C.; Leis, F. Spectrochim. Acta , Part B 1982, 37,381-389. (6C) Barnes, R. M.; Fernando, L.; Jing, L. S.;Mahantl, H. S. Appl. SpectrOSC. 1983, 37,389-395. (7C) Barnes, R. M.; Fodor, P. Spectrochim. Acta, Part B 1983, 38, 1191-1202. (8C) Barnes, R. M.; Mahanti, H. S. Appl. Spectrosc. 1983, 37, 17-19. (9C) Barnhart, S.G.; Waiters, J. P. Appl. Spectrosc. 1983, 37, 537-539. (1OC) Barrett, P.; Fisher, C. G., 111; Barnard, T. W. At. Spectrosc. 1982, 3 , 45-47. (1 1C) Bliliet, H. A. H.; vanDalen, J. P. J.; Schoenmakers, P. J.; DeGalan, L. Anal. Chem. 1983, 5 5 , 847-851. (12C) Brackett, J. M.; Mitchell, J. C.; Vickers, T. J. Appl. Spectrosc. 1983, 37,569-570. (13'2) Brackett, J. M.; Vickers, T. J. Specfrochim. Acta, Part6 1983, 38, 979-985. (14C) Broekaert, J. A. C.; WoDenka, B.; Puxbaum, H. Anal. Chem. 1982, 54, 2174-2179. (15C) Browner, R. F.; Boorn, A. W.; Smlth, D. D. Anal. Chem. 1982. 5 4 , 1411-1419. (16C) Caikin, C. L.; Koeplin, S. M.; Crouch, S. R. Appl. Spectrosc. 1982, 36,369-374. (17C) Cammann, K.; Lendero. L.; Feuerbacher, H.; Ballschmifer, K. Fresenius' Z . Anal. Chem. 1983, 376, 194-200. ( l a c ) Carr, J. W.; Blades, M. W.; Hieftje, 0. M. Appi. Specfrosc. 1982, 36, 689-89 1. (19C) Carr, J. W.; Horllck, G. Spectrochim. Acta, Part6 4982, 37, 1-15. (20C) Cerbus, C. S.;Giuck, S . J. Spectrochim. Acta, Part B 1983, 38, 387-397. (21C) Chisholm, C. H.; Stephens, R. Anal. Chim. Acta 1982, 739,267-277. (22C) Choi, E. S.; Kim, H. Appl. Spectrosc. 1982, 36,71-74. (23C) Coleman, G. N.; Allen, A. M. Appl. Spectrosc. 1982, 36, 116-120. (24C) Cope, M. J.; Kirkbright, 0. F.; Burr, P. M. Analyst (London) 1982, 707, 611-616. (25C) Crabi, G.; Cavalli, P.; Achilii, M.; Rossi, G.; Omenetto, N. At. Spectrosc. 1982, 3, 81-88. (26C) Date, A. R.; Gray, A. L. Analyst (London) 1983, 708,159-165. (27C) Davie, R. N., Jr. Appl. Opt. 1983, 22, 1667-1869. (28C) Delaney, M. F.; Warren, F. V., Jr. Spectrochim. Acta, Part 6 1983, 38,399-406. (29C) Dobb, D. E.; Jenke, D. R. Appl. Spectrosc. 1983, 37, 379-384. (30C) Douglas, D. J.; Quan, E. S. K.; Smith, R. G. Spectrochim. Acta, Part 8 1983, 38,39-48. (31C) Ediger, R.; Barrett, P. At. Spectrosc. 1982, 3 , 146-146. (32C) Engman, S.; Lindblom, P. Appl. Opt. 1982, 27, 4356-4362. (33C) Engman, S.; Lindbiom, P. Appl. Opt. 1982, 27, 4363-4367. (34C) Ensman, R. E.; Carr, J. W.; Hieftje, G. M. Appl. Spectrosc. 1983, 37, 571-573. (35C) Erickson, L. E.; Monnon, R. E. Rev. Sci. Instrum. 1983, 5 4 , 70 1-705. (36C) Estes, S. A,; Uden, P. C.; Barnes, R. M. Anal. Chem. 1982, 5 4 , 2402-2405. (37C) Farnsworth, P. B.; Hleftje, G. M. Anal. Chem. 1983, 55, 1414-1417. (38C) Fujinaga, T.; Kuwamoto, T.; Isshiki, K.; Matsubara, N.; Nakayama, E. Spectrochim. Acta, Part B 1983, 38, 1011-1019. (3%) Garbarino, J. R.; Taylor, H. E. Spectrochlm. Acta, Part B 1983, 38, 323-335. (40C) Gardiner, P. E.; Bratter, P.; Negretti, V. E.; Schulze, G. Spectrochim. Acta, Part B 1983, 38,427-436. (41C) Gardner, W. S.; Landrum, P. F. Anal. Chem. 1982, 54, 1196-1198. (42C) Gll, M. A.; Simon, J. M. Appl. Opt.1983, 22, 152-158. (43C) Goode, S. R.; Chambers, B.; Buddin, N. P. Appl. Spectrosc. 1983, 37,439-443. (44C) Goulden, P. D.;Anthony, D. H. J. Anal. Chem. 1982, 5 4 , 1678-1681. (45C) Gray, A. L.; Date, A. R. Analyst (London) 1983, 108, 1033-1050. (46C) Greenfield, S . Spectrochim. Acta, Part B 1983, 38, 93-105. (47C) Gustavsson, A. Spectrochim. Acta, Part 6 1983, 38, 995-1003. (48'2) Hagen, D. F.; Beilsle, J.; Marhevka, J. S . Spectrochim. Acta, Part 8 1983, 38, 377-385. (49C) Haisch, V.; Laqua, K.; Hagenah, W.-D.; Waechter, H. Fresenlus' 2. Anal. Chem. 1983, 376, 157-169. (50C) Houk, R. S.; Fassei, V. A,; Svec, H. J. Dyn. Mess Spectrom. 1981, 6 , 234-251. (51'2) Houk, R. S.; Fassel, V. A.; Svec, H. J. Org.Mass Spectrom. 1982, 77,240-244. (52C) Houk, R. S.;Thompson, J. J. Am. Mlneral. 1982, 67,238-243. (53C) Houk, R. S.;Thompson, J. J. Biomedical Mass Spectrom. 1983, 70, 107-1 12. (54C) Houk, R. S.;Montaser, A.; Fassel, V. A. Appl. Spectrosc. 1983, 37, 425-428. (55C) Huimston, P. Analyst (London) 1983, 708,166-170. (56C) Hutton, R. C.; Preston, B. Analyst (London) 1983, 708,1409-1411.
