Anal. Chem. 1982, 5 4 , 276 R-293 R (5Q) Connors, W. J.; Sarkanen, S.; McCarthy, J. L. Holzforschung 1980, 34, 80-85; Chem. Abstr. 1980, 93, 97090k. (6Q) Cunnlngham, A. F.; Heathcote, C.; Hillman, D. E.; Paul, J. I.Chromatogr. Scl. 1980, 13 (Llq. Chromatogr. Polym. Relat. Mater. 2), 173-196. (7Q) Holt, C.; Mackie, W.; Sellen, D. B. Polymer 1978, 19, 1421-1426. (8Q) Lindstrom, T. Colloid Polym. Scl. 1979, 257, 277-285. (9Q) Lora, J. H.; Wayman, M. J . Appi. Polym. Scl. 1980, 25, 589-596. ( l o a ) Maansson, P. ”Ekman-Days 1981, Int. Symp. Wood Pulping Chem.”; SPCI: Stockholm, 1981; Voi. 5, pp 94-95; Chem. Abstr. 1981, 95, 117308j. (11Q) Minor, J. L. J. Liq. Chromatogr. 1979, 2, 309-318. (12Q) Sjobom, R. A.; Oresten, H. G. Propellants Explos. 1980, 5 , 105-110. (l3Q) Tae, I.M.; Inagakl, H. Polymer 1980, 21. 309-316. (14Q) Vyas, N. G.; Shashikant, S.; Patel, C. K.; Patel, R. D. J. Polym. Sci., Polym. Phys. Ed. 1979, 17, 2021-2029. (150) Dreher, T. W.; Hawthorne, D. B.; Grant, B. R. J. Chromatogr. 1979, 174, 443-446. (16Q) Ekekov, Y. A.; Strakhova, N. M.; Kalal, J.; Peska, J.; Stamberg, J. J. Polym. Sci., Polym. Symp. 1981. 68, 247-251. (l7Q) Lynn, M. M.; Stannett, V. T.; Gilbert, R. D. J . Polym. Sci., Polym. Chem. Ed. 1980, 18, 1967-1977. (180) Meuser, F.; Klingler, R. W.; Niediek, E. A. Ber. Tag. Getreidechem. 1979, 30, 52-60; Chem. Abstr. 1980, 93. 28135s. (l9Q) Papantonakis. M. Coat. Conf. 1980, 81-86; Chem. Abstr. 1980, 93, 48947m. (20Q) Stone, R. G.; Krasowskl, J. A. Anal. Chem. 1981, 53, 736-737. (21Q) Waniska, R. D.; Kinsella, J. E. J . Food Sci. 1980, 45, 1259-1261. (22Q) Hashlmoto, T.; Sasakl, H.; Aiura, M.; Kato, Y. J . Polym. Sci., Polym. Phys. Ed. 1978, 16, 1789. (230) Ibdam, N.; Furusawa, K.; Yamaguchl, N.; Komuro, S. J. Appi. Polym. Sci. 1979, 23, 3631. (24Q) Onda, N.; Furusawa, K.; Yamaguchi, N.; Komuro, S. J . Appi. Polym. SCi. 1979, 23, 3631-3638. (25Q) Onda, N.; Furusawa, K.; Yamaguchi, N.; Tokiwa, M.; Hirai, Y. J. Appl. Polym. Scl. 1980, 25, 2363-2372. (26Q) Alfredson, T.; Wehr, C. T. Polym. Prepr., Am. Chem. Soc., Div. Polym. Chem. 1980, 21 (2), 103-104. (27Q) Barford, R. A,; Sliwlnski, B. J.; Rothbart, H. L. Chromatographia 1979, 12, 285-288. (28Q) de Ligny, C. L.; Gelsema, W. J.; Roozen, A. M. P. J. Chromatogr. Sci. 1981, 19,477-479. (29Q) Dimenna, G. P.; Segall, H. J. J. Liq. Chromatogr. 1981, 4 , 639-649. (30Q) Gooding, D. L.; Chatfleld, C.; Coffin, 8. Am. Lab. (Fairfield, Conn.) 1980, 72 (E), 48-61. (31Q) Haller, W.; Gschwender, H. G.; Peters, K. R. J . Chromatogr. 1981, 211, 53-59. (320) Imamura, T.; Konishl, K.; Yokoyama, M.; Konishl, K. J . Liq. Chromatogr. 1981, 4, 613-627. (33Q) Leach, B. S.; Collawn, J. F.; Fish, W. W. Biochemistry 1880, 19, 5741-5747. (34Q) Montelaro, R. C.; West, M.; Issel, C. J. Anal. Biochem. 1981, 114, 398-406.
(35Q) Murakami, K.; Ueno, N.; Hirose, S. J . Chromatogr. 1981, 225, 329-334. (38Q) Molko, D.; Derbyshire, R.; Guy, A.; Roget, A.; Teoule, R.; Boucherle, A. J. Chromatogr. 1981, 206, 493-500. (370) Nelson, M. Altex Chromatogram 1980, 3 , 4-5. (38Q) Okazaki, M.; Shlraishi, K.; Ohno, Y.; Hara, I.J . Chromatogr. 1981, 223, 285-293. (39Q) Renck. B.; Einarsson, R. J. Chromatogr. 1980, 797, 278-281. (40Q) Rivier, J. E. J . Chromatogr. 1980, 202, 211-222. (41Q) Shmukler, H. W.; Soffer, E.; Kwong, S. F. Report, Rept. No. NADC79085-60, NTIS NO. AD-A069 626/OSL, 1979. (42Q) Shmukler, H. W.; Kwong, S. F.; Soffer, E., Zawryt, M. G. Report, Rept. NO. NADC-79008-60, NTIS NO. AD-A067 327/7SL, 1979. (43Q) Somack, R.; McKay, V. S.; Giles, J. W. ACS Symp. Ser. 1980, No. 138 (Slze Excluslon Chromatogr.), 285-297. (44Q) UI, N. J . Chromatogr. 1981, 215, 289-294. (45Q) Wehr, C. T.; Abbott, S. R. J . Chromatogr. 1979, 165, 453-462. (46Q) Welinder, B. S. J . Liq. Chromatogr. 1980, 3, 1399-1416. (47Q) Bixby, B. Report, OWRT-A-048-NH, NTIS No. PB81-113896, 102 pp, 1979; Chem. Abstr. 1981, 95, 49082d. (480) Hart, 0. 0. Water Sci. Techno/. 1981, 13, 525-536. (49Q) Jewett, M. A.; O’Brlen, D. J. Proc.-AWWA Annu. Conf. 1979 (Pt,l), 531-538; Chem. Abstr. 1980, 93, 13763211. (50Q) Rodgers, D. H.; Kopfler, F. C.; Bombaugh, K. J.; Ogle, L. D. Prepr. Pap., Am. Chem. SOC., Div. Environ. Chem. 1979, 19, 59-62. (51Q) Thurman, E. M.; Malcolm, R. L. Envlron. Sci. Techno/. 1981, 15, 463-466. (52Q) Toledo, A. P. P.; Jordan, I.; Ferreronl, M. C. An. Acad. Bras. Cienc. 1980, 5 , 31-33; Chem. Abstr. 1980, 93, 135494e. (53Q) Barth, H. G. J . Llq. Chromatogr. 1980, 3 , 1481-1496. (54Q) Barth, H. G.; Smith, D. A. J . Chromatogr. 1981, 206, 410-415. (55Q) Chow, C. D.; Jewett, G. L. J . Llq. Chromatogr. 1980, 3 , 419-426. (56Q) Domard, A.; Rlnaudo, M.; Rochas, C. J . Polym. Sci., Phys. Ed. 1979, 17, 673-681. (57Q) Dubln, P. L.; Levy, I. J. Polym. Prepr., Am. Chem. Soc., Div. Polym. Chem. 1981, 22 (l), 132-134. (58Q) Hashimoto, T.; Sasaki, H.; Alura, M.; Kato, Y. J . Polym. Sci., Phys. Ed. 1978, 16, 1789-1800. (59Q) Kato, Y.; Sasaki, H.; Aiura, M.;Hashimoto, T. J. Chromatogr. 1978, 153, 546-549. (60Q) McCormick, C. L.; Park, L. S. J. Appi. Polym. Sci. 1981, 26, 1705-1 7 17. (610) Forget, J. L.; Booth, C.; Canham, P. H.; Duggleby, M.; King, T. A. J. Polym. Sci., Phys. Ed. 1979, 17, 1403-1411. (62Q) Sasaki, T.; Kushlma, K.; Matsuda, K.; Susuki, H. Bull. Chem. SOC. Jpn. 1980, 53, 1864-1866. (63Q) Akltt, J. W.; Farthlng, A. J . Chem. Soc., Dalton Trans. 1981, 7, 1606-1 608. (64Q) Messer, B.; Yarnltzky, C.; Schmuckler, G. Anal. Chim. Acta 1981, 126, 229-232. (65Q) Noda, H.; Saitoh, K.; Suzukl, N. Chromatographia 1981, 14, 189-191. (66Q) Parrott, L.; Young, J. F. Cem. Concr. Res. 1981, 11, 11-17.
Atomic Absorption, Atomic Fluorescence, and Flame Spectrometry Gary Horlick Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada T6G 2G2
The first year covered by this review (1980) saw the celebration of the 25th anniversary of Alan Walsh’s landmark paper entitled “The Application of Atomic Absorption Spectra to Chemical Analysis” published in Spectrochimia Acta (30A). To commemorate the publication of this paper a two-part special issue of Spectrochimica Acta has been published with the general title “Atomic Absorption Spectroscopy, Past, Present and Future” (22A, 23A). The papers in these two issues are highly recommended to all working in the general area of analytical atomic spectroscopy. To highlight a few: In an excellent article Walsh (31A) presented some personal recollections and speculations on atomic absorption spectrometry. He indicated that the conception of atomic absorption was slowed over the decades before 1955 by such factors as a lack of photoelectric detection, a misinterpretation of Kirchoff‘s law, thinking only of continuous sources and a failure to “avoid being stupid”. The key was the hollow 276 R
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cathode lamp which put the resolution in the source and allowed, although one would not necessarily believe so today when viewing modern commercial instruments, very simple measurement systems to be utilized. Since 1955 essentially only two major advances have occurred, electrothermal atomization and the N20-C2H2flame although the modern microprocessor-based instruments could well be added to this list. What has expanded is the range of applications and it has been a continuing source of amazement and even surprise to Walsh that the method has been so important in the analysis and characterization of the elemental composition of such a wide range and diversity of samples. A companion paper to the introductory comments of Walsh is a reprint of his 1974 A-page article from Analtyical Chemistry entitled “Atomic Absorption Spectrometry-Stagnant or Pregnant” (32A). The issue continues with general interest papers by Willis (34A) on recollections of the early days of atomic ab0 1982 American Chemical Society
ATOMIC ABSORPTION. ATOMIC FLUORESCENCE, AND FLAME SPECTROMETRY
Qary norlsk is a ole^ 01 Ehemisby at me univwrsny of Alberta. He recsived hls 0,s. &gee ha me IJnivaonv ot Abeam in 1965 and hla R.D.degree horn hUnivnsny 01 ~iiinoish 1970 under hdkectlon of H. v. Maimalndt He Joined me 1acuny at hUnivnrny 01 A i m in Dscember 1969. Research interesls are in me general area of anawical s p e c b o s ~ p ywlth emphasis an me development and applkatkm 01 atomic
spectochamicai measurement systems. A cment locus l a several 01 group's research projects b me inductivehl coupled , plasma (ICP). studies under way include spatial characterizatmn ot ICP mission. development 01 new sample intrcd~ctlonsystems lor the ICP based on laser vaporkatbn. elecbomwmai vapotbatiar and direct wmpb i n m . assessmen1 01 me analytical capabilnies 01 Ne-Ar and 0,Ar mixed gas I C P s and mea~~rement 01 me noise characteristics 01 me ICP. Many of mew studies have been lacllltated by utilizatbn of unique specnochemical measurement systems developed in M I labaatory based on photcdlode arrays and Fourier transform spectrometers. specific pmwts are aim under way in mese two areas aimed at the further development of photcdkde array based instrumentatin 1w munichannel specnometric measurements and tor spectraihl resobed spathi distributbn measurements and hdeveiopmem and application 01 ~ouriertransform spectrometers lor me measurement 01 atomic emidon spectra. photoacwstic spectra. and I R emission spectra. Throughresearch projects Cmebtion-based measurement and out ~everal01 dam handling techniques are being utilized and minicomputer- and microproCBSSM-~BSB data ~ acquirMcn systems are Standard Subcomponents 01 most experiments. He i s h North American edna of Specnochimica Acta. Parf B . and is a member of the ednorhl boards of Applied Spclroscopy. Mkrochimica Acts. and Canadian Jownal of Speclroscopy.
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sorption spectroscopy. some reminiscences and lessons to be learned by Alkemade (/A) and a brief history of atomic absorption spectroscopy by Koinyohann (IIA). Fuwa and Vallee @A) also add some historical perspective on cyanogen flame emission and long pathlength atomic absorption spectrometry. The rest of the papem in the special h u e are current technical papers and are referenced in appropriate sections of this review. I n addition M this special issue, another special issue of Specrrorhimica Acta was devoted to atomic spectroscopy in Japan (24A). This iasue was ublished on the occasion of the 9th ICAS and XXII CSI helain Tokyo in September of 1981 and contains many interesting technical papers which, again, are cited in appropriate sertions of the review. Of general incerest however is a history of spectrochemical analys!s in Japan presented by Fuwa and Kamada ( 7 A I . Finally I, vov (Ih'A) has also written a summary paper on the occasion of the 25th anniversary of analytical atomic absorption spectrometry and Koirtyohann (I2A) has reviewed the rurrent status and future needs in atomic absorption instrumentation. The aim of this review, as stated 2 years ago 1 9 4 is t n he reasonat)ly complete in dealing with the fundmental aspects of the field and representative. but not comprehensive, with the applications aspect of the field. I n addition, journal coverage has k e n limited, although not completely, to those thought to he of reasonable accessibility to the majority of the readers of Analyrical Chmirfr). The Rt,yal Society of Chemistry continues to publish its nimprehensire rewews r6A) although the $92.00 prire tag was a hit steep this time around. Lawrenre aLw rontinues u)cumpile semiannual bibliographies in atomic spertroscopy (13A-15A). In terms of hooks Van Loon (27A) authored one entitled "Analytical Atomic Ahsorption Spertroscopy: Selected Methods". Robindon (21A1 covered "Atomic Absorption Spectroscopy' i n the 2nd edition of the Elving, Meehan, and Kolthoff Treatise on Analytical Chemistry, and -Atomic Absorption Spertrometry Vol. 2, Application to Chemical Analvsis, 2nd Edition" by Pinta (I9A) appeared. Also of general interest is a dimmion of the health and safety aspects of analytical atomic ahsorption by Price 12bA1.an anirk on the formulation of standard analytical procedures by Van Dalen et al. t2fiA), and an inventory of atomic absorption npectroscnpic instrumentation by Rroekaert GA). From an educational point of view, prwedures for atomic absorotion exDerimenlq have heen oublished 14A. IOA. 18A) and a'series of professionally preparid slide presentations are available which were not mentioned in the last review (3A, 28A, 29A, 33A).