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(57C) Irgoiic, K. J.; Stockton, R. A.; Chakraborti, D.; Beyer, W. Spectrochim. Acta, Part B 1983, 38,437-445. (58C) Ishizuka, T.; Uwamino, Y. Spectrochim. Acta, Part B 1983, 38, 519-527. (59C) Janssens, E.; DeDonder, J.; Taylor, P.; Dams, R.; Hoste, J. Spectrochlm. Acta, Part 8 1983, 38,865-872. (60C) Janssens, E.; Schutyser, P.; Dams, R.; Hoste, J. Spectrochim. Acta, Part B 1983, 38,337-347. (6lC) Jinno, K.; Tsuchida, H. Anal. Lett. 1982, 75, 427-437. (62C) Jinno, K.; Tsuchida, H.; Nakanishi, S.; Hirata, Y.; Fujimoto, C. Appl. Spectrosc. 1983, 37,256-261. (63C) Jolly, G. S.; Stephens, R. Anal. Chim. Acta 1982, 739,323-327. (64C) Jordan, S. W.; Krull, 1. S., Smith, S. B., Jr. Anal. Lett. 1982, 75, 1131-1148. (65C) Kaye, W. Anal. Chem. 1983, 55, 2018-2021. (66C) Kaye, W. Anal. Chem. 1983, 55, 2022-2025. (67C) Keiisohn, J. P.; Deutsch, R. D.; Hieftje, G. M. Appi. Spectrosc. 1983, 37, 101-104. (68C) Kennedy, W. R. Appi. Spectrosc. 1983, 37,478-479. (69C) Klrkbright, G. F.; Li-Xing, 2. Analyst (London) 1982, 707,617-622. (70C) Kirkbright, 0. F.; Snook, R. D. Appl. Spectrosc. 1983, 37, 11-16. (71C) Kirkbrlght. G. F.; Walton, S . J. Analyst(London) 1982, 707,276-261. (72C) Kitazume, E. Anal. Chem. 1983, 55, 602-805. (73C) Kovacic, N.; lkonomov, J. Fresenlus' Z. Anal. Chem. 1983, 375, 602-604. (74C) Kubota, M.; Fujishlro, Y.; Ishlda, R. Spectrochim. Acta, Part B 1982, 37,649-857. (75C) Layman, L. R.; Lichte, F. E. Anal. Chem. 1982, 5 4 , 638-642. (76C) Li-Xing, 2.; Kirkbright, G. F.; Cope, M. J.; Watson, J. M. Appl. Spectrosc. 1983, 37, 250-254. (77C) Long, S.E.; Snook, R. D. Analyst (London) 1983, 708,1323-1330. (78C) Long, S. E.; Snook, R. D. At. Spectrosc. 1982, 3 , 171-173. (79C) Marks, J. Y.; Fornwalt, D. E.; Yungk, R. E. Spectrochim. Acta, Part B 1983, 38, 107-113. (8OC) Marshall, J.; Girl, S.K.; Littlejohn, D.; Ottaway, J. M. Anal. Chim. Acta 1983, 747, 173-184. (81C) Mathews, S . E.; Ekimoff, D.; Waiters, J. P. Appl. Spectrosc. 1982, 36, 617-626. (82C) Mattoon, T. R.; Piepmeier, E. H. Anal. Chem. 1983, 55, 1045-1049. (63C) McCaffrey, J. T.; Michei, R. G. Anal. Chem. 1983, 55, 2175-2179. (84C) McCaffrey, J. T.; Wu, M. W.; Michei, R. G. Analyst (London) 1983, 708,1195-1208. (85C) McDonald, D. C.; Neil, R. S. Anal. Chim. Acta 1982, 138, 145-151. (86C) McDowell, M. W.; Bouwer, H. K. Spectrochim.Acta, Part B 1983, 38, 1311-1317. (87C) McGeorge, S.W.; Salin, E. D. Spectrochim. Acta, Part B 1983, 38, 633-636. (88C) Moore, G. L.; Watson, A. E.; Humphries-Cuff, P. Spectrochim. Acta, Part B 1982, 37, 835-837. (89C) Muliigan, K. J.; Zerezhgi, M.; Caruso, J. A. Spectrochim. Acta, Part B 1983, 38,369-375. (9OC) Na, H. C.; Niemczyk, T. M. Anal. Chem. 1983, 55, 1240-1245. (91C) Nash, D.L. Spectrochim. Acta, Part B 1983, 38, 1255-1257. (92C) Ng, K. C.; Caruso, J. A. Analyst (London) 1983, 708,476-480. (93C) Ng, K. C.; Caruso, J. A. Anal. Chem. 1983, 5 5 , 1513-1516. (94C) Nobile, A., Jr.; Shuler, R. G.; Smith, J. E., Jr. At. Spectrosc. 1982, 3 , 73-75. (95C) Oisen, S. D.; Strashelm, A. Spectrochim. Acta, Part B 1983, 38, 973-975. (96C) Papp, L. Spectrochim. Acta, Parts 1983, 38, 1203-1208. (97C) Qlng-Yu, 0.; Guo-Chuen, W.; Ke-Wei, 2.; Wei-Lu, Y. Spectrochlm. Acta, Part B 1983, 38,419-425. (98C) Rezaaiyaan, R.; Hieftje, 0. M.;Anderson, H.; Kaiser, H.; Meddings, B. Appl. Spectrosc. 1982, 36,627-631. (99C) Rice, G. W.; Richard, J. J.; D'Silva, A. P.; Fassel, V. A. Anal. Chim. Acta 1982, 742, 47-54. (1OOC) Riska, D. D.; Estes, S. A,; Beyer, J. 0.; Uden, P. C. Spectrochim. Acta, Part B 1983, 38,407-417. (101C) Schmidt, C. E.; Sacks, R. D. Spectrochim. Acta, Part B 1983, 38, 557-571. (102C) Shoaeb, A. M.; Heimi, M. S.;Eigamal, I. M. Spectrochim. Acta, Part B 1983, 38, 1005-1010. (103C) Smith, D. D.; Browner, R. F. Anal. Chem. 1982, 5 4 , 533-537. (104C) Smith, S. B., Jr.; Schleicher, R. G.; Dennlson, A. G.; McLean, G. A. Spectrochim. Acta, Part6 1983, 38, 157-163. (105C) Sobei, C. B. Appl. Spectrosc. 1982, 36,691-693. (106C) Stieg, S.; Dennis, A. Anal. Chem. 1982, 5 4 , 605-607. (107C) Strashelm, A,: Thaln, M. E.; Waiters, N. M.; Claase, C.; Human, H. G. C.; Ferreira, N. P. Spectrochim. Acta. Part B 1983, 38, 921-936. (108C) Summerhays, K. D.; Lamothe, P. J.; Fries, T. L. Appl. Spectrosc. 1983, 37,25-28. (109C) Tait, B. A. R. Appl. Spectrosc. 1982, 3 6 , 693-696. (llOC) Wallace, G. F. At. Spectrosc. 1983, 4 , 186-192. (111C) Whaiey, B. S.;Snable, K. R.; Browner, R. F. Anal. Chem. 1982, 54, 162-165. (112C) Wunsch, G.; Hegenberg, C.;Czech, N. Spectrochim. Acta, Part B 1983, 38, 1135-1141. (113C) Zalewski, E. F.; Duda, C. R. Appl. Opt. 1983, 22, 2867-2873. STANDARDS, SAMPLES, NOMENCLATURE, CALIBRATION, CALCULATIONS
(1D) Alverez, R.; Rasberry, S. D.; Uriano, G. A. Anal. Chem. 1982, 5 4 , 1226A-1 244A. .- - -. . .. .. .. (2D) Anderson, T. A,; Forster, A. R.; Parsons, M. L. Appl. Spectrosc. 1982, 36. 504-509. (3D) Belchamber, R. M.; Horllck, G. Spectrochim. Acta, Part 6 1982, 3 7 , 1037-1 046.