In general, the state of the field is pretty healthy. While one still looks over one's shoulder at the ICP, the basic simplicity of AA and hence, low cost, coupled with the power of electrothermal atomization are yet to be matched by the ICP. In fact the ICP has been proposed as a reservoir for AAS (27A) and atomic absorption measurements on I C P s have aided fundamental studies of metastable argon populations in an ICP (25A). In the last 2 years, major progress has been made in our understanding, at a fundamental level, of electrothermal atomization and we see a beginning of the elimination of the abject emperism that has dominated this technique. New limits of detection are beine reached. oarticularlv_ bv atomic , fluorescence spectrometry, where the measure becomes 'numher uf atoms" rather than such a large unit as parts per billion (1:1@). An excellent general paper in this area entitled "Single Atom Detection" by Alkemade @ A ) is highly recommended. It is curious, in a way, that we have, to date, found detection limits in the parts-per-billion to parts-per-million range, an inordinately large number of atoms when one considers that single photon events can be detected with a photomultiplier tube. Perhaps we should readjust our sights and research goals down by a few orders of magnitude. Finally, I would like to comment briefly on events and developments that I see fundamentally altering the role and/or need of reviews such as these published by Analytical Chemistry. World wide data networks are now being contemplated and localized tests of such two-way data systems are now being carried out in several North American centers. Such systems will access "yellow papers", sports, news, banking, and general information data bases. So why not Chemical Abstracts. Some access now exists though DIALOG run by Lockheed Corp. and in fact most of the references in this review (author, title, journal) were found by utilizing this system. The data base can be searched from an on campus location and hits, if numerous, printed at Lockheed and sent by mail arriving in about a week. However, what one would like is access to tbis fde and abstract information at one's desk utilizing a small business computer such as the Apple. Then one could set up very customized searches and display desired abstracts under data base management control. Perhaps such a science data network will be a reality in a few years. Also optical disks (video disk) with single sided capacities of 10 gigabits are on the drawing boards. This would allow distribution of vast literature data files directly in a computer accessible format (a video disk the size of a phonograph record) that could easily plug into a computer in the scientific office. Well, such scenarios are not quite here, so on with the review. ~~
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ANALYTICAL FLAME EMISSION AND ATOMIC ABSORPTION SPECTROMETRY While undoubtedly the flame continues to be a very widely used source for analytical atomic spectrometric determinations, the reports of such work are now seldom seen in the analytical literature except for the area of atomic fluorescence spectrometry covered later in this review. In this section articles with primary emphasis on flame emission and absorption will be discussed. For an update on flame emission spectrometry the chapter by Syty in the second edition of the "Treatise on Analytical Chemistry" should be consulted (398). An interesting article discussing the combination of a miniature flame (N,O-C,HJ and a graphite cup atomizer has been published by Hughes and Fry (19B), and Warren (438) has published on a system of similar concept in which a tungsten filament vaporizer was used to introduce samples into an oxyhydrogen flame. Several fundamental and practical studies of flame systems continue to be carried out in Hieftje's laboratories at the University of Indiana. Relative free atom fractions in helium*xygen-acetylene and &acetylene flames have been measured (348). The helium-oxygen-acetylene flame is intermediate to the AIR C2H, and N,O/C,H, flames with a maximum temperature o 2812 K and it was suggested that it might be a good flame for atomic fluorescence spectrometry. Russo and Hieftje (318) studied the effects of gas composition and sheathing on velocity profiles of laminar analytical acetylene flames. Several schlieren photographs of flames are presented in this manuscript. Following on their fundamental work on desolvation of droplets in a flame, Hieftje and co-workers are now working on the deliniation of solute particle vaporization. An approximate model for the
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liberation and ionization of atoms from individual NaC1, KC1, and CsCl solute particles in flames has been presented (7B). Vaporization rate constants are presented. Several other laboratories have been active in basic emperial and theoretical studies of flame systems. Ramsey (30B) has published a theoretical model dealing with the effects of atom density distributions and concentration fluctuations (i.e., analyte flicker) in flame spectrometry and Li has continued his theoretical modeling of dissociation and vaporization phenomena in analytical flames (24B,25B). Bassyouni and colleagues (5B, 6B) discussed the effect of a 3-kG magnetic field on Lorentz collisions of Li, Na, K, Mg, and Ca in AIRCzHz flames and also studied spectral line broadening and shifts by collisions. In an excellent study Borgers et al. (12B) critically evaluated the particle track method of measuring flame rise velocity. Powdered mol bdinite (MoS,) was used to measure the rise velocity (15 ms-7) in a CO-AIR flame that has a temperature of about 2000 K. In a series of three articles Chang and Penner (8B,15B, 16B) carried out article size measurements using laser light scattering altiough the flames studied (CzH2/02, CzH6/02, CH4/02)are not of current majnr analytical interest. Critical to the practical utilization of flame methods is an understanding of and an ability to control vaporization interferences. A rather nice fundamental study of an old problem was presented by Smets (36B) in which the vaporization interferences of sulfate and phosphate anions on the calcium signal in flame atomic absorption spectrometry were studied. It appears that species such as CaO-S03 and 2Ca0.PzO5are formed and the standard addition method fails to correct for these effects. Switching to N20-C2H2from AIR-C2H2 solves the problem. Aggett and O’Brien (2B, 3B) present a good two-part fundamental study on the formation of chromiwn atoms in air-acetylene flames dealing with atom formation from pure chromium compounds in which they discuss the nature of the solid phase formed upon desolvation and the effect of matrix electrolytes. Kitagawa et al. (22B) also studied atomization processes and interelement effects on the flame emission (AIR-C,H2) of Cr and Fe. In a sense their work was an emission study of a normal atomic absorption flame. The excitation temperature and degree of atomization were determined. An interesting study on the determination of iron by atomic absorption spectrometry in AIR-C2H2 flames was presented by Thom son and Wagstaff (41B). In fuel-rich flames both Fe(I1) aniFe(II1) gave nonlinear analytical curves and they show that a fuel-lean flame was best with respect to linearity but a t a sacrifice of sensitivity. The inhibition release titration method has been used to study inteference effects in flame spectrometry (29B). Stojasnovic and Winefordner (37B) found that La reacts before Sr or Ca to release Mg from phosphate and Taddia (40B)used an inhibition titration procedure involving Ca and La for the determination of traces of titanium. Some determinations reported by flame methods include calcium in cement using strontium as an internal standard (17B),Fe in hernodialyzed liquids (4B),Li in small animal tissues (28B),and uranium with the addition of cobalt nitrate as an interference agent (35B). A somewhat fuel-rich NzOCzHzflame has been found useful for the improved determination of Hf, Nb, Ta, and Zr (42B). Two thorough studies on the determination of several trace elements in foodstuffs were published by workers at the Laboratory of the Government Chemist (18B). Digestion procedures, burners, height of radiation beam, flame conditions and extraction procedures were all studied. Metals studied included Cu, Fe, Mn, Zn, Co, Cr, and Ag. Ivanova et al. (20B) presented a procedure to extract Cu, Zn, Ni, Co, Mn, and Fe from alkali salts before flame atomic absorption determinations. Procedures for flame-based analyses offish tissue (IB),feeds (33B),dolomite (23B),vanadium pentoxide catalysts (44B),and aerosols (38B) have been presented. An extensive study of molecular emission in flames for the determination of F-, C1-, Br-, and I- was presented by Marquardt et al. (26B). Species investigated include InF, GaF, AlF, TlC1, TlBr, TlI, GaI, GaBr, InC1, and InBr with the conclusion that InX species were best. Flames studied included a H,-N2 diffusion flame, H,-AIR and propane-AIR flames. Several papers were published in the general area of molecular emission cavity analysis (MECA). These include 278R
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the determination of sulfite in soft drinks ( I I B ) ,studies on optimization and interference in sulfate and sulfur determi14B),and the determination of boron (13B)and nations (IOB, boron and selenium (9B). Two indirect determinations using MECA were reported. Amines were determined by reaction with formaldehyde-sulfite with subsequent observation of S2 emission (32B) and phenol was determined by generation of tribromophenol with the subsequent production of InBr and observation of emission at 376 nm in an AIR-H,-N2 flame (27B).
DEVELOPMENTS AND STUDIES IN INSTRUMENTATION, MEASUREMENT TECHNIQUES, AND PROCEDURE General Developments. Howarth et al. (15C) described the design and performance of an improved pneumatic concentric nebulizer and Routh (20C) presented results on its aerosol characterization. The aerosol was studied by using low angle forward scattering of laser light and parameters studied included impact bead position, spray chamber droplet conditioning, burner head temperature, nebulizer driving pressure, and uptake rate, overall quite a nice study of aerosol generation variables. Fernandez et al. (11C) discussed a new burner system and compared impact bead performance with the utilization of flow spoilers. Codding et al. (7C) presented a thorough characterization of a photodiode array spectrometer for atomic absorption spectrometry. The PDA system was electronic readout noise limited and had an overall sensitivity comparable to conventional spectrometers. An echelle monochromator system for the measurement of carbon furnance atomic emission signals was described (18C) and an effective scanning system for an echelle monochromator was developed ( 2 0 . A complete computer coupled atomic absorption spectrometer has also been described (18C). A new approach for a wavelengthspecific photoelectric detector has been described by Stephens (24C). Using a rotary valve, Patterson (19C)was able to modulate sample introduction into a flame at a rate of 0.2 Hz. Wavelength modulation was implemented by Michel et al. (17C) using a rotating quartz chopper with different thicknesses of quartz placed around the chopper. A unique modulation system for flame emission spectrometry was described by Downey et al. (9C)for the reduction of spectral interferences by selective spectral line modulation. A simplified design for an isolated droplet generator has been presented (21C). Such systems have, of course, been used for many fundamental studies of atomization processes in flames. A very elegant and potentially powerful experimental system for implementing numerous fundamental studies on flames has been described by Steinhoek and Yeung (23C). In this system spatial mapping of concentrations in a spectrochemical source is carried out by use of a collimated dye laser beam and a vidicon. The same approach was used to obtain spatially resolved temperature profiles of a flame (29C). Background correction in atomic absorption spectrometry continues to be a problem not yet fully solved (14C) and in fact is one of the major driving forces in the development a Zeeman systems reviewed later in this section. Dewalt et al. (8C) described a system for the correction of broad band background emission and absorption. Background absorption caused by organic solvents was studied by Betz et al. (3C). Vajda (27C) indicated that a matrix line within the band-pass of the monochromator can absorb during the background correction cycle and result in an over correction. Siemer (22C) described a modification to the BCGE Varian-Techtron background correction system that allowed accurate monitoring of the baokground absorption signal. In Part I11 of a review and tutorial discussion of noise and signal-to-noise ratios in analytical spectrometry Alkemade et al. ( I C ) discussed multiplicative noises. In an excellent paper Bower and Ingle (4C) presented an experimental and theoretical comparison of precision in flame atomic absorption, fluorescence, and emission spectrometry. At the detection limit AF and AE are limited by background emission shot and flicker noise and AA by flame transmission lamp flicker noise. At higher signal levels all methods are analyte flicker noise limited. Some noise power spectra are also presented. Liddell and Widly (16C) have compared single and double beam atomic absorption spectrometers from the point of view of
ATOMIC ABSORPTION, ATOMIC FLUORESCENCE, AND FLAME SPECTROMETRY
noise. The same limits as those found by Bower and Ingele are seen and at the detection limit the single beam instrument was slightly better. Harnly and Ollaver described an approach based on offline absorption measurements for extending the dynamic range of analytical calibration curves in atomic absorption spectrometry (12C). The off-line measurements were accomplished by using their wavelength modulated instrument, and families of analytical curves are presented. Epstein and Winefordner (IOC) simply used burner rotation to extend the upper range of AA. determinations, and their results show that precision is normally maintained. An interesting study on internal standardization in flame atomic absorption spectrometry was published by Takada and Nakano (25C). They studied atomization efficiencies degree of atomization as a function of temperature and absorbance as a function of water introduction in an attempt to establish criteria for selection of an internal standard. The standard addition method was critically studied by Timn et al. (26C) and an overview of signal and data processing for atomic absorption spectrometry was presented by Whiteside et al. (28C). Boyle and Ryan (6C, 6C) presented computer programs for standard addition methods. Sources. A major critical review of the hollow cathode discharge has been presented by Pillow (38C) and it is recommended reading for all using and studying these discharges. Excitation temperature i n the hollow cathode discharge were measured by Melw and Niemczyk (35C). Freeman et al. (32C) indicated that the As 193.76-nm line is subject to a spectral interference problem from Ne I1 193.89 and 193.01 nm in a Ne filled hollow cathode lamp. Parker et al. (37C) presented a procedure for regenerating old lamps by converting them to a demountable format. There is continuing and even growing interest in the pulse operation of hollow cathode type discharges. Araki et al. (30C) combined the pulsed mode with the additional application of a 150-MHz rf burst to a pulsed hollow cathode lamp just after the end of thie dc current pulse. Pulsed hollow cathode lamps for copper (Cu I 324.7 nm) (31C) and uranium (U I 591.5 nm) (34C) were all30 studied. A comparative atudy of‘hollow cathode lamps, electrodeless discharge lamps, and metal vapor discharge lamps for atomic absorption spectrometry was carried out by Mohamed and Petrakiev (36C). ’Waltern and Smit (40C) described thermostated rf excited (150 MHz) Cd and Zn electrodeless discharge lamps. Their intended use was for atomic fluorescence spectrometry. A simple method to re’uvenate Westinghouse EDL’s was descriibed by Siemer (396). Controlled temperature gradient lamps for As, Cd, P, K, Rb, Se, Na, S, and Zn were characterized by Gough and Sullivan (33C). In generd they were more intense than EDL‘s and exhibited sharper lines and, in particular, excellent lamps could be made for As and Se. Developments in Sample Introduction Techniques. In this section a number of developments in sample introduction techniques will be discussed. Systems applicable to both flames and electrothermal atomizers will be presented as many ideas are applicable to both systems. There is considerable interest in the introduction of small sample volumes into flames and plasmas. Cresser (52C) has reviewed the area of discrete sample nebulization in atomic spectroscopy and as well has studied, along with Malloy and Keliher (67C), the changes in efficiency (an increase) of pneumatic nebulization when introducing small discrete samples. An area where the analysis of small volumeEi is critical is in the analysis of biological fluids of infants. Makino and Takahara (66C) applied discrete nebulization to tlhe determination of plasma copper and zinc in infants utilizing sample volumes in the 10-20 pL range. Uchida et al. (83C) used a small Teflon funnel to introduce 75-100-pL aliquiots into a flame or plasma, and also with a long absorption tube in combination with discrete nebulization he achieved graphite furnace type sensitivities with 100 WLof solution (82C). Such sample introduction systems generate, of course, transient signals and Uchida and colleagues have presented measurement systems for correctly integrating such signals (58C, 84C). A simple but very unique device has been presented by Shabushnig and H ieftje (77C) that is capable of dispensing small volumes of liquid samples with high precision and accuracy (40nL delivered at a precision of *1.5%). Such a