E MI SS I O N SPECTROMETRY (4D) Bowker, P. C.; Manheim, F. T. Appl. Specfrosc. 1982, 36, 378-382. (5D) Bratter, P.; Berthold, K. P.; Gardiner, P. E. Specfrochlm. Acta 1983, 38, 221-228. (6D) Bubert, H.; Klockenkamper, R. Spectrochim. Acta, Part E 1983, 38, 1087- 1098. (7D) Butler, L. R. P. Spectrochlm. Acta, Part E 1983, 38, 913-919. (ED) Cairns, T.; Rogers, W. M. Anal. Chem. 1983, 55, 54A-57A. (9D) Capelle, E.; Mermet, J. M.; Robln, J. Appl. Specfrosc. 1982, 36, 102- 106. (10D) Cassatt, E. Anal. Chem. 1982, 54, 778A. (11D) Chiba, K.; Haraguchi, H. Anal. Chem. 1983, 55, 1504-1508. (12D) Chiba, K.; Yoshida, K.; Tanabe, K.; Ozakl, M.; Haraguchl, H.; Winefordner, J. D.; Fuwa, K. Anal. Chem. 1982, 54, 761-764. (13D) Crock, J. G.; Lichte, F. E. Anal. Chem. 1982, 54, 1329-1332. (140) Dellefieid, R. J.; Martin, T. D. A t . Specfrosc. 1982. 3, 165-170. (133) deKreuk, H.; Pronk, H. F.; Wijker, J. Specfrochim. Acta, Part E 1983, 38, 831-833. (16D) Eckhoff, M. A.; McCarthy, J. P.; Caruso, J. A. Anal. Chem. 1982, 54, 165- 168. (17D) Fakes, L. M.; Apel, C. T.; Nlemczyk, T. M. Appl. Specfrosc. 1983, 37. 558-563. (18D)' Forster, A. R.; Anderson, T. A.; Parsons, M. L. Appl. Specfrosc. 1982, 36, 499-504. (19D) Goidberg, J.; Sacks, R. Anal. Chem. 1982, 54, 2179-2186. (20D) Hahn, M. H.; Woinik, K. A.; Fricke, F. L. Anal. Chem. 1982, 54, 1048-1052. (21D) Han, H. E.; Kaiser, G.; Tolg. G. Anal. Chlm. Acta 1982, 734, 3-11. (22D) Harterstein, S.D.; Swaidan, H. M.; Christlan, G. D. Analyst (London) 1983, 706,1323-1330. (23D) Hlettje, G. M. J. Chem. Educ. 1982, 59, 900-909. (24D) Howard, C.; Plilow, M. E.; Steers, E. E. M.; Ward, W. W. Analyst (London) 1983, 708,145-152. (25D) Inman, E. L., Jr.; Voigtman, E.; Winefordner, J. D. Appl. Specfrosc. 1982, 36, 99-102. (26D) Jones, J. S.; Harrington, D. E.; Leone, E. A.; Bramstedt, W. R. At. Specfrosc. 1983, 4, 49-54. (27D) Klockenkamper, R.; Bubert, H. Spectrochlm. Acta, Part E 1982, 37, 127-144. (28D) Korte, N.; Hollenbach, M.; Donivan, S. A t . Specfrosc. 1982, 3,
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(29D) Long, G. L.; Volgtman, E. G.; Kosinski, M. A.; Winefordner, J. D. Anal. Chem. 1993, 55, 1432-1434. (30D) Long, G. L.; Wlnefordner, J. D. Anal. Chem. 1983, 55, 712A-724A. (31D) Maessen, F. J. M. J.; Baike, J. Specfrochim. Acta, Part E 1982, 37, 37-44. _ . ... (32D) Mahantl, H. S.; Barnes, R. M. Appl. Specfrosc. 1983, 37, 261-263. (33D) Marathe, S. M.; Murty, P. S.; Sreenivasa Rao, M.; Subba Rao, K. V. Fresenius' 2.Anal. Chem. 1982, 377,507-510. (34D) Montaser, A.; Fassel, V. A. Appl. Specfrosc. 1982, 36, 454-459. (35D) Montaser. A.; Fassei, V. A. Appl. Specfrosc. 1982, 36, 613-617. (36D) Moody, J. R. Anal. Chem. 1982, 54, 1358A-1376A. (37D) Myers, S. A.; Tracy, D. H. Specfrochim. Acta, Part E 1983, 38, 1227-1253. (38D) Nakahara, T. Appl. Specfrosc. 1983, 37, 539-545. (39D) Nygaard, D. D.; Chase, D. S.; Lelghfy, D. A. Appl. Specfrosc. 1983, 37, 432-435. (40D) Oisen, S. D.; Edge, R. A.; Bohmer, R. G. Spectrochim. Acta, Part E 1982, 37, 303-308. (41D) Pruszkowska, E.; Barrett, P.; Ediger, R.; Wallace, G. At. Specfrosc. 1983, 4 , 94-98. (42D) Roederer, J. E.; Bastlaans, G. J.; Fernandez, M. A.; Fredeen, K. J. Appl. Spectrosc. 1992, 36, 383-389. (43D) Rybarczyk, J. P.; Jester, C. P.; Yates, D. A,; Koirtyohann, S. R. Anal. Chem. 1982, 54, 2162-2170. (44D) Schmidt, G. J.; Slavin, W. Anal. Chem. 1982, 54, 2491-2495. (45D) Schramel, P.; LI-Qiang, X. Anal. Chem. 1982, 54, 1333-1336. (46D) Schramel, P.; Ll-Qiang, X. Fresenius' 2. Anal. Chem. 1983, 374, 67 1-677. (47D) Svehla, G.; Dickson, E. L. Anal. Chim. Acfa 1982, 736,369-372. (48D) Taylor, J. K. Anal. Chem. 1983, 55, 600A-808A. (49D) Thompson, M.; Ramsey, M. H.; Coles, E. J. Analyst (London) 1982, 707. 1286-1288. (50D) Win&, R.X.; Fassei, V. A.; Peterson, V. J.; Floyd, M. A. Appl. Specfrosc. 1982, 36, 210-221. (51D) Xu, J.; Kawaguchi, H.; Mizulke, A. Appl. Spectrosc. 1983, 37, 123- 127. (52D) Zhlgiinsky, A. G.; Bodin, N. S.; Kalmakov, A. A.; Tsaryev, V. I.Spectrochlm. Acta, Part E 1982, 37, 1029-1035. EXCITATION SOURCES
(IE) Abdailah, M. H.; Couiombe, S.; Mermet, J. M.; Hubert, J. Spectrochlm. Acta, Part E 1982, 37, 583-592. (2E) Abdallah, M. H.; Mermet, J. M. Specfrochim. Acta, Part E 1982, 37, 391-397. (3E) Aeschbach, F. Specfrochim. Acta, Part E 1982, 37, 987-998. (4E) Ageev, V. A.; Pryakhin, S. S.; Khlopkov, Yu. V. Zh. Prikl. Spekfrosk 1982, 37, 727-733. (5E) Alkemade, C. Th. J. Specfrochlm. Acta, Part E 1983, 38, 1395-1409. (BE) Allen, A. M. Diss. Abst. I n f . 6 1983, 43, 3581. (7E) AI-Tamrah, S. A.; AI-Zamll, A. 2.; Townshend. A. Anal. Chim. Acta 1982. 143, 199-207. (8E) AI-Zamll, I. 2.; Townshend, A. Anal. Chim. Acta 1982, 142, 151-157. (9E) Apel, C. T.; Keiier, R. A.; Zalewski, E. F.; Engelman, R., Jr. Appl. Opt. 1982, 27, 1465-1467. (10E) Barnes, R. M.; Fodor, P.; Inayaki, K.; Fodor, M. Specfrochim. Acta, Part E 1983, 38, 245-257.
(11E) Barnes, R. M.; Khosah, R. P.; Mahantl, H. S.; Ullman, A. H. Specfrochim. Acta, P a r t s 1983, 38, 291-295. (12E) Barnes, R. M.; Mahanti, H. S. Specfrochim. Acta, Part E 1983, 38, 193-197. (13E) Barnett, N. W.; Chen, L. S.; Kirkbright, G. F. Anal. Chim. Acfa 1983, 749, 115-121. (14E) Batal, A.; Jarosz, J.; Mermet, J. M. Specfrochim. Acta, Part E 1982, 37, 511-516. (15E) Batai, A.; Mermet, J. M. Can. J . Specfrosc. 1982, 27, 37-45. (16E) Bauer, G. F.; Skogerboe, R. K. Specfrochim. Acta, Part E 1983, 38, 1125- 1 134. (17E) Belchamber, R. M.; Horlick, G. Spectrochlm. Acta, Part E 1982, 37, 17-21. (18E) Belchamber, R. M.; Horlick, 0. Specfrochim. Acta, Part E 1982, 37, 71-74. (19E) Belchamber, R. M.; Horlick, G. Spectrochim. Acta, Part E 1982, 37, 1075-1078. (20E) Belyl, V. A.; Meshkov, V. V.; Myshkin, N. K.; Sviridenok, A. I. Dokl. Akad. Nauk SSSR 1982. 265, 1121-1124. (21E) Benetti, P.; Bonnelli, A.; Camblaghi, M.; Frigleri, P. Specfrochim. Acta, Part E 1982, 37, 1047-1053. (22E) Berglund, E.; Thelin, E. Analyst (London) 1982, 707, 867-871. (23E) Berndt, H.; Messerschmidt, J. Fresenius ' Z. Anal. Chem. 1982, 3 7 7 , 365-366. (24E) Berry, T.; Macleod, K. C.; Christle, A. C.; Cunningham, J. A. Analyst (London) 1983, 108, 189-195. (25E) Blades, M. W. Appl. Specfrosc. 