system has clear potential application in several atomic spectrometric systems. Samples placed on and/or adsorbed to metal wires have been introduced into both flames and graphite furnaces. The platinum-loop in flame sample introduction system has been discussed by Berndt and colleagues (43C, 44C, 59C) and tungsten wires have been used to introduce samples into a graphite furnace (68C),graphite rods (87C),and heated quartz tubes (48C). In the graphite furnance work (68C) the basic goal was to be able to introduce a sample into a furnance that had already reached a constant preset temperature while the heated quartz tube system (48C) although limited to a maximum temperature of 1500 K allow some basic studies of atomization with controlled temperatures and atmospheres. Several workers have combined electrochemical preconcentration with wire sample insertion systems. Czobik and Matousek (53C) discussed electrodeposition on a tungsten wire for separation and preconcentration of Cd, Zn, Ag, Pb, and Cu from NaCl solutions. A 1.5-15-fold improvement was realized. The wire was run in a carbon rod furnace. Batley and Matousek (41C) also investigated direct electrodeposition of Cr on pyrolytic tubes. Such a step allows speciation of Cr I11 and Cr VI. Holen et al. (60C, 61C) investigated the electrochemical preconcentration of Se on a Pt wire filament with subsequent insertion into a flame with the application of iR heating to the Pt wire. Torsi et al. (80C) described an interesting system in which in situ electrolytic preconcentration on a glassy carbon furnance from flowing solutions was possible. Pb in seawater was analyzed by using their system. Another approach to sample preconcentration is to continuously apply a nebulized sample to a heated (low temperature) graphite rod or furnace. King et al. (64C) utilized this approach to determine aluminum in blood serum. Chaunsaz et al. (49C) also investigated this approach with both low- and high-temperature furnance application. With direct application to the high-temperature continuously heated furnace desolvation was necessary and there were many interferences. Direct aerosol deposition on the low temperature furriance as a preconcentration step with subsequent hightemperature atomization worked quite well. In the same group (West a t the Macaulay Institute for Soil Research) work continues on “atom-trapping” in a flame using a water-cooled silica tube as a “preconcentration”techinque (62C,63C). They believe that sputtering may, in part, be a mechanism for removal of trapped species and studied many elements that were released as metals, silicates, or oxides. With this system sensitivity improvements of 1 to 2 orders of magnitude were obtained for As, Cd, Pb, Se, and Zn. Finally with respect to preconcentration two approaches to electrostatic accumulation havie been developed (67C, 79C). We are beginning to see the marriage of flow injection analysis techniques and several spectrochemical methods (42C, 56C, 81C). Such a combination can result in a very powerful and efficient sample introduction system and work in this area whille generally at a preliminary or first application stage is sure to rapidly expand. In a somewhat related area Ure et, al. (85C) have developed a three-channel flame atomic absorption/emission spectrometer for the determination of Ca, Mg, and Na. Utilizing two nebulizers ionization suppressant can be added via one of them and as well; with a branched input to the second nebulizer, La can be added as a releasing agent on stream. Similar in concept was the multichannel peristaltic pump system of Layman et al. (65C) with which sample, buffering or releasing agent, and or diluent could be simultaneously delivered at a considerab e savings in sample preparation time. Without question one of the most interesting sample introduction systems presented was that of Cox and Carnahan (50C, 5 1 0 Their system consisted of a tubular cation exchange membrane that was simply coiled in the solution to be analyzed. A dialysis solution is continuously pumped through the tube and into the nebulizer. Sampling consists of Donnan dialysis of an ion into the coiled tube out of the sample solution where it is then directly transported to the nebulizer. Clearly this concept has many exciting possibilities and awaits innovative implementation. On the heals of the success and wide spread utility of hydride methods some researchers are developing analogous sample introduction systems with the goal of more wide spread applicability. Black and Browner (45C) studied the use of
i
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ATOMIC ABSORPTION, ATOMIC FLUORESCENCE, AND FLAME SPECTROMETRY
volatile metal-chelate systems (fluorinated P-diketonates) for the introduction of Fe, Zn, Cu, Mn, and Cr into an ICP. Such an approach should also be applicable to flame based systems. Vijan (86C)presented some very preliminary results for the introduction of Ni as its volatile carbonyl. Laser vaporization of samples for spectrochemical analysis has taken on many forms over the years with most systems developed around emission techniques. Recently two laboratories have developed laser vaporization sampling systems coupled to atomic absorption measurement systems. In one system the vaporized sample (ruby laser) is carried in an argon stream to a hot graphite furnace (55C). The other system (78C) is based on a YAG laser and is used as an AA microprobe in histochemistry. Some new studies have also been reported that used the so-called “Delves” cup method. The method has been automated and applied to the determination of Pb in urban air particulates (72, 73C). A disk of the cellulose filter used to collect the particulates is simply punched out, placed in a nichrome microsampling cup, and inserted into an AIR/C2H2 flame. Ag, Pb, and Cd have also been determined by using a Delves cup approach in combination with a quartz tube (47C)and open carbon cuvettes in a flame have been used for the determination of beryllium (TIC). It remains quite difficult to successfully introduce inhomogeneous samples into atomic spectrochemical sources such as flames and plasmas. Emulsified oil-water mixtures have been analyzed (determination of Pb in gasoline) with the object of being able to use aqueous inor anic standards (75C). Such an approach has also been applier! to the determination of Zn in undecenoate ointments (74C) and Ca in lubricating oils (54C). Slurries containing a large amount of undesolved solids (animal tissue) have been introduced directly into flames after homogenization by using a Babington nebulizer (70C) and Fuller et al. (57C) have compared flame, electrothermal, and ICP atomization techniques for the direct analysis of slurries. Eisentrant’s group has shown [Saba et al. (76C)l that it is very difficult to transport iron particles in wear metal oil samples through typical nebulizer-spray chamber arrangements. In the 7-14 pm level only 62% of the iron particles make it to the flame or plasma. A disolution procedure using HF-aqua regia with ultrasonic agitation solved their problem (46C). Aerosol Characterization and Studies. Several fundamental studies on aerosols with specific reference to atomic analytical methods have been carried out by Browner and his colleagues. An aerosol monitoring system for the size characterization of droplet sprays produced by pneumatic nebulizers has been described by Novak and Browner (95C, 96C). It consists of a cascade impactor in series with an electronic aerosol analyzer and had a size range from 0.1 to 10 cLm. The importance of the aerosol transport system is stressed by these authors. Cresser and Browner (9OC) described a method by which aqueous droplets in the range of 05-10 pm in diameter could be studied in cascade impactor systems with minimal evaporation effects. One simply uses high salt (10000 pg mL-l Na) solutions which stops evaporation of the droplets. Cresser and Browner (91C) also studied the effect of impact beads, mixer paddles, and auxiliary oxidant on droplet distributions using the standard Perkin-Elmer system for flame spectrometry [see also the papers by Fernandez et al. ( I I C ) and Routh (2OC)l. ,Boom, Cresser, and Browner also presented a very interesting article on droplet size distribution effects caused by the evaporation characteristics of various organic solvent aerosols (89C). Mohamed and Fry (93C) and Mohamed et al. (94C) characterized and utilized a commercial (Leeds and Northrup) laser Fraunhofer diffraction system for aerosol droplet size measurements. This system was useful in the 2-200 pm range. Finally the effect of detergents (88C) and surfactants (92C)on atomic absorption signals was studied. The surfactants (sodium dodecyl sulfate, SDS, and dodecyltrimethylammonium chloride, DTAC) altered droplet size resulting in improved sensitivity. Extraction. Many examples of extraction procedures are presented in the applications section later in the review. In this section a few articles are highlighted to emphasize extraction systems, schemes, or studies. Clark and Viets (97C) described a multielement extraction system for the determination of 18 trace elements in geochemical samples. The key reagent is methyl isobutyl ketone-amine syner gistic 280R
ANALYTICAL CHEMISTRY, VOL. 54, NO. 5, APRIL 1982
iodide complex or MAGIC as they liked to call it and Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Ga, In, T1, Sn, Pb, As, Sb, Bi, Se, and Te can all be separated at once from interfering matrices. Clark and Viets (98C) also describe back-extraction procedures associated with their separation scheme. The stability of APDC-MIBK extracts was studied by Subramanian and Meranger (103C)and the accuracy of acid extraction (90% HN03-10% HC1) for trace metals in sediments was studied by Sinex et al. (102C). A complex scheme was presented for extraction and determination of Pt, Pd, Rh, Ir, and Au in platinum metals (99C). Magnusson and Westerlund described general purpose dithiocarbamate-based solvent extraction procedures combined with back-extraction for trace metal determinations by atomic absorption spectrometry (IOOC). An automated extraction system for flame atomic absorption spectrometry was described by Nord and Karlberg (101C). Liquidlliquid extraction from an aqueous phase to an organic phase was automated with subsequent injection of an organic plug into a flowing aqueous stream. Magneto-optic Phenomena i n Analytical Atomic Spectrometry-Zeeman, Faraday, and Voigt Effects. There has been continued strong interest in the application and development of magneto-optic effects to atomic spectrochemical measurements. The main effect of interest remains the Zeeman effect but both the Voigt effect and the Faraday effect are now being extensively investigated. In a detailed mathematical paper Kankare and Stephens (118C) analyzed the Zeeman, Faraday, and Voigt effects in an effort to provide a unified theory of magneto-optic phenomena as applied to analytical atomic spectroscopy. Stephens (129C) also presented a major review on Zeeman modulated atomic absorption spectroscopy as did Yasuda et al. (13IC)and De Loos-Vollebregt (106C). In the last 2 years there has been considerable interest in the further development of commercial Zeeman-based atomic absorption instruments (pioneered by Hitachi) as the background correction capabilities of such instruments are, in many cases, clearly superior to the continuum source background correction systems. Fernandez et al. (111C, 112C) of Perkin-Elmer Corp. compare 44 elements with respect to background correction and found many examples of the superiority of the Zeeman method over continuum source approaches. Carnrick et al. (105C), also from Perkin-Elmer, present a thorough study of the conditions for the determination of manganese in seawater utilizing Zeeman background correction in conjunction with the L’vov platform. Brodie and Liddell (104C),from Varian Techtron, present results for 66 elements and in general the Zeeman method provided better background correction than D2 lamp methods but was, in certain situations, susceptible to double valued analytical curves. Work also carried out at Varian Techtron by Liddell and Brodie (126C)was also presented detailing the application of a modulated magnetic field (longitudinal field) to a graphite furnace for Zeeman effect measurements that resulted in significantly better background corrections than previous configurations. De Loos-Vollebregt and De Galan (109C)also presented the design and performance of an ac modulated magnet for Zeeman effect studies. It was a 10-kG magnet, modulated at 50 Hz and dissipated about 0.7 kW. Background levels of up to 2 absorbance units could be corrected. De Loos-Vollebreght and De Galan (107C, 108C) also presented results of a detailed study of the shape of analytical curves in Zeeman Atomic absorption spectroscopy. Strong ac modulated magnetic fields were desirable, but absorption maxima were seen as a potential problem. In some configurations of the Zeeman AA experiment the source is placed in a magnetic field rather than the analyte atomic vapor. However a hollow cathode lamp cannot be operated at dc in a magnetic field. Oishi et al. (I28C)showed that a hollow cathode lamp could be operated at an rf modulation frequency of 100 MHz in a 3.8-kg field and provide a stable output signal. Koizumi et al. (125C) presented a Zeeman instrument with a magnet around a flame cell and showed that very accurate background correction was possible, in a sense, an ideal double beam system. Koizumi et al. (224C)showed that the Zeeman shifted Zn 213-nm line could be used for the determination of SO2 and not be sensitive to scattering caused by smoke particles, In the atomic absorption analysis of biological fluids,
ATOMIC ABSORPTION, ATOMIC FLUORESCENCE, AND FLAME SPECTROMETRY
Table 1. Determinations of Specific Elements A1 Ag
wood pulp liquors Cu-Pb metalr; and alloys and in Zn and Se
Au Au Au B Be Bi Ca Ca Cd
geological materials anode slime river water meterorites water phosphate rock lubricating oils silicates
Co( 11)
seawater
co
cu
cu Cr Cr( VI) Cr Cr cs
Eu Ge, V, Ti Li Mo Mo
P P Pb Pb Pb Pb Pb Pb Pb Pd Pr Sn Sn Sn
Tl Zn, Pb
comments
imatrix
element
ores, rocks, iron, steel, nonferrous alloys river and seawater silicates
extraction of Ag as tri-n-octylmethylammonium-AgBr
19E 25E 39E extraction procedure (TOA, TOMA (Br)) 40E 4 2E flotation separation 28E 17E 9E KOH in 2-ethylhexanoic acid as an ionization suppressor 31E fluoboric-boric acid matrix Co(II), Co(III), CN- added 14E preconcen tration with 1-nitroso-2-naphthol 37E 5E extraction, Cu plated out of Zn dust 2,9-dimethyl-l,lO-phensmthroline 2E 22E, 23E EDTA to control chloride interference extraction with thiosemicarbazide 43E wet ash and extraction 7E comprehensive study, tested on a large number of reference materials 13E coprecipitant with stannous chloride and Ilg
monitor nuclear plant, removed Fe, Co good introduction isotope abundances, 6Li hollow cathode lamp
botanicals ores, iron and steel edible oils biological materials phosphate matrix geostandard rocks drinking water rat whole blood canned foods preserved duck eggs canned grapefruit juice
ref 30E 3 8E
comprehensive study, a-benzoinoxinol or xanthate extraction lanthanum-2-4-pentadionate added charing temperature raised by phosphoric acid matrix 900-2600 “C dithizone extraction ammonium tetramethylenedithiocarbamate Triton X-100, TMAH sampling compared to anodic stripping voltammetry
16E 24E 34E 8E 29E 11E 33E 21E 6E 36E 27E 1E 35E 20E 32E 15E
PVC compounds environmental, biological and water samples ores, iron, steel and nonferrous alloys minerarls, coal
new method for HGA-2200
18E 26E 10E
comprehensive study, separation, and extraction as the iodide
12E
separation procedure AG50W-X8 cation-exchange separation
3E 41E
background correction may be a serious problem. Frigieri and Trucco (113C) illustrated the utility of Zeeman-based background correction to the analysis of blood plasma. Also Magyar and Vonmont (127C) presented examples of matrices (0.1 M KNOBor NaC1O4 and urine) where deuterium lamp background correction failed and a Zeeman-based approach succeeded. Several interesting papers have appeared discussing the application of the Fraday and/or Voigt effects to analytical atomic spectrometry. The term “coherent forward scattering” is also used in reference to the Faraday and Voigt effects. The basic effect is the rotation of polarized light by atomic vapor which is placed in a magnetic field and thus another name seen associated with the field is “atomic magneto-optical rotation spectroscopy”. A good beginning paper is that by Ito (116C) in which he discusses a continuum source based system for coherent forward scattering. With a continuum source multielement analysis is possible and Yamamoto et al. (130C) and Debus et al. (IIOC)further discussed this aspect of these measurement systems. Several analytical applications of Faraday and Voigt effect systems have been presented including the determination of copper and P b in steels, zinc, and tin (114C, 115C), the determination of Sb, Bi, Ag, and Cu using a pulsed hollow cathode lamp (123C), the determination of P b by electrothermal atomization illustrating background correction capabilities (122C), and the determination of Ag (120C). An added dimension was provided by Yasuda and Murayama (13.2C) who spatially resolved the atom density distributions in a graphite tube furnace using coherent forward scattering simply by changing the magnet position.
In another interesting paper Jolly and Stephens (117C) constructed a Voigt effect filter for the sodium 589-nm line. Finally some comparisons of the capabilities and characteristics of Faraday, Voigt, and Zeeman effect instruments have been presented (119C, 121C). Laser-Enhanced Ionization Spectrometry. The general area of resonance ionization spectroscopy was outlined and reviewed by Hurst (136C). In the specific area of laser-enhanced ionization spectrometry in flames Havrilla and Green (135C) and Green et al. (134C) studied electrode geometries and electrical interferences. Flat electrodes tended to be superior. Turk (138C) studied matrix induced ionization interferences which were found to be very severe although running the laser beam close to the cathode surface helped somewhat. Trask and Green (137C) showed that mineral acids could produce both enhancements and suppressions. van Dijk et al. (133C) studied the two-step laser-associated ionization of sodium in a hydrogen-oxygen-argon flame and Zalewski et al. (139C) used the optogalvanic effect (old name now) as a detector for intracavity atomic absorption in a CW dye laser.
ELECTROTHERMAL ATOMIZATION PERFORMANCE STUDIES AND TECHINQUE DEVELOPMENT Performance Characterization. Considerable research
effort is now being applied to fundamental studies of electrothermal atomization and powerful techniques such as mass spectrometry (360) are even being coupled to furnace systems in order to study analyte vaporization characteristics. Frech ANALYTICAL CHEMISTRY, VOL. 54, NO. 5, APRIL 1982
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ATOMIC ABSORPTION, ATOMIC FLUORESCENCE, AND FLAME SPECTROMETRY
-
Table 11. Determinations of Elements in Specific Matrices matrix Ag (high purity) boron oxide brewing brewing- beer environmental atmospheric particulates soil dust, fiberglass general samples food vegetable oils chewing gum rice kernel foods foods, liver forensic gunshot residue gunshot residue gallium (high purity)
elements
comments isopropyl-N-methylthiocarbamineseparation
Cr, Cu, Fe, Ni
overview article
Zn, Cu,Fe, Pb
sampling As by hydride
Pb, Zn, Cd, As Cd, Mn, Ni, Ag Fe
solvent system consisting of 4-methyl-2-pentanone and ethanol, aqueous inorganic standards
Ni, Mn, Cu, A1
distribution of elements collaborative study, digestion system H,SO, addition allowed 980 "C dry ash
Pb, Cd, Cu, Zn, As, Se Pb, Cd, Cu
automated
Sb, Ba, Pb Sb. Ba AI,' Bi, Cd, Cr, Cu, Mn, Ni, Pb, Zn
geological coal, coke, ash, and mineral matter Venezuelan laterites rocks and sediments silicate rocks and minerals rocks hair hair hair
major constituents Ag, Bi rare earths Yt and rare earths Cd, Cr, Hg, pb, Zn
comparison to X-ray methods demountable hollow cathode lamp ion-exchange separation from Ca, Fe, Al, Na coprecipitation with Ca and Fe as carriers
Ca, Mg, Cu, Fe, Zn
sex differentiation no anatomical variations between scalp and pubic hair
hair lubricating oils
T1, Cd Ba, Ca, Zn, Cu, Fe
metallurgical Pb/Sn solder steel
nonferrous alloys Au
review article
co
Na (metallic) Na (metallic) NaCl brines organic solvents propylene carbonate and tetrahydrofuran phosphate plant materials pottery Romano-Bri tish Aegian ceramics seawater seawater
As, Sb, Se, Te
seawater
Zn
seawater seawater seawater
Mn Co, Cu, Mn Cd
Fe, Ni, Cr Ca, Mg
Cu, Mn, Zn
Cd Cd, Pb, Ni, Cu, Zn
Cd
seawater seawater seawater
Mo
seawater sludge (anode) sludge (sewage)
Fe, Mn, Zn Pb Ag, Co, Mn, Mo, Sn
sludge (sewage) sludge (sewage)
Cd, Cr, Cu, Ni, Pb, Zn
soil
Cd, Co, Cu, Mn, Ni, Pb, Zn CU,Pb, Cd, Ni, c o Cu, Zn
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chloroform extraction of 1-nitroso-2-naphthol complex volatilization characteristics of Na salts NaCl electively voltilized at 1100 "C Na, Li, K determined
seawater
soil soil soil and plant sunscreen
isobutyric acid dissolves both oil and H,O and allows use of aqueous inorganic standards review
Ti
p, absorption a problem dry ash general article thera, Greece EDTA reduces atomization temperature compares APDC-DDDC-freon extraction to Chelex-100 citric acid matrix modifier, good introduction on seawater pretreatments preconcentration with 8-hydroxyquinoline ascorbic acid (1%)as a matrix modifier EDTA, citric acid, histidine, lactic acid and aspartic acid as matrix modifiers, citric best comparison of isotope dilution spark source mass spec, GFAAS and ICP and preconcentration methods intercalibration study comparison, carbamate separation through study of APDC-MIBK and ('helex 100 preconcentrations an exchange of comments tri-n-octylmethylammonium tetrabromopalladate monitor because application of sludge to agricultural land may reduce crop yields nitric digestion compared dry ash and HNO,, "0,-II,O, and HNO, (high pressure) wet ashes, wet best acetate extracts EDTA extracts + solvent extraction procedure APDC-MIBK solvent extraction general overview article iron oxide interference
ANALYTICAL CHEMISTRY, VOL. 54, NO. 5, APRIL 1982
ATOMIC ABSORPTION, ATOMIC FLLIORESCENCE, AND FLAME SPECTROMETRY
Table I1 (Continued) matrix
elements
water water
Na, K, Ca, Mg, Sr, Fe, Ba, Si, A1 Cd, Pb, Cr Fe, Mn, Ni, Al, Cr, Cu, Cd
water uranium
Li, Na, K, Cu
water
comments
ref
oil field injection water and suspended solids
7 7E
estuarine water freeze drying preconcentration method as effective as solvent extraction or chelating ion exchange review on preconcentratioin
99E 62E
et al. (130)have reviewed and summarized chemical reactions that occur in furnaces and rods as used in atomic absorption spectrometry and in a continuing series of papers Frech and Cedergren (1.20) presented a good fundamental study of the ) vaporization behavior of Si, Persson and Frech (280studied phosphorus considering reactions between P, C, 0, H, N, Ca, and Ar as well as volatile mono- and dioxides, and Koreckova et al. (190)studied arsenic looking a t Ni and La as vaporization stabilizers as well as using platform techinques. An excellent paper by Smets (330)on atom formation and dissipation in electrothermal atomization was published. He indicated that sublimation of the metal generated by carbon reduction of the oxide or the reduction rate itself were rate limiting steps in atom formation. For AI, the gas-phase diswas the rate limiting step. Falk and Tham sociation of A1203 (100)in an experimental study of the expansion process of the vapor cloud from a m open atomizer indicated the convection was more important than diffusion. Maney and Lucian0 1240) studied the effects of K, B, Ca, Mg, and C1 on the time evolution of the P b absorption signal. Salmon et al. (3113)felt that chemisorbed O2caused time shifts and double peaks for Pb. Two active sites on the carbon surface were suggested which could be altered by 02. This paper has a good introduction and is an interesting study. Mueller-Vogt and Wend1 (270)investigated the reaction kinetics of Si in graphite furnaces. Up to 1650 "C silicate was reduced to Si, but above that temperature silicon carbide was formed. Niobium coated tubes helped to reduce carbide formation. Riandey et al. (290)found that rapid heating (2000 "C s-l) was beneficial fix the determination of Cd and Pb. L'vov and Peliera (230)carried out a thermodynamic study of gaseous monocyanides (i.e., BCN, AlCN, GaCN, etc.) in an electrothermal atomizer, in all, 38 elements were studied. Several studies of a theoretical nature were reported. L'vov et al. (220)in a long paper presented a niacrokinetic theory 20) presented of sample vaporization. Akman et al. (ID, theoretical analyses of atom formation-time curves and sample-loss mechanisms for the HGA-74 graphite furnace. Cenc et al. (140)presented a theoretical analysis of Mn, Cr, and P b atom formation-time curves for the HGA-74 furnace. In any studies of time behavior associated with electrothermal atomizers, considerable attention must be paid to the speed of the meaciurement electronics particularly if sensible and accurate mechanisms and models are to be developed. Without question, not enough attention has been paid to this aspect of the experimental system in the past. Lundberg and Frech (210)address thiri point and emphasize that high-frequency response is a mus,t for fundamental studies. In a good paper Siemer and Baldwin (320)also discuss the effects of instrument response on measurement accuracy. Erspamer and Niemczyk (81))indicate modifications to the Varian AA-6 system to improve its response for graphite furnace work. Kitagawa et al. (170)measured the degree of atomization of Cu in an electrothermal atomizer using the emission lines of copper atoms and CuCl molecules. Estimates of degree of atomization for Ni, Cr, ,and P b were also presented. In an interesting article Sturgeon and Bermaii (340)measured analyte ionization in a graphite furnace. They measured both emission and absorption signals. Analyte ionization was small and electron concentration was high. In another paper by these same authors (350)electron concentrations in graphite and tantalum tubs atomiizers were measured by using attenuation of microwaves. The source of electrons was thermionic emission and the electron concentrations were in the range of 1011-10'2 electrons/cm3. The overall goal is to obtain data that would help clarify ionization interferences in furnaces. In a series of papers Chakrabarti and colleagues discussed the development, applications, and capabilities of capacitive
76E 86E
discharge heating in graphite furnace atomic absorption spectrometry (40,50). Heating rates are rapid with this system 100 "C ms and matrix effects are minimized (60). An extensive stu y of atomization mechanisms in their system has been published (70). An extensive study of interelement interference effects was reported on by Voninovitch et al. (380).A detailed study of the formation of the monohalides of Al, Ga, and In in an electrothermal carbon furnace was carried out by Tsunoda et al. (370).The study was 2-fold: one aspect, a study of an interference; the second looking at the potential for halide determinations. Karwowska et al. (160)studied the effect of CC14 on iron atomization. Lawson and Woodriff (200) indicated that in addition to chemical modifications, selective volatilization, and standard addition methods, atomizer design was important for the reduction of matrix interferences. Koirtyohann et al. (280)showed that when perchloric acid was used for dissolution the absorption signal for many elements, particularly group 3A (Al, Ga, Tl), was suppressed. The mechanism was unclear. Beaty et al. (30)discussed the use of O2during the ash cycle as a "matrix modifier" and found that it aided the analysis of difficult samples such as serum. In a general review, Matousek (250)discussed the elimination and control of interferences in electrothermal atomization atomic absorption spectrometry and Feinberg and Ducauze ( 1 l D ) presented a statistical method for the evaluation of interferences. .A two-stage thermal atomizer for metal speciation analysis has been described by Robinson and Rhodes (300)and Kantor et al. (15D)discussed a furnace-in-flame atomizer. A new approach to emission was described by Falk et al. (90).This system called FANES, for furnace atomic nonthermal excitation spectrometry, is a combination of an electrothermal atomizer with a glovv discharge device thus allowing independent atomization and excitation. This atomization/vaporization role of the furnace has also been used to introduce samples into the IC€' and in fact may indicate a future important utilization of electrothermal vaporization systems. In a somewhat related study (but in the opposite sense of Falk's) McCamey and Niemczyk (260)presented very preliminary results on the use of sputter atomization for atomic absorption measurements. Atomizer Structure, Form, and Composition. The key component of an electrothermal atomizer is the atomizer itself. Considerable research effort is being spent in the study and development of new structures, forms, and compositions for atomizers. Considerable work has focused on pretreatment of the graphite surface with both pyrolytic and metal treatments. A study was presented by Slavin et al. (530)in which the problems associated with the porosity of graphite and the fragility of pyrolytic graphite protective coatings was discussed. This article has a good introduction to this general problem and area. The use of pyrolytically coated graphite tubes in conjunction with the addition of ammonium nitrate as a matrix modifier for the determination of Cu, Fe, and Mn in seawater was studied by Montgomery and Peterson (430). The use of ",NO3 initially helps but after about 15 runs the tube performance significantly declines. Veillon et al. (610)found that there was considerable Cr retention when running ashed urine but that performance was much better with pyrolytically coated tubes. In determining P b and Cd in fish and clam tissue, Poldoski et al. (480)pretreated a pyrolytic graphite atomizer with both Mo and La. Wahab and Chakrabarti (650,660)found that carbidizing pyrolytic tubes with Ta, Zr, or La facilitates the determination of yttrium which, itself, tends to form a carbide. Zirconium-coated graphite atomizers have been used for the determination of Pb in digested soils and sediments (500) and for the analysis
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Table 111. Determinations in Human Biological Matrices element
matrix
A1 A1
blood plasma or serum human serum
A1 AU Be
serum tissue and feces blood
Cu, Mn, Fe, Ca Ca Ca Cd Cd Cd Cd Cd, pb Cd Cd
brain human leukocytes kidney blood, urine blood semen urine, perspiration urine blood, urine urine blood
comments gel filtration chromatography, brain levels for Alzhermer’s disease dialysis dementia in hemodialysis prep. isotachophoretic system to find elements in specific protein fractions solubilized with Soluene 350 lymphocytes radid extraction technique Zeeman background correction low temp. rf ashing
ref
109E 157E 151E
121E 138E 154E 144E 113E 16 2E 145E wet and dry ashing 134E automated 152E “,NO, and Triton X-100 111E Cd matrix modification with ammonium phosphate t 116E ashing in an 0, atmosphere Cd, Cu, Pb, Mn human kidney cortex Zeeman background correction 143E Cd, Cu, Pb, T1 liver and kidney tissue enzymic digestion 112E Cd, Cu, Hg, Pb, Zn blood storage time, temp, container type 139E co blood wet oxidation, good references 11OE Cr human milk and urine low and high temp ash comparison 131E Cr urine electrothermal + H, diffusion flame 146E Cr urine, blood valency of Cr in urine 141E Cr plasma 155E Cr blood serum distribution among serum proteins 122E cu automated bovine serum 133E cu automated, 50-110 pL, 240 samples/h serum 158E cu urine 124E Cu, Zn serum comparison of procedures 153E Cu. Zn‘ serum, dialysate hemodialysis patients 136E, 137E Cui Mn, Fe, Ca solubilized with Soluene 350 brain 121E Fe serum 4 0 : l dilution 140E Li reference method serum 159E ionized, complexed, and protein-bound plasma 150E Mg Mn serum, urine 123E Ni serum 161E Ni Ni separated from Fe and Cu biological samples 118E IUPAC reference method Ni serum, urine 127E silanization of reagent tubes Pb blood 114E Pb bone 164E cisplatin Pt tissue 117E Pt extraction procedure serum, ul traf iltrate 125E Pt biological fluids 147E Zn, Cu gel filtration, speciation of protein bound species 119E human blood serum Zn, Cu microliter volumes serum, urine 135E, 160E Zn study of 104 normal subjects serum 129E Zn acid extraction feces 132E Zn protein status serum, plasma 130E Zn an exchange of comments 128E, 149E plasma biological and clinical materials a review 115E blood evacuated collection tubes 163E bovine liver Teflon bomb decomposition 126E of organolead (620) and tin and or anotins (630, 640). Hulanicki et al. (460) tried Ta, Si, NE, Zr, W, and La pretreatment coating procedures for vanadium determinations with little success. Pyrolytic graphite with added CH4 in the sheath gas seemed to provide the best conditions. Tantalum-coated carbon furnace tubes have been used for the determination of Si (470)and with added NHINOBfor P b in seawater (440). Lead in urine has been determined by using Mo treated tubes with orthophosphoric acid added as a matrix modifier (450). In a somewhat different and interesting system gold-plated graphite furnace tubes have been used to facilitate the determination of mercury by furnace atomic absorption spectrometry (510). Suzuki and colleagues continue to study and utilize their Mo microtube atomizer. In a series of papers they studied barium by emission (580) and Ca and Sn by emission and absorption (560) where the Mo microtube eliminated carbide formation problems. Alkali chloride interferences on Cu and Mn were minimized by the addition of thiourea which prevents formation of CuCl(570). Suzuki et al. (590) also im284R
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proved the sensitivity of their Mo microtube system with the addition of a microcomputer system and they also published a basic study on atom formation processes in the Mo microtube atomizer (600). Another group [Puschel et al. (490)] also continued their work on atomization from metallic surfaces with a study on a tungsten-tube atomizer. Voltage and temperature feedback in combination with rapid heating was utilized. The L’vov platform technique is beginning to be fairly widely utilized. Slaven and Manning (520) discussed the use of the L’vov platform for Pb, Cd, and T1 determinations. Kaiser et al. (410) showed that interferences could be produced by using platform techniques and ammonium phosphate. Fernandez et al. (390), in a general paper, discussed the use of the L’vov platform for furnace atomic absorption applications and Hinderberger et al. (400) utilized matrix modification (NH4N PO4) and the L’vov platform for the determination of Pb, bd, Cr, and Ni in blood, liver, and urine samples. Finally Marshall et al. (420) investigated carbon furnace atomic emission using platform atomization. Slovak
ATOMIC ABSORPTION, ATOMIC FLUORESCENCE, AND FLAME SPECTROMETRY .-
Table IV. Direct Electrothermal Atomization of the “Hydride Forming” Elements comments matrix element antimony arsenic arsenic arsenic, selenium arsenic
biological materials natural waters biological materials
arsenic arsenic Ge, Sb, As, Se
environmental acid matrix
mercury, selenium mercury mercury selenium selenium selenium selenium
seawater fresh and estuarine water infant formula powder nutritional supplements
selenium selenium selenium selenium selenium
urine, blood geological materials: biological water
tellurium As, Sb, Se
ref 185E 180E 183E 177E 169E
wet digestion, As( V ) converted to As( 111), solvent extraction stabilized during ashing with Ag As(”, As( V), monmethylarsonate and dimethylarsinate by chroma tograph y Stabilization with Ni salts, probelms discussed As(III), As( V), ammonium see-butyl dithiophosphate extraction simultaneous separation from matrix by sodium lauryl sulfate and Fe(II1) hydroxide adsorbing colloid flotation good study of stabilization reagents for electrothermal atomization thiols for stabilization activated carbon c’ollection stabilized with 0.2%N i t Ca
166E 167E 168E 17 1E 178E 172E 179E 182E 184E 173E
N i added as matrix. modifier, superior to hydride method extraction with aromatric o-diamine, vaporization stabilized with Ni extensive stabilization study for inorganic and organoselenium solvent extraction wet digestion + Ni stabilization M o microtube atomizer APDC-MIBK solvent extraction with Cu(I1) matrix modification for stabilization test stabilization oil inorganic Te with Cd, Cu, Pd, Pt, Zn, and organic Te with Ag, Pb, Pt As(”, As(V), Sb(III), Sb(V), Se(IV), Se(V1) speciation detailed study of APDC-MIBK system
and Docekal (550) discussed atomization of elements from large amounts of involatile matrices and concluded that a pseudo “platform” effect may be operative. Basic atomizer geometry is also an important variable. Slavin et al. ( 5 4 0 ) found1 that temperature variation along a graphite furnace would be reduced from loo0 to 100 “C simply by contouring the tube in a tapered format toward the ends.
APPLICATIONS OF ELECTROTHERMAL ATOMIZATION ATOMIC ABSORPTION SPECTROMETRY The key strength of any analytical technique is that it must solve chemical problems of interest to science, industry, government, and society. Clearly atomic absorption spectrometry is almost unparalleled in the diversity of its application. In this section a number of representative applications are presented primarily in tabular form. Each table contains element and matrix columns as well as brief comments on most applications. These tables can be efficiently scanned for applications of interest. Determinations of Slpecific Elements. Determinations in which the primary interest was centered on one element are summarized in Table I. No particular major trends are noticeable. Lead remains the most frequently determined element with strong interest in chromium as well. Particularly comprehensive studes were carried out by Donaldson for Cr (13E), Mo ( I I E ) ,,and Sn (12E).Extraction procedures are almost always in evidence indicating continued problems with mutual interferences.
Determinations of Elements in Specific Matrices.