1983, 37, 371-375. (26E) Blades, M. W. Specfrochlm. Acta, Part 6 1982, 37, 889-879. (27E) Blades, M. W.; Hiettje, G. M. Specfrochim. Acta, Part E 1982, 37, 191-197. (28E) Bolton, A.; Hwang, J.; Voet, A. V. Specfrochim. Acta, Part E 1983, 38, 165-174. (29E) Boorn, A. W.; Browner, R. F. Anal. Chem. 1982, 54, 1402-1410. (30E) Borsier, M.; Garcia, M. Specfrochim. Acta, Part E 1983, 38, 123-127. (31E) Botto, R. I. Anal. Chem. 1982, 54, 1654-1659. (32E) Botto, R. I. Specfrochim. Acta, P a r t s 1983, 38, 129-149. (33E) Boumans, P. W. J. M. Specfrochlm. Acta, Part E 1982, 37, 75-82. (34E) Boumans, P. W. J. M.; Lux-Steiner, M. Ch. Specfrochim. Acta, Part E 1982, 37, 97-126. (35E) Boyko, W. J.; Kellher, P. N. Can. J . Spectrosc. 1982. 27, 51-57. (36E) Brackett, J. M.; Vlckers, T. J. Specfrochim. Acta, Part E 1982, 37, 84 1-847. (37E) Brake, M.; Hlnkle, J.; Asmussen, J.; Hawley, M.; Kerber, R. Plasma Chem. Plasma Process. 1983, 3, 63-78. (38E) Brandt, E. Rev. Scl. Insfrum. 1982, 53, 1088-1089, (39E) Broekaert, J. A. C.; Klockenkamper, R.; KO, J. E. Fresenius' 2.Anal. Chem. 1983, 376,256-260. (40E) Broekaert, J. A. C.; Lek, F.; Dincler, G. Analyst (London) 1983, 708, 717-721. (41E) Brown, R. J. Spectrochim. Acta, Part E 1983, 38, 283-284. (42E) Burgudjiev, Z.; Apostolova, M. Spectrochlm. Acta, Part E 1982, 37, 603-609. (43E) Burguera, M.; Burguera, J. L.; Gallignani, M. Anal. Chlm. Acta 1982, 738,137-143. (44E) Burns, D. W.; Murphy, M. P.; Parsons, M. L.; Hickie, L. A,; Staten, R. T. Appl. Spectrosc. 1983, 37, 120-123. (45E) Calkin, C. L. Diss. Abst. I n t . E 1982, 42,3246. (46E) Caiokerinos, A. C.; Hadjiioannou, T. P. Anal. Chim. Acta 1983, 148, 277-283. (47E) Camera Rica, C.; Kirkbright, G. F. Sci. TofalEnv. 1982, 22, 193-198. (48E) Carnahan, J. W. Diss. Abst. I n t . E 1983, 44, 486. (49E) Carnahan, J. W.; Caruso, J. A. Anal. Chlm. Acta 1982, 736, 261-267. (50E) Caroii, S.; Alimonti, A.; Petrucci, F. Anal. Chim. Acta 1982, 736, 269-276. (51E) Caroll, S.; Alimonti, A.; Zimmer, K. Specfrochim. Acfa, Part 6 1983, 38, 625-631. (52E) Caroii, S.; Petruccl, F.; Aiimonti, A. Can. J . Spectrosc. 1983, 28, 156-159. (53E) Caroii, S.; Senofonte, 0.; Femmlne, P. D. Analyst (London) 1983, 708, 196-203. (54E) Casetta, E.; Glaretta, A.; Rampazzo, G. At. Spectrosc. 1983, 4, 152- 154. (55E) Cavalll, P.; Omenetto, N.; Rossi, G. At. Specfrosc. 1982, 3, 1-4. (56E) Cavaiii, P.; Rossl, G.; Omenetto, N. Analysf (London) 1983, 108, 297-304. (57E) Chevrier, G.; Hanai, T.; Tran, K. C.; Hubert, J. Can. J . Chem. 1982, 60, 898-903. (58E) Chiba, K.; Yoshida, K.; Tanabe, K.; Haraguchi, H.; Fuwa, K. Anal. Chem. 1983, 55, 450-453. (59E) Cope, M. J.; Townshend, A. Anal. Chim. Acta 1982, 134, 93-100. (60E) Dalvi, A. G. I.; Sheshaglrl, T. K.; Natarajan, V.; Bhide, M. K.; Babu, Y.; Sastry, M. D.; Joshi, E. D. Fresenius' Z. Anal. Chem. 1983, 375, 353-354. (61E) deBoer, J. L. M.; Maessen, F. J. M. J. Specfrochim. Acta, Part 6 1983, 38, 739-746. (62E) Degner, R. Fresenius' Z. Anal. Chem. 1982, 377, 94-97. (63E) Demeny, D. Magy. Kem. Foly. 1983, 89, 176-180. W E ) Demers, D. R.; Busch, D. A.; Allemand, C. D. Am. Lab. 1982, 74 (3), 167-176. (65E) Demyshev, V. E.; Merkushkln, V. V. Svetotekhnika 1983, 4, 3-4. (WE) deoiivelra, E.; McLaren, J. W.; Berman, S. S. Anal. Chem. 1983, 55, 2047-2050. ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
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EMISSION SPECTROMETRY (67E) devilliers, D. B. Spectrochim. Acta, Part 8 1982, 3 7 , 365-367. (68E) Dingjan, H. A.; deJong. H. J. Spectrochlm. Acta, Part 6 1983, 38, 777-781. (69E) Disam, A.; Tschopel, P.; Tolg, G. Fresenius' 2.Anal. Chem. 1982, 731, 131-143. (70E) Dittrich, K.; Niebergail, K.; Krasnobaewa, N.; Nedjaikowa, N. Spectrochim. Acta, Part B 1983, 3 8 , 461-471. (71E) Dlttrich, K.; Niebergall, K.; Wennrich, R. Spectrochlm. Acta, Part 6 1982, 3 7 , 199-206. (72E) Downey, S.W.; HieftJe, 6. M. Anal. Chim. Acta 1982, 747, 193-205. (73E9 Eastwood, D.; Hendrick, M. S.; Miller, M. H. Spectrochlm. Acta, Part 6 1982, 3 7 , 293-302. (74E) Eaton, A.; Oelker, G.; Leong, L. At. Spectrosc. 1982, 3 , 152-156. (75E) Ecker, G. NATO Adv. Sci. Inst. Ser., Ser. B 1983, 8 9 , 167-179. (76E) Eckert, H. V.; Danieisson, A. Specfrochim. Acta, Part B 1983, 3 8 , 15-27. (77E) Eckhoff, M. A.; Ridgway, T. H.; Caruso, J. A. Anal. Chem. 1983, 55, 1004- 1009. (78E) Ehrlich, G.; Stahlberg, V.; Scholze, H. Spectrochim. Acta, Part 6 1982, 3 7 , 45-51. (79E) Ed, M. A.; EIBehery, K. M.; Fakhry, A. A.; EIAnany, F. A. Spectrochim. Acta, Part 6 1983, 38, 495-502. (80E) Endo, Y.; Sakao, N. Tetsu to Hagane 1982, 68, 2578-2584. (81E) Eroshenko, L. E.; Dem'yanchuk, A. S. Zh. Prlkl. Spektrosk 1983, 3 9 , 15-21. (82E) Estes, S. A. Dlss. Abst. Int. 6 1982, 42, 4780-4781. (83E) Evans, W. H.;Deliar, D. Analyst (London) 1982, 707, 977-993. (84E) Fabec, J. L.; Ruschak, M. L. Anal. Chem. 1983, 55, 2241-2246. (85E) Farnsworth, P. B.; Walters, J. P. Anal. Chem. 1982, 5 4 , 885-890. (86E) Farnsworth, P. 8.; Waiters, J. P. Spectrochim. Acta, Part 6 1982, 37, 773-788. (87E) Feeney, C. M.; Anderson, J. W.; Tindail, F. M. At. Spectrosc. 1983, 4 , 108-1 10. (88E) Fernando, L. A. Spectrochim. Acta, Part 6 1982, 3 7 , 859-868. (89E) Ferreira, N. P.; Strauss, J. A.; Human, H. G. C. Spectrochlm. Acta, Part 6 1982, 3 7 , 273-279. (90E) Ferreira, N. P.; Strauss, J. A.; Human, H. 0. C. Spectrochim. Acta, Part6 1983, 38, 899-911. (91E) Fischer, J.; Boyd, D. A.; Cavaiio, A,; Benson, J. Rev. Sci. Instrum. 