Determinations in which the primary interest was centered on analysis of a particular matrix for several elements are presented in Table 11. Again there are no major new trends although interest in seawater is evident. Determinations of Elements in Human Biological Matrices. Clinical applications of atomic absorption spectrometry are listed in Table 111. In addition to the traditional heavy metals such as Zn, Cd, and Pb, elements such as Al, Pt, and Li are of interest due to their utilization in certain therapies. Direct Electrothermal Atomization of the “Hydride Forming” Elements. There has been major interest in determinations of Sb, As, and Se by direct electrothermal atomization over the last 2 years in direct competition with the so-called “hydride” procedures. The applications are summarized in Table IV. Much of the work centers on the
16 5E 176E 175E 174E 170E 186E
18lE
Table V. Indirect Determinations analyte l,%-diols epoxide hydrolase iodide nitrates phosphorus, arsenic sulfate sulfate sulfite or
method
ref
reacted with excess periodate, 194E precipitated with Pb; Pb deter mined same as l,2-diol method 193E decomposition of HgJ, reduction with Cd metal molybdenum heteropoly acids BaSO, ZnS based Hg displacement reaction
191E 188E 195E, 196E 187E,190E 192E 189E
SO,
development of volatilization stabilization techniques, Nibased approaches being the most popular. Indirect Determinations. Indirect determinations often require clever chemical ingenuity, a few examples of which are presented in Table V. Direct Analysis of Solid Samples. There has been a considerable increase in the last 2 years in the utilization of electothermal atomizers for the direct analysis of solid samples. The driving force is to eliminate the costly and time-consuming steps necessary to put many matrices into solution form. The main problems remain standardization, accuracy, and precision. With auxiliary vaporization such as that provided by lasers (214E)atomic absorption determinations have been carried out on solid samples for some years although such systems are not common. This approach and most other current sytems for the direct analysis of solid by atomic absorption spectrometry have recently been reviewed (209E, 217E). In this section emphasis will be on direct analysis of solid samples by electrothermal atomization with little or no sample preparation. Price et al. (213E)compared graphite and plastic cups for introducing solid samples with an electrothermal atomizer with graphite finally being chosen. Nichols and Woodriff (212E) coprecipitated heavy metals directly in small graphite crucibles which where then inserted directly into a “woodriff” furnace. Headridge (206E)presented a good review of the determination of trace elements in metals by the introduction of solid samples into furnaces and Headridge (197E, 198E)and ANALYTICAL CHEMISTRY, VQL. 54,
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Table VI. Hydride Generation Techniques and Determinations element
matrix
As As As As As
urine, water urine, feces organic and biologic a1
As As As As As As
biological samples seaweed biological samples
As As As
acrylic fibers
comments a review with 240 references, hydride AAS, flame EA, NAA, OES, X-ray, AFS, electrochemical arsine evolution-electrothermal AA dry ashing with added Nig(NO,), Ni added arsine evolution-electrothermal AA, 1,lO-phenanthroline eliminated N i and Co effects elimination of Ni, Co, and Ca interference by pyridine-2-aldoxime Perkin-Elmer MHS-1 effect of Se(IV) on As(II1) and As(V) removed by Cu total arsenic removal of Ag(I), Au(III), Fe(III), Pt(IV), Sb(III), Sr(II), F- and Sinterfences, somewhat complex removal of antimony oxide with a benzene extraction
fish, shellfish, fish products
As waste waters marine organisms and sediments
As
As As As Ge Pb
natural waters drinking waters
Pb Sb Sb Sb Sb Sb Sb Se Se Se
urine organic matter steel natural waters geological materials biological matrices inorganic and organic matrices
Ye Se
corn, lettuce, potatoes, soybeans, wheat food composite, bovine liver, wheat flour
Se Se Se
biological materials, rocks, and soils
Se Se Sn As, Sb
geological materials seawater
As, Sb As, Sb, Se As, Se As, Se
plants
As, Se As, Se As, Se As, Bi, Pb, Sb, Se, Sn Se, Bi Sb, As, Bi, Se, Te, Sn
soils and sediments
geological materials foods
rocks, soils metallurgical samples, low-alloy steels
9F 39F 33F 23F 13F 14F 26F 46F 40F 5F 25F 3 1F 6F 27F 24F 2 8F
arsenic speciation, problems with methylated As As(III), As( V), methylarsenic, dimethylarsenic GeH, enters heated (2600 “C) furnace, N, trap to preconcentrate Cu and Ni interfere, MnO, coprecipitation, compared to DPASV, FARS, GFAAS inorganic, triethyllead, die thyllead wet oxidation, sulfite to generate only Sb(111) KI masks out effect of stannous chloride different sensitivities for Sb(II1) and Sb(V) Sb(II1) and Sb(V) determined Sb(II1) and Sb( V) determined Sb(III), Sb( V), and methylantimony species
19F 21F 4F 43F 51F 52F 4 8F 4 5F 3OF 50F 3F 36F 3 2F 29F
total selenium
10F 17F
tested dry and wet ashing, Mg(NO,), as a dry ashing aid, H,PO,, HNO,, H,O, wet ash fast and best, low temp 0, plasma to slow
34F
method test with radiotracer, silanized glass best decomposition in pure 0,
3 5F 18F
compared electrically and flame heated quartz tubes Se(IV), Se(VI) speciation, Cu( II), Ni( II), Fe( 111) interferences
4lF 4 2F 3 8F 49F
As(III), As(V), Sb(III), Sb(V), for As(III), Sb(III), Ag’, CU”, Snz+,Se4+, and Te4+interfere atom trap preconcentration automated method 28 labs, 1 6 hydride generators, 700 analyses, 1 3 reference food samples, interesting study
15F 44F 37F 22F IF 7F 2F
flame heated silica t tube
20F
many interferences studied, comprehensive
11F 47F
his colleagues presented results for the determination of Bi, Pb, and T e in Cu and Ag and T1 in nickel-base alloys by direct solid analysis using an induction furnace. As, Sb, and Bi have been adsorbed on glycol methacrylate gels with bound thiol groups and the resulting suspension directly injected into an electrothermal atomizer for analysis (215E). Kowalska e t al. determined Pb in graphite (208E) and Favretto e t al. (204E) determined P b in biological materials with direct solid or slurry sample addition. A good 286R
8F
timing consideration with respect to As(V) intralaboratory study, organic and inorganic As inorganic and methylated arsenic, ion-exchange chromatography
nitrogen oxide interferences fish tissue
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ANALYTICAL CHEMISTRY, VOL. 54, NO. 5, APRIL 1982
discussion of running solid samples by graphite furnace AAS is also presented by these last authors. Silver has been determined in silicate rocks by direct atomization of powdered samples (202E). Sampling errors associated with 10 wm size powdered samples are discussed and the standard addition method was used. Trace metals were determined in aluminum oxide with the direct injection of aqueous suspensions (216E). Lead in dry ground vegetation has been determined with an aqueous slurry placed in an Ni microsampling cup which was
ATOMIC ABSORPTION, ATOMIC FLUORESCENCE, AND FLAME SPECTROMETRY
_______
-
Table VII. Chromatographic-Atomic Absorption Techniques and Determinations comment species element Dionex anion column, heated quartz tube, hydride arsenite, arsenate, monomethyl arsonate, As dimethyl arsinate, p-aminophenyl arsonate HPLC- graphite furnace arsenite, arsenate, methylarsonic acid, As dimethylarsinic acid HPLC-graphite furnace (sample injected) soil arsenical residues As HI’LC-graphite furnace, Teflon flow through cup arsenical pesticide residues As placed directly into furnace gas-solid Chromatography As, Se, Ge, Sn hydrides nebulizer interface of LC to flame Cd InCl flame emission c1 methylcyclopen tadienylmagnanesetr icar bony1 gas chromatography. air samples, gasoline additive Mg (MMT)
P Pb Pb Pb Pb Pb Pb, Sn Sn Zn, Cd
organophosphorous compounds te traalkyllead tetraalkyllead, gasoline te traalkyllead, air .tetraalkyllead, petrol te traalk.yllead, fish, vegetation sediment, water organolead and organotin Sn tetraalkyls, alkyltin chlorides metalloproteins, me tallothioneine
then insereted in an AIR1-C H2 flame (207E). Freeze-dried pancreatic islets have been Arectly analyzed for Ba, La, and Mg by electothermal atomic absorption spectrometry (199E). Pb and Bi have been determined directly in solid steel samples by Frech et al. (205E) who also comment on the roblem of obtaining appropriate standards. Langmyhr and &re (211E) have determined Cr, Co, and Ni in fish protein concentrate and dried fish solubles by solid sampling atomic absorption spectrometry. The same group has also directly analyzed coal and petroleum coke for Cu, Ni, and V with powdered sample introduction (210E). Lead in mussels has been determined by solid microsampling into a tantalum cup with subsequent vaporization in a flame (203E). Oyster tissue has been directly analyzed for Cd, Pb, Zn, (3.1, Co, and Fe from the solid state using the graphite furnace platform technique (201E). In a similar procedure bovine liver was directly analyzed for Cu, Zn, Pb, Co, Fe, and Cd with (NH4)2S04used to stabilize Cd as CaS04 (200E).
HYDRIDE GENERATION TECHNIQUES AND DETERMINATIONS Hydride methods are now widely used and a summary of determinations is presented in Table VI. As and Se are the most frequently determined elements and it is evident from the table that valence state and speciation (inorganic-organic) information is often sought. A general review on hydride methods has been presented by Godden and Thomerson (16F) and in a general technique paper Dedina and Rubeska ( 1 2 9 discussed the use of a hydrogen-oxygen flame burning in a quartz tube atomizer as an aid to complete atomization of hydrides for atomic absorption measurements.
HG COLD VAPOR TECHNIQUES AND DETERCMINATIONS Numerous studies continue to be published in the area of Hg cold vapor atomic absorption reflecting the importance of this determination and element. Two re orts were published dealing with the vacuum-ultraviolet &termination of mercury at the 185.0-nm line (24G). In fact, vacuum was unnecessary, the system being purged with argon. Nondispersive instrumentation was utilized (9G) coupled to a CsI (solar blind) PMT. A new absorption cell shape which is tapered to match the light ray profile has been described (26G). Gold is frequently used as a collector material for Hg cold vapor determinations. Aldrighetti et al. evaluated the efficiency of gold sponge as a collection medium at the submilligram level (1G)and gold wire collectors were described by Scott and Ottaway (21G) and Wittmann (28G). The evaluation of magnesium perchlorate as a desiccant in the syringe injection technique was carried out by Gardner (8G) and it was found to be unnecessary. Szakacs et al. (23G) showed that methylnnercury(I1) chloride could be broken down
HFLC-graphite furnace (fraction collector) gas-liquid chromatography, graphite furnace liquid chromatography- AIR/C,H, flame gar; chromatography gar, chromatography chromatographic system liquid chromatography gas and liquid chromatography HPLC, gel permeation column, flame AA for che purpose of cold vapor determinations by hydrochloric acid.-permangate or bromine monochloride. Sanemasa et al. (20G) presented a preconcentration technique for Hg using an anion-exchange resin. Juddendorf (22G) studied the depressing effect of Se arid Te on Hg cold vapor determinations. Oda and Ingle (16G) described a selective reduction method for the speciation of inorganic and organic mercury and the same authors described a continuous flow system for Hg cold vapor determinations (15G). Mercury cold vapor determinations were described for fish (3G,25G), biological tirisues and samples (ZG, 7G),hair (27G), methylmercury ( I I G ) ,urine and blood (4G, 17G),sediments and soils (19G),natural waters (12G, 13G), air (6G, 18G), environmental standard reference materials (5G),seaweed (IOG), and milk products and plastics (14G).
SOME CHROMATOGRAPHY CONNECTIONS In order to study and measure inorganic and organic forms of metal species, many workers have developed combination systems involving chromatographic separation and atomic absorption detection (16H). These studies are summarized in Table VII.
ATOMIC FLUORESCENCE SPECTROMETRY Research interest in atomic fluorescence spectrometry remains strong, a commercial atomic fluorescence spectrometer is now avilable with an ICP atomization cell and many applications of atomic fluorescence have been published since the last review. The present status and future prospects of atomic fluorescence spectrometry have recently been reviewed by Van Loon (331) and Ullman (301) reviewed multielement atomic fluorescence spectrometry. In a discussion of the application of tunable lasers to analytical atomic spectrometry Falk (91) included a section on atomic fluorscence spectrometry as well as covering resonance ionization spectrometry and intracavity atomic absorption spectrometry. One of the more interesting recent developments in atomic fluorescence spectrometry is the utilization of the inductively coupled plasma as the atomization cell (31, 71). In fact a commercial instrument (Baird Corp.) is available based on this approach which uses pulsed hollow cathode lamps for excitation (31). In somewhat of an opposite sense the ICP has been used as an excitation source for flame atomic fluorescence spectrometry (81).One can almost predict a dual ICP excitation source-ICP atomization cell configuration for multielement atomic fluorescence as the next configuration. Horvath et al. (251,160 compared nebulizerspray chamber arrangements and nebulizer-burner systems for atomic fluorescence. Flame type and modulation approaches were evaluated with respect to sources of noise in multielement atomic fluorescence spectrometry (251). Many basic studies of processes, characteristics, and phenomena of flames and species in flames continue to be carried ANALYTICAL CHEMISTRY, VOL. 54,
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out utilizing atomic fluorescence measurements. Several of analytical interest are summarized here. Flame temperature measurements have been carried out based on the redistribution of rotational population of the OH radical in a methane-air flame utilizing laser excited fluorescence (371) and a new technique for local (spatially resolved) flame temperature measurements based on thermally assisted fluorescence has been described (361). An experimental study of saturation in analytical atomic fluorescence has been presented by Olivares and Hieftje (231) and saturation has been modeled by van Dijk et al. (321). In a very interesting study Frulholz and Gelbwachs (121) presented a measurement approach that could discriminate against excitation source scattered light. Their system requires near-saturation laser excitation. When modulated, the atomic fluorescence signal has harmonic components but none are generated in the scattered signal. Thus tuning a lock-in amplifier to the second harmonic of the modulation frequency results in selective detection of the fluorescence signal with respect to the scattered signal. All in all quite an interesting paper. Theoretical and experimental aspects of laser saturation broadening in flames has been discussed by Omenetto et al. (241). Alkemade and colleagues continue their extensive and detailed study of sodium atomic vapor utilizing laser excited atomic fluorescence techniques. Collision assisted off resonance absorption of sodium was studied in a H2-02-Ar flame (311)and collisional broadening of the Na D lines was studied in a two-part article (181,191). The fluorescence-excitation profiie was studied up to lo00 cm-l from the line center. Laser excited fluorescence spectra of YO molecules in H2-02-Ar flames was also studied by the Alkemade group (341). Laser-induced fluorescence w&.also studied in liquid fuel flames such as kerosine/air and gasoline/air by Fujiwara et al. (13I). Many practical analytical determinations were carried out by using atomic fluorescence techniques. Wear metals in jet engine lubricating oils were determined by wavelength modulated, continuum-source excited atomic fluorescence spectrometry. Samples were introduced by using an electrothermal atomizer (351). Fleming (111) described an on-line atomic fluorescence monitor for magnesium, Ebdon et al. (41)described a mercury cold vapor determination based on atomic fluorescence and Ferrara et al. (231)also determined Hg using atomic fluorescence spectrometry with a high-frequency electrodeless discharge lamp. Nickel and tin were determined by laser-excited atomic fluorescence in a N2 separated AIRC2H2flame (61). Tin was excited at 300.9 nm and fluorescence was observed at 317.5 and 380.1 nm. Nickel when excited at 300.24 nm exhibited fluorescence at several lines. Stokes direct-line atomic fluorescence of iron with excitation at 296.7 nm and fluorescence observation at 373.5 nm was also reported (51). Iron could be determined at the 0.06 ng/mL level, equivalent to about lo4 atoms in the beam. An even lower level of lead was determined by Bolshov et al. (21) usin atomic fluorescence. Concentrations of 0.05 pg/mL were etected equivalent to 250 atoms/cm3. The inherent simplicity of atomic fluorescence is perhaps most evident in nondispersive configurations (141). Hutton and Preston (171) described a nondispersive AFS for mercury using cold vapor generation. Arsenic was determined in soil digests by nondispersive AFS in conjunction with hydride generation techniques and an argon-hydrogen flame. An arsenic EDL was used as the source (11). Antimony(II1) and -(V) were determined again by hydride methods and nondispersive AFS (261). Antimony and arsenic depth profiles in semiconductor silicon were determined by using chemical etching, hydride generation and nondispersive AFS (271,281). An Ar-H2-entrained AIR flame was the atomization cell. A unique indirect determination of phosphorus was described by Tsujii et al. (291). Phos hate was converted to molybdoantimonylphosphoric acib) and antimony determined by nondispersive graphite furnace atomic fluorescence spectrometry. Finally Nakahara et al. (201,211,221)presented methods for the nondispersive atomic fluorescence spectrometry of selenium and tellurium using hydride generation techniques.
d
ACKNOWLEDGMENT The secretarial assistance of Annabelle Wiseman in the preparation of this review is gratefully acknowledged. 2881
ANALYTICAL CHEMISTRY, VOL. 54,
NO. 5,
APRIL 1982
LITERATURE CITED INTRODUCTION (1A) Alkemade, C. Th. J. Spectrochlm. Acta, PartB 1980, 358, 671. (2A) Alkemade, C. Th. J. Appl. Spectrosc. 1981, 35, 1. (3A) Amos, M. "Furnace and Vapor Generation Methods in Atomic Absorption"; SAVANT Fullerton, CA, 1978; 50 slides. (4A) Anderson, J. L.; Grohs, J.; Frick, D. J. Chem. Educ. 1980, 57, 521. (5A) Broekaert, J. A. C. Spectrochlm. Acta, Part 8 1981, 368, 931. (6A) Dawson, J. B., Sharp, B. L., Eds. "Annual Reports on Analytical Atomic Spectroscopy"; The Royal Society of Chemistry: London, 1980; Vol. 9, Reviewing 1979, p 345. (7A) Fuwa, K.; Kamada, H. Spectrochim. Acta, Part B 1981, 368, 597. (8A) Fuwa, K.; Vallee, B. L. Spectrochim. Acta, Part 8 1980, 358, 657. (9A) Horlick, G. Anal. Chem. 1980, 52,290R. (10A) Hosklns, L. C.; Reichardt, P. B.; Stolzberg, R . J. J. Chem. Educ. 1981, 58, 580. (11A) Koirtyohann, S.R. Spectrochim. Acta, Part 8 1980, 358,663. (12A) Koirtyohann, S.R. Anal. Chem. 1980, 52,736 A. (13A) Lawrence, D. M. At. Spectrosc. 1980, 1 , 94. (14A) Lawrence, D. M. At. Spectrosc. 1981, 2 ,22. (15A) Lawrence, 0. M. At. Spectrosc. 1981, 2 , 101. (16A) L'vov, B. V. Zh. Anal. Khlm. 1980, 35, 1575. (17A) Magyar, B.; Aeschbach, F. Spectrochim. Acta, Part 8 1980, 358, 839. (18A) Plnnell, R. P.; Zanella, A. W. J. Chem. Educ. 1981, 58,444. (19A) Pinta, M. "Atomic Absorption Spectrometry, Vol. 2: Application to Chemlcal Analysis", 2nd ed.; Masson: Paris, 1980; p 434. (20A) Price, W. J. Anal. Proc. 1980, 17, 402. (21A) Robinson, J. W. Treatise Anal. Chem. 1981, 1 , 729. (22A) Spectrochim. Acta. P a r t 8 1980, 358,No. 11/12. (23A) Spectrochlm. Acta, Part 8 1981, 368,No. 5. (24A) Spectrochlm. Acta, P a r t 8 1981, 368,No. 7. (25A) Uchlda, H.; Tanabe, K.; Nojiri, Y.; Haraguchi, H.; Fuwa, K. Spectrochim. Acta, Part 8 1980, 358,881. (26A) Van Dalen, H. P. J.; De Galan, L. Analyst (London) 1981, 706, 695. (27A) Van Loon, J. C. "Analytical Atomic Absorption Spectroscopy: Selected Methods"; Academlc Press: New York, 1980; p 337. (28A) Walsh, A. "Princlples of Atomic Absorption, Emisslon and Fluorescence, AA101"; SAVANT: Fullerton, CA, 1979; 49 slides. (29A) Walsh, A. "Instrumentatlon for Atomic Absorption, AA102"; SAVANT: Fullerton, CA, 1978; 52 sildes. (30A) Walsh, A. Spectrochim. Acta 1955, 7 ,108. (31A) Walsh, A. Spectrochim. Acta, Part 8 1980, 358,639. (32A) Walsh, A. Spectrochim Acta, Part 8 1980, 358,643. (33A) Willis, J. "Atomic Absorption Techniques and Applications,AA103"; SAVANT: Fullerton, CA, 1978; 52 slides. (34A) Willis, J. B. Spectrochim. Acta, Part 8 1980, 358, 653.
.
ANALYTICAL FLAME EMISSION AND ATOMIC ABSORPTION SPECTROMETRY (1B) Agemian, H.; Sturtevant, D. P.; Austen, K. D. Analyst (London) 1980, 105,125. (28) Aggett, J.; O'Brien, G. Analyst (London) 1981, 106, 497. (3B) Aggett, J.; O'Brien, G. Ana/yst (London) 1981, 106,506. (48) Aldrighetti, F.; Carelli, G.; Ceriati, F.; Cremona, G.; Pomponi, M. At. Specfrosc. 1981, 2 , 71. (58) Bassyouni, A. H.; Issa, M. A. A,; Hafey, A. F. J. Quant. Spectrosc Radiat. Transfer 1981, 23, 503. (6B) Bassyouni, A. H. J. Quant. Spectrosc. Radiat. Transfer 1981, 26,451. (7B) Bleasdell, B. D.; Wlttlg, E. P.; Hieftie, G. M. Spectrochim. Acta, Part 8 1981, 368,205. (8B) Bleirveiss, M. C.; Chang, P. H. P.; Penner, S. S. J. Quant. Spectrosc. Radlat. Transfer 1981, 26, 273. (9B) Bogdanski, S. L.; Henden, E.; Townshend, A. Anal. Chem, Acta 1980, 116. 93. (lOB) Bogdanksi, S. L.; Townshend, A,; Blanco, P. T. Anal. Chem. Acta 1981, 131,297. (1lB) Bogdanski, S.L.; Townshend, A,; Yenigul, B. Anal. Chem. Acta 1980, 175,361. (128) Borgers, A. J.; Jongerlus, M. J.; Hollander, TI. Appl. Spectrosc. 1980, 34, 46. (138) Burguera, M.; Townshend, A. Anal. Chim. Acta 1981, 127,227. (148) Cardweli, T. J.; Marriott, P. J.; Knowles, D. J. Anal. Chim. Acta 1980, 121, 175. (15B) Chang, P. H. P.; Penner, S. S.J. Quant. Spectrosc. Radiat. Transfer 1981, 25,97. (l6B) Chang, P. H. P.; Penner, S. S. J. Quanf. Spectrosc. Radiat. Transfer 1981, 25, 105. (178) Dulude, G. R.; Sotera, J. J.: Kahn, H. L. Anal. Chem. 1981, 53, 2100. (1881 Evans, W. H.; Dellar. D.; Lucas, B. E.; Jackson, F. J.; Read, J. I. Analyst (London) 1980, 105,529. (19B) Hughes, S.K.; Fry, R. C. Appl. Spectrosc. 1981, 35, 26. (208) Ivanova, E.; Mareva, S.; Iordanov, N. Fresenius' Z. Anal. Chem. 1980. 303. 378. (218) Jackson, F. J.; Read, J. I . ; Lucas, B. E. Analyst (London) 1980, 105, 359. (228) Kitagawa, K.; Yanagisawa, M.; Takeuchi, T. Anal. Chim. Acta 1980, 115, 121. (238) Koscielniak, P.; Walas, S.;Parczewski, A. Fresenius' 2.Anal. Chem. 1980, 302,402. (248) Li, K. P. Anal. Chem. 1981, 53,317. (258) LI, K. P.; Li, Y. Y. Anal. Chem. 1981, 53,2717. (268) Marquardt, D.; Stosser. R.; Henrlon, G. Spectrochim. Acta, Part 8 1981, 368,951. (278) Osibanjo, 0.;Ajayi, S. 0. Anal. Chim. Acta 1980, 120,371. '
ATOMIC ABSORPTION, ATOMIC FLIJORESCENCE, AND FLAME SPECTROMETRY (288) Pickett, E. E.; Hawkins, J. L. Anal. Blochem. 1981, 112,213. (298) Posta, J.; Lakatos, J. Spectochlm. Acta, Part 8 1980, 358, 601. (308) Ramsey, J. M. Anal. Chem. 1980. 52v2141. (318) Russo, R. E. Hieftje, G. M. Spectrochim. Acta, Part 8 1981, 368, 231. (328) Safari, A.; Tawnshendl, A. Anal. Chlm. Acta 1981, 128,75. (338) Sarudi, I.Fresenlus' .Z. Anal. Chem. 1980, 303, 197. (348) Saturday, K. A.; Hieftje, G. M. Anal. Chem. 1980, 52,786. (358) Schiefer, H. P.; Gramaln, P.; Kraeminger, E. Fresenius' 2. Anal. Chem. 1980, 303,29. (368) Smets, Bruno Analyst (London) 1980, 105,482. (378) StoJanovic, D. D.; Winefordner, J. D. Anal. Chlm. Acta 1981, 124, 295. (38B) Stolzenburg, T. R.; Andren, A. W. Anal. Chlm. Acta 1980, 118,377. (39s) Syty, A. "Treatise in Analytical Chemistry"; Wiley: New York, 1981; pp 629-728. (406) Taddia, M. Anal. Chin,. Acta 1981, 129,259. (418) Thompson, K. C.; Wagstaff, K. Analyst (London) 1980, 105, 641. (428) Wallace, G. F.; Lumas, B. K.; Fernandez, F. J.; Barnett, W. B. A t . Spectrosc. 1981, 2, 130. (438) Warren, R. L. Analyst (London) 1980, 105,227. (448) Westerman, D. W. 8.; Ruffio, I. E.; Wainwright, M. S.;Foster, N. R. Anal. Chlm. Acta 1980, i'li', 285. DEVELOPMENTS AND STUDIIES I N INSTRUMENTATION, MEASUREMENT TECHNIQUES, AND PROCEDlJRE General Developments (1C) Aikemade, C. l h . J.; Sneileman, W.; Boutlller. G. D.; Winefordner, J. D. Spectrochlm. Acta, Partk3 1980, 358, 261. (2C) Anderson, D. L ; Forster, A. R.; Parsons, M. L. Anal. Chem. 1981, 53, 770. (3C) Betz, M.; Guecor, S.; Fuohs, F. Fresenlus ' 2.Anal. Chem. 1980, 303, 4. (4C) Bower, N. W.; Ingle, J. D. Appl. Spectrosc. 1981, 35,317. (5C) Boyie, W. G.; Ryan, D. P. €nergyRes. Abstr. 1980, 5, Abstr. No. 4779. (6C) Boyle, W. G.; Ryan, D. P. Energy Res. Abstr. 1980, 5 , Abstr. No. 16245. (7C) Codding, E. G.; Ingle, J. D.i Stratton, A. J. Anal. Chem. 1980, 52, 2133. (8C) Dewait, F. G.; Amend, J. R.; Woodriff, R. Appl. Spectrosc. 1981, 35, 176. (9C) Downey, S. W.; Shabushnig, J. G.; Hieftje, 0. M. Anal. Chlm. Acta 1980, 121, 165. (1OC) Epstein, M. S.;Winefordner, J. D. Talanta 1980, 27, 177. (11C) Fernandez, F. J.; Lumas, 6.; Beaty, M. M. At. Spectrosc. 1980, 1,
55.
(12C) (13C) (14C) (15C)
Harniy, J. M.; O'Haver, T. C. Anal. Chem. 1981, 53, 1291. Harris, M. R.; Lepp, N. W. Analyst (London) 1981, 106,283. Hoenig, M.; Duplre, S.Analusis 1980, 8 , 16. Howarth, H.; McKenzie, T. N.; Routh, M. W. Appl. Spectrosc. 1981, 35, 164. (l6C) Liddell, P. R.; Wildy, P. C. Spectrochlm. Acta, P a r t 8 1980, 358, 193. (17C) Michei, R. G.; Sneddon, J.; Hunter, J. K.; Ottaway, J. M.; Fell, G. S. Analyst (London) 1981, 106,288. (18C) Ottaway, J. M.; Bezur, L.; Marshall, J. Analyst (London) 1980, 105, 1130. (19C) Patterson, J. E. Anal. Chlm. Acta 1981, 125, 193. (20C) Routh, M. W. Appl. Spectrosc. 1981, 35, 170. (21C) Russo, R. E.; Withneii, IR.; Hieftje, G. M. Appl. Spectrosc. 1981, 35, 531. (22C) Siemer, D. D. Anal. Chilm. Acta 1980, 179,379. (23'2) Steinhoek, L. fi.; Yeung, E. S.Anal. Chem. 1981, 53, 528. (24C) Stephens, R. Can. J . Chem. 1980, 58, 1621. (25C) Takada, T.; Nakano, K. Spectrochlm. Acta, P a r t 8 1981, 368, 735. (26C) Timm, J.; Diehi, H.; Harbach, D. Fresenlus' 2. Anal. Chem. 1980, 301, 199. (27C) Vajda, F. Anal. Chlm. Acta 1981, 128,31. (28C) Whiteside, P. J.; Stockdarie, T. J.; Price, W. J. Spectrochim. Acta, Part B 1980. 358 ~ ~ - - -. , 795. - . (29C) Yeung, E. S.;Steenhoek, L. E.; Tong, W. G.; Bobbitt, D. R. Anal. Chem. 1981, 53, 1936. ~
1
Sources (30C) Araki, T.; Waiters, J. P.; Minami, S. Appl. Spectrosc. 1980, 34, 33. (3lC) Dyulgerova, R.; Zhechev, D. Spectrochlrn. Acta, Part 8 1980, 358, 521. (32C) Freeman, G. H. C.; Outrtad, M.; Morris, L. R. Spectrochlm. Acta, Part 8 1980, 358. 687. (33C) Gough, D. S.;Sullivan, &I.V. Anal. Chlm. Acta 1981, 124,259. (34C) LeBlanc, B.; Carleer, M.; Demers, Y.; Gagne, J. M. Appl. Opt. 1980, 19,463. (35C) Mehs, D. M.; Nlemczyk, T. M. Appl. Spectrosc. 1981, 35, 66. (36C) Mohamad, S. Z.; Petrakiev, A. Spectrosc. Len. 1981, 14,47. (37C) Parker. W. C.; Lozada, R.; Labrecque, J. J. Appl. Spectrosc. 1980, 34, 94. (38C) Pillow, M. E. Spectrochlm. Acta, P a r t 8 1981, 368, 821. (39C) Siemer, D. D. Appl. Spoctrosc. 1980, 34,487. (40C) Walters, P. E.; Smit, K. J. Spectrochim. Acta, P a r t 8 1981, 368, 333.
(44'2) Berndt, H.; Messerschmidt, J. Spectrochlm. Acta, Part 8 1981, 368, 845. (4%) Black, M. S.;Browner, R. F. Anal. Chem. 1981, 53,249. (46C) Brown, J. R.; Saba, C. S.;Rhine, W. E.; Elsentraut, K. J. Anal. Chem. 1980, 52,2365. (47C) Bye, R . Fresenlus' 2.Anal. Chem. 1981, 306,30. (48C) Cedergren, A.; Frech, W.; Lundberg, E.; Person, J. A. Anal. Chim. Acta 1981, 128, 1. (49C) Chamsaz, M.; Sharp, B. L.; West, T. S. Talanta 1980, 27, 867. (50C) Cox, J. A,; Carnahan, J. W. Appl. Spectrosc. 1981, 35,447. (51C) Cox, J. A,; Oibrych, E.; Brajter, K. Anal. Chem. 1981, 53, 1308. (52C) Cresser, M. S.Prag. Anal. At. Spectrosc. 1981, 4 , 219. (53C) Czoblk, E. J.; Matousek, J. P. Spectrochlm. Acta, Part 8 1980, 358, 741. (54C) De ia Guardia Cirugeda, M.; Salvador Carreno, A,; Berenguer Navarro, V. Analusis 1980, 8, 448. (5%) Dittrlch, K.; Wennrlch, R. Spectrochlm. Acta, P a r t 8 1980, 358, 731. (56C) Fukarnachi, K.; Ishibashi, N. Anal. Chim. Acta 1980, 119,383. (57C) Fuiier, C. W.; Hutton, R. C.; Preston, B. Analyst (London) 1981, 106, 913. (58C) Goto, K.; Uchida, 'r. Rev. Sci. Instrum. 1980, 51,49. (59C) Guecer, S.; Berndt, H. Talanta 1981, 28,334. (60C) Holen, B.; Bye, R.; Lund, W. Anal. Chlm. Acta 1981, 130,257. (61C) Hoien, B.; Bye, R.; Lund, W. Anal. Chlm. Acta 1981, 131,37. (62C) Khaiighie, J.; Ure, A. M.; West, T. S.Anal. Chim. Acta 1980, 117, 257. (63C) Khaiighie, J.; Ure, A. M.; West, T. S. Anal. Chim. Acta 181, 131,27. (64C) King, S. W.; Wills, M. R.; Savory, J. Anal. Chim. Acta 1981, 128, 221. (65C) Layman, L. R.; Crock, J. G.; Lichte, F. E. Anal. Chem. 1981, 53,747. (66'2) Makino, T.; Takahara, K. Clin. Chem. (Winston-Salem, N . C . ) 1981, 27, 1445. (67C) Malioy, J. M.; Keiiher, P. N.; Cresser, M. S. Spectrochim. Acta, Parl 8 1980, 358, 833. (68C) Manning, D. C.; Siavin, W. Anal. Chlm. Acta 1980, 118,301. (69C) Michaiik, P. A,; Stephens, R. Talanta 1981, 28, 37. (70C) Mohamed, N.; Fry, R. C. Anal. Chem. 1981, 53, 450. (71C) Neidhart, 6.; Lipprnann, C. Fresenlus' 2.Anal. Chem. 1981, 306, 259. (72C) Pachuta, D. G.; Cline Love, L. J. Anal. Chem. 1980, 52,438. (73C) Pachuta, D. G.; Cline Love, L. J. Anal. Chem. 1980, 52,444. (74C) Polo-Diez, L.; Hernandez-Mendez, J.; Rodriguez-Gonzalez, J. A. Ana lyst (London) 1981, 106,737. (75C) Polo-Diez. L.; Hernandez-Mendez, J.; Pedraz-Penaiva, F. Analyst (Lon don) 1980, 105,37. (76C) Saba, C. S.;Rhlne, W. E.; Elsentraut, K. J. Anal. Chem. 1981, 53, 1099. (77C) Shabushnig, J. G.; Hieftje, G. M. Anal. Chim. Acta 1981, 126, 167. (78C) Sumlno, K.; Yamamoto, R.; Hatayama, F.; Kitamura, S.;Itoh, H. Anal. Chem. 1980, 52, 1064. (79C) Torsi, G.; Desimoni, E.; Palmisano, F.; Sabbatini, L. Anal. Chem. 1981, 53, 1035. (8OC) Torsi, G.; Desimoni, E.; Paimisano, F.; Sabbatini, L. Anal. Chlm. Acta 1981, 124, 143. (81C) Tyson, J. F.; Idris, A. B. Analyst (London) 1981, 106, 1125. (82C) Uchida, T.; Iida, C.; Kojima, I. Anal. Chlm. Acta 1980, 113, 361. (83C) Uchida, T.; Kojima, I.; Iida, C. Anal. Chim. Acta 1980, 116, 205. (84C) Uchida, T.; Kojima, I.; Iida, C. Analyst (London) 1981, 106, 206. (85C) Ure, A. M.; Ewen, G.J.; Mitchell, M. C. Anal. Chlm. Acta 1980, 118, 1. (86C) Vljan, P. N. At. Spectrosc. 1980, 1 , 143. (87C) Woiff, E. W.; Landy, M. P.f Peel, D. A. Anal. Chem. 1981, 53, 1566.