1983, 54, 1085-1090. (92E) Fischer, P. T.; Ellgren, A. J. Spectrochim. Acta, Part 6 1983, 3 8 , 309-316. (93E) Fisher, M. T.; Lee, J. Anal. Chim. Acta 1982, 139, 333-339. (94E) Florian, K.; Zlmmer, K. Spectrochlm. Acta. Part 6 1982, 3 7 , 29-36. (95E) Floyd, M. A.; Morrow, A. W.; Farrar, R. B. Spectrochlm. Acta, Part 6 1983, 3 8 , 303-308. (96E) Fodor, P.; Barnes, R. M. Spectrochim. Acta, Part 6 1983, 3 8 , 229-243. (97E) Foss, G. 0.; Svec, H. J.; Conzemius, R. J. Anal. Chim. Acta 1983, 747, 151-162. (98E) Frank, A.; Petersson, L. R . Spectrochim. Acta, Part 6 1983, 3 8 , 207-220. (99E) Fujishiro, Y.; Kubota, M.; Ishida, R. Anal. Chlm. Acta 1982, 742, 173- 182. (100E) Furuta, N.; Horiick, G. Spectrochlm. Acta, Part6 1982, 3 7 , 53-64. (101E) Gao, J.; Yang, F.; Xu, S. FenxiHuaxue 1982, 10, 32-33. (102E) Genna, G. L.; McAninch, W. D.; Reich, R. A. J . Chromatogr. 1982, 238, 103-112. (103E) Gibert, A.; Dupuy, J.; Bayle, M.; Bayie, P. J . Phys. D 1983, 16, 1493-1 506. (104E) Gilbert, T. A,; Penney, B. A. Spectrochim. Acta, Part B 1983, 3 8 , 297-302. (105E) Giri, S . K.; Littlejohn, D.; Ottaway, J. M. Analyst (London) 1982, 707, 1095-1098. (106E) Golloch, A,; Kub, H. M.; Schmitz, K. H.; Simon, L. Fresenius' 2. Anal. Chem. 1983, 376, 51. (107E) Gonzalez Flesca, N.; Diamy, A. M.; Ben-Aim, R. I. Spectrochim. Acta, Part 6 1983, 3 8 , 487-494. (108E) Goode, S . R.; Baughman, K. W. Spectrochim. Acta, Part B 1983, 38, 75-80. (109E) Gregoire, D. C.; Chakrabarti, C. L. Spectrochim. Acta, Part B 1982, 3 7 , 625-632. (IIOE) Griffin, H.; Savoialnen, A. Spectrochlm. Acta, Part 6 1983, 3 8 , 183- 19 1. (111E) Grogan, W. C. Spectrochim. Acta, Part 6 1983, 3 8 , 357-369. (112E) Gunter, W. H.; Visser, K.; Zeeman, P. B. Spectrochlm. Acta, Part 6 1982, 3 7 , 571-581. (113E) Gunter, W. H.; Visser, K.; Zeeman, P. B. Spectrochim. Acta, Part 6 1983, 3 8 , 949-958. (114E) Gustavsson, A. Anal. Chem. 1983, 5 5 , 94-98. (115E) Haas, D. L.; Carnahan, J. W.; Caruso, J. A. Appl. Spectrosc. 1983, 3 7 , 82-85. (116E) Hanamura, S.; Smith, B. W.; Winefordner, J. D. Anal. Chem. 1983, 55, 2026-2032. (117E) Hanzsche, E. Beitr. Plasmaphys. 1982, 2 2 , 325-346. (118E) Hara, L. Y. Diss. Abstr. Int. 6 1983, 4 3 , 2891. (119E) Hasegawa, T.; Haraguchi, H.; Fuwa, K. Chem. Lett. 1983, 3 , 397-400. (120E) Hayakawa, T.; Kikui, F.; Ikeda, S . Spectrochlm. Acta, Part 8 1982, 3 7 , 1069-1073. (121E) He, 2. FenxiHuaxue 1983, 1 1 , 401-405. (122E) Heimer, D. C. Dlss. Abstr. Int. 6 1983, 43, 3967. (123E) Henden, E. Analyst (London) 1982, 107, 872-878. (124E) Heppner, R. A. Anal. Chem. 1983, 5 5 , 2170-2174.
154R
ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
(125E) Herber, R. F. M.; Pieters, H. J.; Elgersma, J. W. Fresenius' 2.Anal. Chem. 1982, 313, 103-107. (126E) Hieftje, G. M. Spectrochim. Acta, Part 6 1983, 38, 1465-1481. (127E) Holclajtner-Antunovic, I.; Cadez, V.; Vukanovic, V.; Georgijevic, V. Spectrochlm. Acta, Part B W82, 3 7 , 889-893. (128E) Holclajtner-Antunovic, I.; Georgljevic, V.; Vukanovic, V. Fresensius ' 2.Anal. Chem. 1982, 312, 126-130. (129E) Holclajtner-Antunovic, I.;Vukanovic, V.; Georgijevic, V.; Cadez, V. Spectrochim. Acta, Part 6 1982, 3 7 , 895-901. (130E) Hoiman, D. W.; Vickers, T. J. Talanta 1982, 2 9 , 419-421. (131E) Horlick, G.; Furuta, N. Specfrochim. Acta, Part 6 1982, 3 7 , 999-1008. (132E) Huczko, A.; Szymanski, A. 2. Phys. Chem. (Leiprig) 1982, 263, 1210-1216. (133E) Huf, F. A.; Jansen, G. W. Spectrochlm. Acta, Part 6 1983, 3 8 , 1061-1064. (134E) Ishii, H.; Satoh, K. Taslanta 1982, 2 9 , 243-248. (135E) Ishii, H.; Satoh, K. Talanta 1983, 3 0 , 111-115. (136E) Issac, R. A.; Johnson, W. C. Spectrochlm. Acta, Part 6 1983, 3 8 , 277-282. (137E) Jenke, D. R.; Woodriff, R. Spectrosc. Lett. 1983, 76, 221-231. (138E) JI, W.; Si, 2.; Dai, X.; Chen, W. Nanjlng Nongxueyuan Xuebaco 1982, 2 . 101-104. (139E) Johnson, G. W.; Sisneros, T. E. Rare Earths Mod. Scl. Techno/. 1982. 3 . 525-529. (140E) Jones, J. B., Jr. Spectrochlm. Acta, Part 6 1983, 38, 271-276. (141E) Jones, J. W.; Capar, S.0.; O'Haver, T. C. Analyst (London) 1982, 707, 353-377. (142E) Jordan, S. W.; Karger, B. J.; Krull, I. S.;Smith, S. B., Jr. Chem. Homed. Environ. Instrum. 1983, 72, 263-274. (143E) Jordan, S. W.; Kruli, I. S.;Smith, S . B., Jr. Anal. Lett. 1982, 15, 1131-1148. (144E) Jurenka, H. J. Appi. Phys. 1982, 5 3 , 6115-6120. (145E) Kabiel, A. M.; Shoaeb, A. M.; Mossaad, M. M.; Nasra, M. K. Spectrochlm. Acta, Part 6 1983, 3 8 , 543-547. (146E) Kagawa, K.; Yokoi, S . Spectrochim. Acta, Part 6 1982, 3 7 , 789-795. (147E) Kaiyi, 2. Spectrosc. Lett. 1983, 76, 565-581. (148E) Kankare, J. J.; Stephens, R. Spectrochim. Acta, Part 6 1983, 3 8 , 1301-1309. (149E) Kato, I.; Hara, S.;Wakana, S . J. Appl. Phys. 1983, 5 4 , 4883-4888. (150E) Kawaguchi, H.; Oshio, Y.; Mizuike, A. Spectrochim. Acta, Part 6 1982, 3 7 , 809-816. (151E) Kawaguchl, H.; Tanaka, T.; Miura, S.;Xu, J.; Mizuike, A. Spectrochim. Acta, Part6 1983, 3 8 , 1319-1327. (152E) Keiiher, P. N.; Boyko, W. J. Recent Adv. Anal. Spectrosc., Proc. Int. Conf. At. Spectroscopy, K . Fuwa, Ed. 1982, 83-91 (see ref 57A). (153E) Kempster, P. L.; Malloch, J. D. R.; deKlerk, M. V. D. S. Spectrochim. Acta, Part B 1983, 3 8 , 967-972. (154E) Kinniburgh, D. 0.; Miles, D. L. Envlron. Sci. Tech. 1983, 77, 362-368. (155E) Kirkbright, G. F. Pergamon Ser. Env. Scl. 1982, 7 , 353-361. (156E) Kirkbrlght, G. F.; Millard, D. L.; Snook, R. D. Spectrochlm. Acta, Part 6 1983, 38, 649. (157E) Kolrtyohann, S . R. Anal. Chem. 1983, 55, 374-376. (158E) Kojima, I.; Iida, C. Anal. Lett. 1982, 15, 543-548. (159E) Koilotzek, D.; Tschopel, P.; Toiig, G. Spectrochlm. Acta, Part 6 1982, 3 7 , 91-96. (160E) Kornblum, G. R.; Klok, A.; deGalan, L. Spectrochim. Acta, Part 6 1983, 3 8 , 1363-1366. (161E) Kornblum, G. R.; Smeyers-Verbeke, J. Spectrochlm. Acta, Part 6 1982, 3 7 , 83-87. (162E) Kosinski, M. A. Dlss. Abstr. Int. 6 1983, 44, 488. (163E) Koslnski, M. A.; Uchida, H.; Winefordner, J. D. Anal. Chem. 1983, 55,688-692. (164E) Kosinski, M. A.; Uchida, H.; Winefordner, J. D. Talanta 1983, 30, 339-345. (165E) Kouimtzis, Th. A. Anal. Chim. Acta 1982, 742, 329-332. (166E) Krasnobaeva, N.; Nedyalkova, N.; Peshev, P.; Klrkova, E.; Nikolova, L.; Velichkov, S. Spectrochim. Acta, Part 6 1982, 3 7 , 829-833. (167E) Kretschmer, M.; Koch, K. H.; Grunenberg, D. Fresenius' Z . Anal. Chem. 1983, 374, 226-234. (168E) Krull, I. S.;Bushee, D.; Savage, R. N.; Schleicher, R. G.; Smith, S. B., Jr. Anal. Lett. 1982, 15, 267-281. (169E) Kuennan, R. W.; Woinik, K. A,; Fricke, F. L.; Caruso, J. A. Anal. Chem. 1982, 54, 2146-2150. (170E) Kumamaru, T.; Riordan, J. F.; Vaiiee, B. L. Anal. Blochem. 1982, 726, 208-213. (171E) Kurochkin, V. D. Zh. Prikl. Spektrosk. 1982, 37, 200-205. (172E) Lancione, R. L.; Drew, D. M. Ind. Res. Dev. 1983, 25, 100-104. (173E) Leary, J. J.; Brookes, A. E.; Dorrzapf, A. F., Jr.; Golightly, D. W. Appl. Spectrosc. 1982, 3 6 , 37-40. (174E) Liu, K.; Shi, C.; Zhang, Li Fenxi Huaxue 1982, 70, 16-21. (175E) Lohau, K.; Bosch, H.: Lemm, H. Thyssen Tech. 6 e r . 1982, 7 4 , 99-104. (176E) Lomdahl, G. S.;McPherson, R.; Sullivan, J. V. Anal. Chlm. Acta 1983, 148, 171-180. (177E) Lovett, R. J. Spectrochlm. Acta, Part 6 1982, 3 7 , 969-985. (178E) Loving, T. J.; Harrison, W. W. Anal. Chem. 1983, 5 5 , 1523-1526. (179E) Lyons, D. J.; Roofayel, R. L. Analyst (London) 1982, 707, 331-335. (180E) Maessen, F. J. M. J.: Balke, J.; deBoer, J. L. M. Spectrochim. Acta, ' Pak 6 1982, 37, 517-526. (181E) Mahanti, H. S.; Barnes, R. M. Anal. Chem. 1983, 5 5 , 403-405. (182E) Mahanti, H. S.; Barnes, R. M. Anal. Chim. Acta 1983, 749, 395-400.
EM I SS I O N SPECTROMETRY (183E) Mahanti, H. S.;Barnes, R. M. Anal. Chim. Acta 1983, 757, 409-417. (184E) Marode, E. NATOAdv. Sci. Inst. Ser., Ser. 6 1983, 89, 119-166. (185E) Marshall, L.; Littlejohn, D.; Ottaway, J. M.; Harnley, J. M.; Miiler-Ihli, N. J.; O'Haver, T. C. Analyst (London) 1983, 708, 178-188. (186E) Martynov. A. T. Zh. Prikl. Spektrosk. 1983, 39, 13-15. (187E) Mathews, S. E. Diss. Abstr. Int. 6 1982, 43, 1482-1483. (188E) McCarthy, J. P.; Caruso, J. A.; Wolnlk, K. A.; Frlcke, F. L. Anal. Chim. Acta 1983, 147,163-172. (189E) McDonald, D. C. Anal. Chem. 1982, 54, 1057-1059. (190E) McDonald, D. C. Spectrochim. Acta, Part 6 1982, 37, 747-758. (191E) Meubus, P.; Elayoubi, M. Can. J. Phys. 1983, 67,683-690. (192E) Mlanzhi, 2.; Barnes, R. M. Spectrochim. Acta, Part 6 1983, 38, 259-269. (193E) Miljevic, V. I. Appl. Opt. 1983, 22, 904-907. (194E) Minoia, C.; Pozzoli, L.; Angelera, S.;Tempini, G.; Candura, F. At. Spectrosc. 1982, 3 , 70-72. (195E) Miyazaki, A.; Kimura, A.; Bansho, K.; Umezakl, Y. Anal. Chim. Acta 1982, 744, 213-221. (l96E) Miyazaki, A.; Kimura, A.; Umezaki, Y. Anal. Chlm. Acta 1982, 738, 121-127. (197E) Mohan, M. S.;Zingaro, R. A.; Micks, D.; Clark, P. J. Infern. J . Env. Anal. Chem. 1982, 7 7 , 175-187. (198E) Motooka, J. M.; Sutley, S. J. Appl. Spectrosc. 1982, 36,524-533. (199E) Mulllgan, K. J. Dlss. Abstr. I n t . 6 1983, 43, 3584-3585. (200E) Na, H. C.; Nlemczyk. T. M. Anal. Chem. 1982, 54, 1839-1843. (201E) Nakajima, S.;Kosasa, K.; Maruyama, Y.; Kawai, S. Spectrochlm. Acta, Part 6 1982, 37,685-690. (202E) Natansohn, S.; Czupryna, G. Spectrochlm. Acta, Part 6 1983, 38, 3 17-322. (203E) Nestor, J. P. Appl. Opt. 1982, 27, 4154-4157. (204E) Ng, K. C.; Caruso, J. A. Anal. Chlm. Acta 1982, 743,209-222. (205E) Nl-Chung, R.; Wu-Mln, C.; Zu-Cheng, J.; Yun-E. 2 . Spectrochim. Acta, Part 6 1983, 38, 175-182. (208E) Nojiri, Y.; Tanabe, K.; Uchida, H.; Haraguchi, H.; Fuwa, K.; Winefordner, J. D. Spectrochlm. Acta, Part6 1983, 38,61-74. (207E) Novak, J. P.; Shoucri, M. M. J. Appl. Phys. 1982. 53,4695-4703. (208E) Nygaard, D. D.; Lowry, J. H. Anal. Chem. 1982, 54. 803-807. (209E) Oiesik, J. W.; Walters, J. P. Appl. Spectrosc. 1983, 37, 105-119. (210E) Ottaway, J. M.; Marshall, J. Talanta 1983, 30,571-577. (211E) Owens, J. W.; Gladney, E. S.;Knab, D. Anal. Chim. Acfa 1982, 135, 169-1 72. (212E) Page, A. G.; Godbole, S.V.; Madraswala, K. H.; Kulkarni, M. J.; Mailapurkar, V. S.;Joshi, B. D. Anal. Lett. 1983, 76, 1005-1012. (213E) Page, A. G; Madraswala, K. H.; Godbole, S.V.; Kulkarni, M. J.; Mallapurkar, V. S.;Joshi, B. D. Fresenius' 2 . Anal. Chem. 1983, 375,38-41. (214E) Paksy, L.; Lakatos, I. J. Specfrochim. Acta, Part 6 1983, 38, 1099-1114. (215E) Prack, E. R.; Bastiaans, G. J. Anal. Chem. 1983, 55, 1854-1680. (216E) Que Hee, S.S.;Finelli, V. N.; Frlcke, F. L.; Wolnlk, K. A. Intern. J. Environ. Anal. Chem. 1982, 73, 1-18. (217E) Quentmeler, A,; Demeny, D.; Laqua, K. Fresenlus' 2.Anal. Chem. 1983, 374,235. (21%) Raaijmakers, I.J. M. M.; Boumans, P. W. J. M.; Van Der Sijde. B.; Schram, D. C. Spectrochlm. Acta, Part 6 1983, 38, 697-706. (219E) Radermacher, L.; Beske, H. E. Spectrochlm. Acta, Part 6 1982, 37, 769-772. (220E) Radic-Perk J. Spectrochlm. Acta, Part 6 1983. 38, 1021-1030. (221E) Radic-Peric, J. Spectrochim. Acta, Part 6 1983, 38, 1031-1039. (222E) Radziemski, L. J.; Cremers, D. A.; Loree, T. R. Spectrochlm. Acta, Part 6 1983, 38,349-355. (223E) Ramsey, M. H.; Thompson, M.; Coles, B. J. Anal. Chem. 1983, 55, 1626-1829. (224E) Ripson, P. A. M.; deGalan, L. Spectrochim. Acta, Part6 1983, 38, 707-726. (225E) Ripson, P. A. M.; deGalan, L.; deRuiter, J. W. Spectrochim. Acta, Part 6 1982, 37,733-738. (226E) Romanov, G. S.;Stepdnov, K. L.; Syrkin, M. I. Opt. Spektrosk. 1982, 53, 842-648. (227E) Safavi, A.; Townshend, A. Anal. Chlm. Acta 1982, 142, 143-150. (228E) Savoie, R.; Pigeon-Gosselin, M. Can. J . Spectrosc. 1983, 28, 133- 138. (229E) Scheeiine, A.; Tran, T. V. Appl. Spectrosc. 1982, 36,25-29. (230E) Schramel, P. Spectrochim. Acta, Part 6 1983, 38, 199-206. (231E) Schramel, P.; Kiose, B.J.; Hasse, S. Fresenius' 2 . Anal. Chem. 1982, 370, 209-216. (232E) Schramel, P.; Li-Qiang, X.; Wolf, A.; Hasse, S. Fresenius' 2.Anal. Chem. 1982, 373,213-216. (233E) Seeverens, P. J. H.; Klaassen, E. J. M.; Maessen, F. J. M. J. Spectrochim. Acta, Part 6 1983, 38, 727-737. (234E) Smythe, L. E. Rev. Anal. Chem. 1982, 6 , 1-11. (235E) Stephens, R. Spectrochim. Acta, Part 6 1983, 38, 1077-1086. (238E) Strauss, J. A.; Ferreira, N. P.; Human, H. 0. C. Spectrochlm. Acta, Part B 1982, 37,947-954. (237E) Sugimae, A.; Mizoguchi, T. Anal. Chim. Acta 1982, 744, 205-212. (238E) Tanabe, K.; Haraguchi, H.; Fuwa, K. Spectrochlm. Acta, Part 6 1983, 38, 49-60. (239E) Tayior, G. W.; Dowdy, E. J.; Bieri, J. M. Anal. Chim. Acta 1982, 736, 277-284. (240E) Teraoka, H. Fresenius' 2.Anal. Chem. 1982, 313, 108-115. (241E) Thierlg, D. Fresenius' 2.Anal. Chem. 1982, 310, 154-159. (242E) Thompson, M.; Ramsey, M. H.; Pahlavanpour, B. Analyst (London) 1982. 707,1330-1334. (243E) Tracy, D. H.; Myers, S. A. Spectrochim. Acta, Part 6 1982, 37, 1055-1068.