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Aerosol Characterlzatlon end Studles (88C) Arpadjan, S.;Stojanova, D. Fresenlus' 2.Anal. Chem. 1980, 302, 206. (89C) Boorn, A. W.; Cresser, M. S.; Browner, R. F. Spectrochim. Acta, Part 8 1980. 358. 823. (9OC) Cresser, M. S.; Browner, R. F. Spectrochlm. Acta, Part8 1980, 358, 73. (91C) Cresser, M. S.; Browner, R. F. Appl. Spectrosc. 1980, 34, 364. (92C) Kodama, M.; Miyagawa, S.Anal. Chem. 1980, 52, 2358. (93C) Mohamed, N.; Fry, R. C. Appl. Spectrosc. 1981, 35, 400. (94C) Mohamed, N.; Fry, H. C.; Wetzel. D. L. Anal. Chem. 1981, 53, 639. (95C) Novak, J. W.f Browner, R. F. anal. Chem. 1980, 52, 287. (96C) Novak, J. W.; Browner, R. F. Anal. Chem. 1980, 52,792. Extraction (97C) Clark, J. R.; Viets, J. G. Anal. Chem. 1981, 53, 61. (98C) Clark, J. R.; Viets, J. G. Anal. Chem. 1981, 53,65. (99C) Dramantatos, A. Anal. Chim. Acta 1981, 131,53. (1OOC) Magnusson, 6.; Westeriund, S. Anal. Chim. Acta 1981, 131, 63. (101C) Nord, L.; Karlberg, B. Anal. Chlm. Acta 1981, 125, 199. (102C) Sinex, S. A.; Cantiilo, A. Y.; Heiz, G. R. Anal. Chem. 1980, 52, 2342. (103C) Subramanian. K. S.; Meranger, J. C. Analyst (London) 1980, 105, 620.
Developments In Sample Introduction Technlques
Magneto-optic Phenomena In Anaiytlcal Atomlc Spectrometry-Zeeman, Faraday, and Volgt Effects
(41'2) Batiey, 0. E.; Matousek, J. P. Anal. Chem. 1980, 52, 1570. (42C) Basson, W. D.; Van Staden, J. F. Fresenlus' Z.Anal. Chem. 1980, 302,370. (43C) Berndt, H.; Mesaerschmidt, J. Spectrochlm. Acta, Part 8 1981, 368, 809.
(104C) Brodie, K. G.; Liddeil, P. R. Anal. Chem. 1980, 52, 1059. (105C) Carnrick, G. R.; Siavin, W.; Manning, D. C. Anal. Chem. 1981, 53, 1866. (l06C) De Loos-Voliebregt, M. T. C. INIS Atomlndex 1980, 1 1 , Abstr. No. 553016. ANALYTICAL CHEMISTRY, VOL. 54, NO. 5, APRIL 1982
289R
ATOMIC ABSORPTION, ATOMIC FLUORESCENCE, AND FLAME SPECTROMETRY (107C) De Loos-Vollebregt, M. T. C.; De Galan, L. Appl. Spectrosc. 1979, 33, 616. (106C) De Loos-Vollebregt, M. T. C.; De Galan, L. Appl. Spectrosc. 1980, 34. 464. (lO9C) De Loos-Vollebregt, M. T. C.; De Galan, L. Spectrochim. Acta, Part B 1980.358. 495. (11OC) Debus, H.; Hanle, W.; Scharmann, A.; Wirz, P. Spectrochlm. Acta, Part B 1981,368, 1015. (1 11C) Fernandez, F. J.; Bohler, W.; Beaty, M. M.; Barnett, W. B. A t . Spectrosc. 1981,2 , 73. (112C) Fernandez, F. J.; Myers, S. A.; Slavin, W. Anal. Chem. 1980,52. 741. (1 13C) Frigieri, P.; Trucco, R. Spectrochlm. Acta, Part B 1980,358, 113. (114C) Hirokawa, K. Anal. Chem. 1980,52, 1966. (115C) Hlrokawa, K.; Namikl, M. Spectrochim. Acta, Part B 1981, 368, 649. (116C) Ito, M. Anal. Chem. 1980,52, 1592. (117C) Jolly, G.; Stephens, R. Anal. Chlm. Acta 1980, 716,365. (118C) Kankare, J. J.; Stephens, R. Spectrochim. Acta, Part B 1980,358, 849. ( l l 9 C ) Kersey, A. D.; Dawson, J. 8. Anal. Proc. (London) 181, 18, 187. (120C) Kersey, A. D.; Dawson, J. B.; Ellis, D. J. Spectrochlm. Acta, Part B 1980,358,865. (121C) Kitagawa, K.; Aol, N.; Tsuge, S. Spectrochim. Acta, Part B 1981, 368, 1097. (122C) Kitagawa, K.; Nanya, T.; Tsuge, S. Spectrochlm. Acta, Part B 1981, 368,9. (123C) Kitagawa, K.; Suzukl, M.; Aci, N.; Tsuge, S. Spectrochlm. Acta, Part B 1981,368,21. (124C) Koizumi, H.; Hadeishi, T.; McLaughiin, R. D Spectrochim. Acta, Part B 1981,368,483. (125C) Koizurni, H.; Yamada, H.; Yasuda, K.; Uchmo, K.; Oishi, K. Specfrochim. Acta, Part B 1981,368, 603. (126C) Liddell, P. R.; Brodle, K. 0. Anal. Chem. 1980,52, 1256. (127C) Magyar, B.; Vonmont, H. Spectrochlm. Acta, Part B 1980, 358, 177. (128C) Oishi, K.; Arai, Y.; Mayama, S.; Murayama, S.; Fukuda, K. Spectrochlm. Acta, Part B 1980,358, 155. (129C) Stephens, R. CRC Crit. Rev. Anal. Chem. 1980,9, 187. (130C) Yamamoto, M.; Murayama, S.;Ito, M.; Yasuda, M. Spectrochlm. Acta, Part B 1980,358. 43. (131C) Yasuda, K.; Koizumi, H.; Ohlshl, K.; Noda, T. Prog. Anal. At. Spectrosc. 1980,3 ,299. (132C) Yasuda, M.; Murayarna, S. Spectrochlm. Acta, Part B 1981,368, 641.
L'vov, 9. V.; Pelieva, L. A. Prog. Anal. At. Spectrosc. 1980,3 ,65. Maney, J. P.; Luciano, V. J. Anal. Chlm. Acta 1981, 125, 183. Matousek, J. P. Prog. Anal. At. Spectrosc. 1981,4, 247. McCamey, D. A.f Niemczyk, T. M. Appl. Spectrosc. 1980,34, 692. Mueiler-Vogt, G.; Wendl, W. Anal. Chem. 1981,53,651. Persson, J. A.; Frech, W. Anal. Chlm. Acta 1980, 119. 75. Rlandey, C.; Gavlnelll, R.; Pinta, M. Spectrochlm. Acta, Part 8 1980, 358, 765. (30D) Roblnson, J. W.; Rhodes, L. J. Spectrosc. Lett. 1980, 13,253. (31D) Salmon, S. G.; Davis, R. H.; Holcombe, J. A. Anal. Chem. 1981,53, 324. (32D) Sierner, D. D.; Baldwln, J. M. Anal. Chem. 1980,52,295. (33D) Smets, 9. Spectrochlm. Acta, Part B 1980,358, 33. (34D) Sturgeon, R. E.; Berrnan, S. S. Anal. Chem. 1981,53, 632. (350) Sturgeon, R. E.; Berman, S. S.; Kashyap, S. Anal. Chem. 1980,52, 1049. (36D) Styris, D. L.; Kaye, J. H. Spectrochlm. Acta, Part B 1981,368,41. (37D) Tsumoda, K.; Haraguchl, H.; Fuwa, K. Spectrochlm. Acta, Part B 1980,358, 715. (38D) Voinovitch, I.; Druon, M.; Legrand, G.; Louvrler, J.; Bouzanne, M.; Sors, M.; Friant, G.; Liagre, J. M. Spectrochlm. Acta, Part B 1980,358, 807. (23D) (24D) (25D) (260) (27D) (28D) (290)
Alomlzer Structure, Form, and Composlllon (39D) Fernandez, F. J.; Beaty, M. M.; Barnett, W. B. At. Spectrosc. 1981, 2 , 16. (40D) Hinderberger, E. J.; Kaiser, M. L.; Koirtyohann, S. R. At. Spectrosc.
l981,2,1.
(41D) Kaiser, M. L.; Kolrtyohann, S. R.; Hinderberger, E. J.; Taylor, H. E. Spectrochim. Acta, Par? B 1981,368,773. (420) Marshall, J.; Bezur, L.; Fakhrul-Aldeen, R.; Ottaway, J. M. Anal. Proc. (London) 1981, 18, 10. (43D) Montgomery, J. R.; Peterson, G. N. Anal. Chim. Acta 1980, 117, 397. (44D) Halllday, M. C.; Houghton, C.; Ottaway, J. M. Anal. Chlm. Acta 1980, 119, 67. (45D) Hodges, D. J.; Skeldlng, D. Analyst (London) 1981, 106,299. (48D) Hulanlcki, A.; Karwowska, R.; Stanczak, J. Talanta 1980, 27, 214. (47D) Lythgoe, D. J. Analyst (London) 1981, 106,737. (48D) Poidoski, J. E. Anal. Chem. 1980,52, 1147. (49D) Puschel, P.; Formanek, 2.; Hlavac, R.; Koiihova, D.; Sychra, V. Anal. Chlm. Acta 1981, 127, 109. (50D) Schmidt, W.; Dietl, F. Fresenlus' 2. Anal. Chern. 1980, 303, 385. (51D) Slemer, D. D.; Hageman, L. Anal. Chem. 1980,52, 105. (52D) Slavin, W.; Manning, D. C. Spectrochlm. Acta, Part B 1980,358, 701. (53D) Slavin, W.; Mannlng, D. C.; Carnrick, G. Anal. Chem. 1981,53, 1504. (54D) Slavln, W.; Myers, S.A,; Manning, D. C. Anal. Chlm. Acta 1980, 117, 267. (55D) Slovak, 2.; Docekal, 9. Anal. Chlm. Acta 1981, 130,203. (56D) Suzukl, M.; Ohta, K. Talanta 1981,28, 177. (57D) Suzuki, M.; Ohta, K.; Yamakita, T. Anal. Chem. 1981,k3, 9. (58D) Suzuki, M.; Ohta, K.; Yamakita, T. Anal. Chem. 1981, 53, 1796. (59D) Suzuki, M.; Ohta, K.; Yamakita, T. Anal. Chim. Acta 1981, 133,209. (80D) Suzukl, M.: Ohta, K.; Yamakita, T.; Katsuno, T. Spectrochim. Acta, Part B 1981,368,679. (6lD) Velllon, C.; Guthrie, B. E.; Wolf, W. R. Anal. Chem. 1980,52,457. (62D) Vlckrey, T. M.; Harrison, G. V.; Ramelow, G. J. At. Spectrosc. 1980, 1 , 116. (63D) Vlckrey, T. M.; Harrison, G V.; Ramelow, G. J.; Carver, J. C. Anal. Lett. 1980, 13,761. (64D) Vlckrey, T. M.; Harrison, 0. V.; Rarnelow, G. R. Anal. Chem. 1981, 53, 1573. (65D) Wahab, H. S.; Chakrabarti, C. L. Spectrochlm. Acta, Part B 1981, 368,463. (66D) Wahab, H. S.; Chakrabarti, C. L. Spectrochlm. Acta, Part B 1981, 368,475.
Laser-Enhanced lonlzatlon Spectrometry (133C) van Dijk. C. A.; Curran, F. M.; Lin. K. C.; Crouch, S.R. Anal. Chem. 1981,53, i275. (134C) Green, R. B.; Harrilla, G. J.; Trask, T. 0. Appl. Spectrosc. 1980,34, 561.
(135C). Harriila, G. J.; Green, R. B. Anal. Chem. 1980,52, 2376. (136C) Hurst, G. S.Anal. Chem. 1981,53, 1449 A. (137C) Trask, T. 0.; Green, R. B. Anal. Chem. 1981,53, 320. (138C) Turk, G. C. Anal. Chem. 1981,53, 1187. (139C) Zalewskl, E. F.; Keller, R. A,; Apel, C. T. Appl. Opt. 1981,20, 1584. ELECTROTHERMALATOMIZATION PERFORMANCE STUDIES AND TECHINWE DEVELOPMENT Performance Characlerlzallon (ID) Akman, S.; Genc, 0.; Balkis, T. Spectrochim. Acta, Part B 1981,368, 1121. (2D) Akman, S.; Genc, 0.; Ozdural, A. R.; Balkis, T. Spectrochim. Acta, Part B 1980,358,373. (3D) Beaty, M.; Barnett, W.; Grobenskl, 2. At. Spectrosc. 1980, 1, 72. (4D) Chakrabarti, C. L.; Hamed, H. A.; Wan, C. C.; Li, W. C.; Bertels. P. C.; Gregolre, D. C.; Lee, S. Anal. Chem. 1880,52, 187. (5D) Chakrabarti, C. L.; Wan, C. C.; Hamed, H. A.; Bertels, P. C. Nature (London) 1980,288, 246. (6D) Chakrabarti, C. L.; Wan, C. C.; Harned, H. A,; Bertels, P. C. Anal. Chem. 1981,53, 444. (7D) Chakrabarti, C. J.; Wan, C. C.; Tesky, R. J.; Chang, S. B.; Harned, H. A.; Berteis, P. C. Spectrochlm. Acta, Part B 1981,368,427. (8D) Erspamer, J. P.; Niemczyk, T. M. Appl. Specfrosc. 1981, 35, 512. (9D) Falk, H.; Hoffmann, E.; Ludke, Ch. Spectrochlm. Acta, Part B 1981, 368, 767. (10D) Falk, H.; Tham, T. K. Specfrochlm. Acta, Part B 1980, 358, 465. (11D) Feinberg, M.; Ducauze, C. Analusis 1980,8 , 185. (12D) Frech, W.; Cedergren, A. Anal. Chlm. Acta 1980, 113,227. (13D) Frech, W.; Persson, J. A,; Cedergren, A. Prog. Anal. At. Spectrosc. 1980,3 ,279. (14D) Genc, 0.; Akman, S.; Ozdural, A. R.; Ates, S.; Balkis, T. Spectrochlm. Acta, Part B 1981,368, 163. (150) Kantor, T.; Bezur, L.; Pungor, E. Mlkrochim. Acta 1981, 1 , 289. (16D) Karwowska. R.; Buiska, E.; Hulanicki, A. Talanta 1980,27, 397. (17D) Kitagawa, K.; Ide, Y.; Takeuchl, T. Anal. Chim. Acta 1980, 113,21. (180) Koirtyohann. S.R.; Glass, E. D.; Llchte, F. E. Appl. Spectrosc. 1981,
35,22. (19D) Koreckova, J.; Frech. W.; Lundberg, - E.; Persson, J.-A.; Cedergren, A. Anal. Chim. Acta 1981, 130,267. (20D) Lawson, S. R.; Woodrlff, R. Spectrochlm. Acta, Part B 1980,358, 753. (210) Lundberg, E.; Frech, W. Anal. Chem. 1981,53, 1437. (22D) L'vov, B. V.; Bagunov, P. A.; Ryabchuk, G. N. Spectrochlm. Acta, Part B 1981,368,397.