(244E) Tracy, D. H.; Myers, S.A.; Balistee, B. G. Spectrochim. Acta, Part 6 1982, 37,739-743. (245E) Tzeng, J. H.; Fernando, Q. Anal. Chem. 1982, 54, 971-974. (248E) Uchida, H.; Kosinski, M. A.; Winefordner, J. D. Spectrochim. Acta, Part 6 1983, 38,5-13. (247E) Ushio, M. Koon Gakkaishi 1982, 8 , 14-23. (248E) VanDalen, H. P. J.; Kwee, B. G.; deGalan, L. Anal. Chim. Acta 1982, 742,159-171. (249E) vanDljk, C.; Smith, B. W.; Winefordner, J. D. Spectrochlm.Acta, Part 6 1982, 37, 759-788. (250E) Wallace, G. F.; Pirc, V. V.; Ediger, R. D. Can. J. Spectrosc. 1982, 27,46-51. (251E) Waiters, J. P.; Eaton, W. S. Anal. Chem. 1983, 55,57-64. (252E) WaRers, N. M.; Strasheim, A.; Oakes, A. R. Spectrochim. Acta, Part 6 1983, 38, 959-965. (253E) Washburn, D. N. Diss. Abstr. Int. 6 l982, 4 3 , 130-131. (254E) Washburn, D. N.; Walters, J. P. Appl. Spectrosc. 1982, 36, 5 10-5 19. (255E) Whitely, R. V., Jr.; Merrill, R. M. Fresenius' 2 . Anal. Chem. 1983, 371, 7-10. (256E) Wichman, M. D.; Fry, R. C.; Mohamed, N. A.m 1983, . / . Spectrosc. . 37,254-258. (257E) Winter, H. J . Phys. E 1982, 75,1007-1009. (258E) Wirz, P.; Debus, H.; Hanle, W.; Scharmann, A. Spectrochlm. Acta, Part 6 1982, 37, 1013-1020. (259E) Wirz, P.; Gross, M.; Ganz, S.; Scharmann, A. Spectrochim. Acta, Part B 1983, 38, 1217-1225. (260E) Wolcott, J. F.; Sobel, C. B. Appl. Spectrosc. 1982, 36, 685-686. (261E) Wrembei, H. 2. Spectrochim. Acta, Part 6 1982, 37,937-946. (262E) Wrembel, H. 2. Talanta 1983, 30, 481-485. (263E) Wuensch, G.; Czech, N.; Hegenberg, G. Fresenius' 2 . Anal. Chem. 1982, 370, 62-69. (264E) Xi-en, S.;Qi-Ian, C. Spectrochim. Acta, Part6 1983, 38, 115-121. (285E) Yoshida, K.; Hasegawa, T.; Haraguchi, H. Anal. Chem. 1983, 55, 2106-2108. (268E) Zadgorska, 2.; Bauer, E.; Nickel, H. Fresenius' 2. Anal. Chem. 1983, 374, 351-355.
SELECTED APPLICATIONS (1F) Broaekaert, J. A. C. Trends in Anal. Chem. 1982, 7 , 249-253. (2F) Camerlynck, R.; Martens, R.; Verloo, M. Bull. Soc. Chlm.
[email protected]. 91,877-684. (3F) Chandola, L. C.; Lordello, A. R. Microchem. J . 1983, 28,87-90. (4F) Chen, X.; He, 2. Fenxi Huaxue 1983, 7 7 , 357-359. (5F) Chryssoulis, S. L. Chem. Geol. 1983, 4 0 , 323-335. (6F) Cremers, D. A.; Radziemski, L. J. Anal. Chem. 1983, 55, 1252-1256. (7F) DeLa GuardiaGirugeda, M.; Legrand, G.; Druon, M.; Louvrier, J. Analusls 1982, 70, 478-480. (8F) Ebdon, L.; Cave, M. R. Analyst (London) 1982, 107, 172-178. (9F) Everett, G. L. Anal. R o c . (London) 1982, 79,86-90. (1OF) Garbarino, J. R.; Taylor, H. E. Anal. Chim. Acta 1982, 734,153-165. (11F) Hale, M.; Thompson, M. Trans. Inst. Min. Metall., Sect. 6 1983, 92, 23-27. (12F) Hart, F. A.; Adams, S. J. Archaeometry 1983, 25, 179-185. (13F) Headridge, J. B. Anal. Proc. (London) 1983, 20, 207-210. (14F) Heine, D. R.; Denton, M. B.; Schlabach, T. D. Anal. Chem. 1982, 54, 81-84. (15F) Huber, L. Vom Wasser 1982, 58, 173-185. (16F) Iwasaki, K.; Uchlda, H.; Tanaka, K. Anal. Chim. Acta 1982, 735, 369-372. (17F) Jones, H. B., Jr. J. Assoc. Off. Anal. Chem. 1982, 65,781-785. (18F) Jordan, J. R. J. CoalQual. 1982, 2 ,20-21. (19F) Kempf, T.; Sonneborn, M. Mikrochlm. Acta 1983, 2 ,445-453. (20F) Kim, W. Y.; Shin, H. C.; Maeng, K. S. Poilimo 1983, 7 , 168-175. (21F) Korte, N.; Hollenbach, M.; Donivan, S. Anal. Chim. Acta 1983, 146, 267-270. (22F) Lee, J. Anal. Chim. Acta 1983, 752,141-147. (23F) Luther, L. C.; Kometani, T. Y. J. Am. Ceram. SOC. 1983, 66, 619-622. (24F) Mainka, E.; Mueiier, H. G.; Geyer, F. Kernforschungszent Karlsruhe 1983, 175-187. (25F) Maksimov, D. E.; Rudnevskll, N. K. Zh. Prikl. Spektrosk. 1983, 39, 5-12. (26F) Martynov, A. T. Zh. Prikl. Spektrosk. 1983, 39, 13-15. (27F) Mazzucotelli, A.; Minoia, C.; Vannucci, R. Ren. SOC. Itel. Mineral. Petrol. 1983, 781-786. (28F) Miles, D. L.; Cook, J. M. Anal. Chim. Acta 1982, 747, 207-212. (29F) Montlel, A.; Weite, B.; Beaulleu, C. Rev. Fr. Sci. Eau 1982, 7 , 3 19-344. (30F) Nadkarni, R. A.; Botto, R. I.; Smith, S. E. At. Spectrosc. 1982, 3, 180- 184. (31F) Norman, J. D.; Stumpe, L. A.; Trlmm, J. R.; Johnson, F. J. J . Assoc. Off. Anal. Chem. 1983, 86,949-951. (32F) Okamoto, K.; Nishlkawa, M.; McLeod, C. W. Kokurltsu Kogal Kenkyusho Kentyu Hokoku 1982, 38, 47-67. (33F) Pyy, L.; Lajunen, L. H. J.; Hakala, E. Am. Ind. Hyg. Assoc. J. 1983, 44, 609-614. (34F) Radziemski, L. J.; Loree, T. R.; Cremers, D. A.; Hoffman, N. M. Anal. Chem. 1983, 55, 1246-1252. (35F) Roura, M.; Bauceiis, M.; Lacort, G.; Rauret, G. Pergamon Ser. Env. S d . 1982, 7 ,377-380. (36F) Slavin, S.;Ediger, R. D.; Wallace, G. F. Pergamon Ser. Env. Scl. 1982, 7 ,363-370. (37F) Spackova, A.; Chaudhri, M. S. Microchem. J. 1982, 27, 97-101. (38F) Spiers, G. A.; Duda, M. J.; Hodgins, L. W. C/ays Clay Miner. 1983, 31, 397-400. ANALYTICAL CHEMISTRY, VOL. 56,
NO. 5,
APRIL 1984
155R
Anal. Chem. 1084, 56, 156R-173R (39F) Strain, W. H.; Varnes, A. W.; Drenski, T. L.; Paxton, C. A.; McKinney, 0 . M. Trace Subt. Envlron. Health 1882, 16, 331-337. (40F) Subramanian, K. S.;Meranger, J. C. Scl. Total Envlron. 1982, 2 4 , 147-1 57. (41F) Tadana. J. Med. Techno\. (Tokyo) 1983, 71, 960-965. (42F) Takeo, T. Nippon Shokuhh Kogyo Gakkaishll982, 29, 733-735. (43F) Takeo, T. Nippon Shokuhln Kogyo Gakkaishl1983, 3 0 , 476-479. (44F) Tao, H.; Iwata, Y.; Hasegawa, T.; NoJiri,Y.; Haraguchi, H.; Fuwa, K. Buli. Chem. Soc. Jpn. 1983, 56, 1074-1079.
(45F) Uchlda, H.; Iwasaki, K.; Tanaka, K.; Iida, C. Anal. Chim. Acta 1982, 134, 375-37%. &fetal/, 1983, 25, 299-307, (46F) Vinot, J. collOq, (47F) Yuan, X.; Ceng, H.; Wu, X.; Wen, H.; Yin, N. Yankuang Ceshi 1983, 2 , 71-75. (46F) Zadgorska, Z.; Nickel, H.; Mazurklewicz, M.; Woiff, G. Fresenius’ Z . Anal. Chem. 1983, 3 7 4 , 356-361. (49F) Zhu, X. Huanllng Kexue 1983, 4 , 62-64.
Molecular Fluorescence, Phosphorescence, and Chemiluminescence Spectrometry E. L. Wehry Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996
As in the previous review in this series ( A I ) ,this survey emphasizes advances in the techniques of molecular luminescence spectrometry and instrumentation related to present or potential analytical luminescence methods. Applications of well-established techniques are cited only when they seem particularly novel or important to this reviewer. The review, prepared with the assistance of a computer search profile of Chemical Abstracts titles and identifiers prepared locally, covers literature indexed by Chemical Abstracts from November 1981 (Vol. 95, issue 21) through October 1983 (Vol. 99, issue 20). Many journals scanned manually by the author are covered up through issues received by November 30,1983. As in the previous review, certain topics are excluded, including virtually all publications concerning atomic fluorescence, molecular luminescence in flames or plasmas, X-ray fluorescence, solid-state phosphor and semiconductor luminescence (both organic and inorganic), radioluminescence, liquid scintillation counting, and photosynthesis and solar energy collection. The immense literature on fluorescent probing of macromolecular and micellar systems, much of which could quite properly be considered as “analytical chemistry”, has been excluded except for citation of a few general reviews. Certain other subject matter areas, noted in the appropriate sections of the review, are covered in a very arbitrary manner. To keep the number of references and length of the review from becoming overly preposterous, arbitary exclusion of much interesting work was necessary. I apologize to those authors whose work may appear to have been slighted. BOOKS AND REVIEWS OF GENERAL INTEREST A monograph on ”standards in fluorescence spectrometry” contains useful discussions of such matters as criteria for defining the sensitivity of fluorescence spectrometers, spectral correction and quantum-yield measurement procedures, and stray light effects in fluorometry (A2). Mielenz has edited a monograph entitled ”Measurement of Photoluminescence”, dealing with radiometric calibration, spectral correction techniques, measurement of luminescence photon yields, and data handling in fluorometry in a highly authoritative manner (A3). Chapters on luminescence spectrometry and the formation and decay of electronically excited states in a lengthy treatise on experimental methods in photochemistry and photophysics are of interest (A4). Lengthy, but very readable, chapters on the use of lasers in luminescence spectrometry by Wright (A5) and Harris and Lytle (A6) are valuable. Instrumentation and measurement procedures in luminescence spectrometry have been reviewed by Mielenz ( A n . The 1983 Chemical Society “Specialist Periodical Report” on photochemistry contains a 156 R
chapter on “Developments on Instrumentation and Techniques” which contains much material related to the practice of fluorescence and phosphorescence spectrometry (A8). Warner and McGown have reviewed various aspects of the analysis of mixtures by fluorometry, with special emphasis on time- and phase-resolved fluorescence, selective modulation, excitation-emission matrices and synchronous fluorescence, and data reduction techniques (A9). Ho, Rollie, and Warner have surveyed “multiparametric detection” in fluorometry, emphasizingthe combined use of the large number of variables (spectral, temporal, and polarization) inherent in the luminescence phenomenon to extract useful analytical data from mixtures (AIO). A review of recent developments in the analytical applications of phosphorescence by Hurtubise includes consideration of the various room-temperature phosphorescence phenomena, instrumentation for both low- and room-temperature phosphorescence, and synchronous phosphorescence techniques ( A l l ) . Fink has provided an overview of chemical reactions, using nonfluorescent derivatization reagents, for producing fluorescent molecules from nonfluorescent analytes. Such procedures are to be distinguished from fluorescent labeling procedures (e.g., those involving fluorescamine or dansyl chloride) in which the same fluorescent structural entity is present in both the reagent and the product (A12). A review of spectrometric methods for analysis of polycyclic aromatic hydrocarbons contains detailed discussions of the many different luminescence techniques which have been applied to this problem (A13). A review (in German), with 208 references, surveys the use of fluorometric methods in the quantitative analyses of organic compounds (A14). Schulman and Sturgeon have reviewed the use of fluorescence and phosphorescencein pharmaceutical analysis in great detail (A15). A short survey of the applicability of fluorometry to routine clinical analyses includes reagent cost comparisons (with UV-visible absorptiometry) and consideration of appropriate fluorometric instrumentation for routine clinical use (A16). The use of fluorescence methods in forensic science has been reviewed (A17). A short review of fluorescence procedures for speciation of aquatic pollutants (especially humic materials) has been given by Seitz (A18). The luminescence of organic molecules under high pressure has been reviewed (A19). The fluorometric determination of inorganic anions has been reviewed in detail by Gomez-Hens and Valcarcel (A20). Thorburn Burns has surveyed the analytical use of‘ the fluorescence of inorganic compounds (A21). A review of the application of luminescence methods to inorganic analysis contains 746 literature citations, many of which are to Eastern European publications (A22). Many other reviews, dealing
o o o 3 - 2 7 o o / a 4 / o 3 5 ~ - i ~ ~ ~ ~ o 60. ~1984 o ~ oAmerican
Chemical Society