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APPLICATIONS OF ELECTROTHERMAL ATOMIZATION ATOMIC ABSORPTION SPECTROMETRY Delermlnatlons of Speclflc Elements (IE) Aungst, 8. J.; Dolce, J.; Fung, H.-L. Anal. Lett. 1980, 13,347. (2E) Battistonl, P.; Bruni, P.; Cardeliini, L.; Fava, G.; Gobbl, G. Talanta 1980, 27,623. (3E) Berndt, H.; Messerschmldt, J.; Alt, F.; Somrner, D. Fresenlus' 2.Anal. Chem. 1981,306,385. (4E) Bertenshaw, M. P.; Gelsthorpe, D.; Wheatstone, K. C. Analyst (London) 1981, 106,23. (5E) Calhoun, W. 0.; Hurley, R. B. Anal. Chem. 1980,52, 1551. (6E) Callio, S. At. Spectroc. 1980, 1 , 80. (7E) Chao, S.S.; Pickett, E. E. Anal. Chem. 1980,52,335. (8E) Chapman, J. F.; Dale, L. S.; Fraser, H. J. Anal. Chlm. Acta 1980, 116, 427. (9E) Dits, J. S. Anal. Chlm. Acta 1981, 130,395. (10E) Dogan, S.;Haerdi, W. I n t . J. Envlron. Anal. Chem. 1980,8, 249. (11E) Donaldson, E. M. Talanta 1980,27,79. (12E) Donaldson, E. M. Talanta 1980,27,499. (13E) Donaldson, E. M. Talanta 1980,27, 779. (14E) El-Defrawy, M. M. M.; Posta, J.; Beck, M. T. Anal. Chirn. Acta 1980, 115, 155. (15E) Fazakas, J. Anal. Lett. 1981, 14, 535. (16E) Friaierl. P.: Trucco. R.: Claccollni, I.; PamDurini, G. Analyst (London) 1880,705, 651. (17E) Gllksman, J. E.; Gibson, J. E.; Kandetzski, P. E. At. Spectrosc. 1980, 1, 166. ~
ATOMIC ABSORPTION, ATOMIC FLUORESCENCE, AND FLAME SPECTROMETRY (18E) Horsky, S. J. A t . Spectrosc. 1980, 7, 129. (19E) Kontas, E. At. Spectrosc. 1981, 2 , 59. (20E) Krinltz, B.; Tepedino, N. J . Assoc. Off. Anal. Chem. 1981, 64, 1014. (21E) Longmhyr, F. J.; Dahl, I.M. Anal. Chim. Acfa 1981, 737. 303. (22E) Matsusaki, K.; Yoshlno, T.; Yamamoto, Y. Anal. Chim. Acta 1980, 7 73, 247. (23E) Matsusaki, K.; Yoshino, T.; Yamamoto, Y. Anal. Chim. Acfa 1981, 724, 163. (24E) Mauucotelli, A.; Frache, R. Analyst (London) 1980, 705, 497. (25E) Meier, A. L. J . Geochom. Explor. 1980, 73, 77. (26E) Mendiola Ambroslo, J. lit; Gonzaiez Lopez, A. Rev. Plast. Mod. 1981, 4 7 , 550. (27E) Mltchum, R. PI. Analysi' (London) 1980, 705, 43. (28E) Nakashima, S. Fresenirus' 2.Anal. Chem. 1980, 303, 10. (29E) Neuman, D. R.; Munshlower, F. F. Anal. Chlm. Acta 1981, 723, 325. (30E) Persson, J. A.; French, W.; Pohl, G.; Lundgren, K. Analyst (London) 1980, 705, 1163, (31E) Rantala, R. T. T.; Lorirng, D. H. At. Spectrosc. 1980, 7 , 163. (32E) Rouseff, R. L.; Tlng, S V. J. Fwd Sci. 1980, 45, 965. (33E) Slikkerveer, F. J.; Braad, A. A.; Hendrikse, P. W. At. Spectrosc. 1980, 7, 30. (34E) Studnicki, M. Anal. Chem. 1980, 5 2 , 1762. (35E) Suddendorf, Fi. F.: Wright, S. K.; B o w , K. W. J . Assoc. Off. Anal. Chem. 1981, 64, 657. (38E) Sugisaki, H.; Nakamura, H.; Hirao, Y.; Kimura, K. Anal. Chlm. Acta iga'i. 125 203 .- - ., .- - , - - - . (37E) Terada. K.; Nakamura, K. Talanta 1981, 2 8 , 123. (38E) Tsukahara, I.; Tanaka, M. Talanta 1980, 2 7 , 237. (39E) Tsukahara, I.;: Tanaka,,M. Talanta 1980, 2 7 , 655. (40E) Van der Geugten, R. F'. Fresenius' Z.Anal. Chem. 1981, 306, 13. (41E) Victor, A. H.; Streiow, F. W. E. Talanfa 198'1, 28, 207. (42E) Vilcsek, E.; Lohmann, (5. Fresenius ' 2.Anal. Chem. 1980, 304, 395. (43E) Wang, W . J . Anal. Chim. Acta 1980. 779, 157. Determinations of Elements Iln Speclflc Matrices (44E) Armannsson, H.; Ovenlden, P. J. Int. J. Environ. Anal. Chem. 1980, 8, 127. (45E) Bagllano, G.; Benischek, F.; Huber, I . Anal. Chim. Acta 1981, 723, 45. (46E) Bomgardner, I): L. Occas. Pap.-Br. Mus. 1981, 79, 93. (47E) Borriello, R.; Iiciaudono, G. At. Spectrosc. 1980, 7, 131. (48E) Chapman, J. F.; Leadbeatter, B. E. Anal. Left. 1980, 73, 439. (49E) De Antonio, 8. M.; Katz, S. A.; Schelner, D. M.; Wood, J. D. Anal. Proc. (London) 1981, 78,162. (50E) Dikeman, E.; Bechtel, D. B.; Pomeranz, Y. Cereal Chem. 1981, 56, 148. (51E) Doolan, K. J.; Belcher, C. B. Prog. Anal. At. Spectrosc. 1980, 3 , 125. (52E) Eskell, C. J.; Pick, M. E. Anal. Chlm. Acta 1980, 777, 275. (53E) Farag, R. S.; El-Aassar, S. T.; Mostafa, M. A.; Abdel Rahim, E. A. J. Drug. Res. 1980, 72, 217'. (54E) Farag, R. S.;El-Aassar, S. T.; Soliman, M. M. J. Drug. Res. 1980, 12, 227. (55E) Feinberg, M.; Ducauze,,C. Anal. Chem. 1980, 5 2 , 207. (56E) Garbett, K.; Goodfellow, G. L.; Marshall, 0. B. Anal. Chlm. Acfa 1981, 726, 135. (57E) Garbett, K.; Goodfellow, G. I.; Marshall, G. B. Anal. Chlm. Acta 1981, 126, 147. (58E) Guerra, R. At. Spectrossc. 1980, 7, 58. (59E) Guevremont, R.; Sturgieon, R. E.; Berman, S. S. Anal. Chim. Acta 1980, 775, 163. (60E) Guevremont, R. Anal. Chem. 1980, 5 2 , 1574. (61E) Guevremont, H. Anal. Chem. 1981, 5 3 , 9111. (62E) Hall, A.; Godlnho, M. C. Anal. Chim. Acta 1980, 773, 369. (63E) Heanes, D. L. Analyst (London) 1981, 706, 182. (64E) Holak, W. J . Assoc. O'ff.Anal. Chem. 1980, 63,485. (65E) Hon, P. K.; Lau, 0. W.; Luk, S.F.; Mok, C. S.Anal. Chlm. Acfa 1980, 773, 175. (68E) Hon, P. K.; Lau, 0. W.; Mok, C. S. Ana/yst(London) 1980, 705, 919. (67E) Hubert, J.; Candelaria. R. M.; Applegate, H. G. At. Spectrosc. 1980, 7 , 90. (68E) Hydes, D. J. Anal. Chem. 1980, 52, 959. (69E) Isaac, R. A. J. Assoc. Off. Anal. Chem. 1980, 6 3 , 788. (70E) Iyengar, S. S.; Martens, D. C.; Mlller, W. P. Soil Scl. 1981, 737, 95. (71E) Katz, S.A.; Jennlss, S. W.; Mount, T.; Tout, R. E.; Chatt, A. Int. J . Environ. Anal. Chem. 1981, 9 , 209. (72E) Klinkhammer, G. P. Anal. Chem. 1980, 5 2 , 117. (73E) Kupchella, L.; Syty, A. J . Agrlc. FoodChem. 1980, 2 8 , 1035. (74E) Labrecque, J. J.; Schorin, H. Appl. Spectrosc. 1980, 3 4 , 39. (75E) Lepage, M. J. Am. Sol:. Brew. Chem. 1980, 38. 116. (76E) Leyden, D. E.; Wegscheider, W. Anal. Chem. 1981, 53, 1059A. (77E) Lleu, V. T.; Woo, D. H. At. Spectrosc. 1980, 7 , 149. (78E) Magalousis, N. M.; Gritton, V. Occas. Pap.-Br. Mus. 1981, 19, 103. (79E) Mason, J. T. J. Pharm. Sci. 1980, 6 9 , 101. (80E) Mazzucoteiii, A.; Fracho, R. Mikrochim. Acta 1981, 2 , 323. (81E) Mills, J. C.; Belcher, C. B. frog. Anal. At. Spectrosc. 1981, 4, 49. (82E) Monlen, H.; Bovenkerk, R.; Kringe, K. P.; Rath, D. Fresenius' 2.Anal. Chem. 1980, 300, 363. (83E) Newbury, M. L. J.-Can., SOC. Forensic Scl. 1980, 13, 19. (84E) Newton, J. T. J. Forencric Scl. 1981, 2 6 , 302. (85E) Noller, B. N.; Bloom, ti;Arnold, A. P. Prog. Anal. At. Specrrosc. 1981, 4 , 81. (86E) Patel, B. M.; Gupta, N.; Purohit, P.; Joshl, B. D. Anal. Chim. Acta 1980, 778,163. (87E) Pedersen, B.; Willems, hd.; Storgaard Joergensen, S. Analyst (London) 1980, 705, 119.
(88E) Petrov, I.I.; Tsalev, D. L.; Barsev, A. I. At. Spectrosc. 1980, 7, 47. (89E) Ramamurty, C. K.; Kaiser, G.; Toelg, G. Mlkrochim. Acta 1980, f , 79. (90E) Rasmussen, L. Anal. Chim. Acta 1981, 725, 117. (91E) Rath, H. J. Fresenius' 2.Anal. Chem. 1980, 302, 275. (92E) Robinson, J. W.; Weiss, S. J. Environ. Sci. Health 1980, A75, 663. (93E) Saeed, K.; Thomassen, Y. Anal. Chim. Acta 1981, 730, 281. (94E) Segar, D. A.; Cantlllo, A. Y. Anal. Chem. 1980, 5 2 , 1766. (95E) Sen Gupta, J. G. Talanta 1981, 2 8 , 31. (96E) Smith, M. R.; Coctaan, H. B. At. Spectrosc. lS81, 2, 97. (97E) Sperllng, K. R.; Behr, B. Fresenius' Z.Anal. Chem. 1981, 306, 7. (98E) Startseva, E. A.; Popova. N. M.; Yudelevich, I . G.; Vanifatova, N. G.; ZolOtOv, Yu. A. Fresenius' Z.Anal. Chem. 1980, 300, 28. (99E) Stein, V. B.; Canelll, E.; Richards, A. H. I n t . J. Environ. Anal. Chem. 1980, 8 , 99. (100E) Stein, V. B.; McClellan, B. E. Environ. Sci. Techno/. 1980, 74, 872. (101E) Sterritt, R. M.; Lester, J. N. Analyst (London) 1980, 705, 618. (102E) Sturgeon, R. E.; Berman, S. S.; Desaulniers, J. A. H.; Mykytiuk, A. P.: McLaren, J. W.; Russell, D. S. Anal. Chem. 1980, 5 2 , 1585. (103E) Sturgeon, R. E.; Berman, S.S.; Desauiniers, A.; Russell, D. S. Talanta 1980, 2 7 , 65. (104E) Sturgeon, R. E.; Berman, S. S.;Desaulnlers, A.; Russell, D. S.Anal. Chem. 1980, 5 2 , 1767. (105E) Thompson, K. C.; Wagstaff, K. Analyst (London) 1980, 705, 883. (106E) Tsukahara, I.; Tanaka, M. Anal. Chim. Acta 1980, 176, 383. (107E) Tubb, A.; Parker, A. J.; Nlckiess, G. Archaeometry 1980, 2 2 , 153. (108E) Varma, A. At. Spectrosc. 1980, 7, 123. Delermlnallons of Elements in Human Biological Matrices (109E) Alderman, F. R.; Gltelman, H. J. Clln. Chem. (Winston-Salem, N . C . ) 1980, 2 6 , 258. (llOE) Barfoot, R. A.; Pritchard, J. G. Analyst (London) 1980, 705, 551. (111E) Bruhn, C.; Navarrete, G. Anal. Chim. Acta 1981, 130, 209. (112E) Carpenter, R. C. Anal. Chim. Acta 1981, 725, 209. (113E) Carter, G. F.; Yeoman, W. B. Analyst (London) 1980, 705, 295. (114E) De Haas. E. J. M.; De Wolff, F. A. Clin. Chem. (Wlnston-Salem, N . C . ) 1981. 2 7 . 205. (115E) Delves, H. T. Prog. Anal. At. Spectrosc. 1981, 4, 1. (116E) Delves, H. T.; Woodward, J. At. Spectrosc. 1981, 2 , 65. (117E) Denniston, M. L.; Sternson, L. A,; Repta, A. J. Anal. Left. 1981, 74, 451. (118E) Dornemann, A.; Kleist, H. Fresenius' 2. Anal. Chem. 1980, 300, 197. (119E) Gardlner, P. E.; Ottaway, J. M.; Fell, G. S.;Burns, R. R. Anal. Chim. Acta 1981, 724, 281. (120E) Gardlner, P. E.; Ottaway, J. M.; Fell, G. S.;Halls, D. J. Anal. Chim. Acta 1981, 726, 57. (121E) Goldberg, W. J.; Alien, N. Clin. Chem. (Winston-Salem, N.C.)1981, 2 7 , 582. (122E) Graf-Harsanyi, E.; Langmyhr, F. J. Anal. Chim. Acta 1980, 776,105. (123E) Halls, D. J.; Fell, G. S. Anal. Chim. Acta 1981, 129, 205. (124E) Hails, D. J.; Fell, G. S.; Dunbar, P. M. Clin. Chim. Acta 1981, 714, 21. (125E) Hull, D. A.; Muhammad, N.; Lanese, J. G.; Relch, S.D.; Finkelstein, T. T.; Fandrich, S. J. Pharm. Sci. 1981, 70, 500. (126E) Iida, C.; Uchida, T.; Kojlma, I.Anal. Chlm. Acfa 1980, 773, 365. (127E) IUPAC Ciinlcal Chemistry Dlvlsion Pure Appl. Chem. 1981, 5 3 , 773. (128E) Kelson, J. R. Clin. Chem. (Winston-Salem, N.C.)1980, 2 6 , 349. (129E) Kiiierich, S.;Christensen, M. S.; Naestoft, J.; Christlansen. C. Clln. Chim. Acta 1980, 705, 231. (130E) Klllerich, S.; Christensen, M. S.; Naestoft, J.; Christiansen, C. Clin Chlm. Acta 1981, 714, 117. (131E) Kumpulainen, J. Anal. Chim. Acta 1980, 173, 355. (132E) Ladefoged, K. Clin. Chlm. Acta 1980, 700, 149. (133E) Lawrence, C. B.; Phillippo, M. Anal. Chim. Acta 1980, 776, 153. (134E) Legotte, P. A.; Rosa, W. C.; Sutton, D. C. Talanta 1980, 2i', 39. (135E) Levi, S.;Fortin, R. C.; Purdy, W. C. Anal. Chim. Acta 1981, 127, i n2 .--. (136E) Levi, S.; Purdy, W. C. Ciln. Biochem. 1980, 73, 253. (137E) Levi, S.;Purdy, W. C. Anal. Chim. Acta 1980, 776,375. (138E) Lichtman, A. H.; Segel, G. 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Anal. Chem. 1982, 5 4 , 293 R-322 R (13G) Minagawa, K.; Takizawa, Y.; Kifune, I.Anal. Chim. Acta 1980, 775, 103. (14G) Narasaki, H. Anal. Chim. Acta 1981, 725,187. (150) Oda, C. E.; Ingle, J. D. Anal. Chem. 1981, 53,2030. (16G) Oda, C. E.; Ingle, J. D. Anal. Chem. 1981, 53,2305. (17G) Oster, 0. J. Clin. Chem. Clin. Biochem. 1981, 79, 471. (18G) Pollock, E. W. At. Spectrosc. 1980, 7, 78. (19G) Randiesome, J. E.; Aston, S. R. Environ. Techno/. Lett. 1980, I , 3. Takagui, E.; Deguchi, T.; Nagai, H. Anal. Chim. Acta (20G) Sanemasa, I.; 1981, 730,149. (21G) Scott, J E.; Ottaway, J. M. Analyst (London) 1981, 706, 1076. (22G) Suddendorf, R. F. Anal. Chem. 1981, 5 3 , 2234. (23G) Szakacs, 0.; Lasztifij, A.; Horvath, 2s.Anal. Chim. Acta 1980, 727, 219. (24G) Tanabe, K.: Takahimhi, J.; Haraauchi, t i : Fuwa. K. Anal. Chem. 1980, 52,453. (25G) Tong, S. L.1 Leo, W. K. Anal. Chem. 1980, 52, 581. (26G) Tuncel, G.; Yavuz Ataman, 0. At. Spectrosc. 1980, 7 , 128. (27G) Wigfieid, D. C.; Croteau, S. M.; Perkins, S. L. J. Anal. Toxlcol. 1981, 5. 52. (28Gj Wittmann, Zs. Talanta 1981, 28 271. SOME CHROMATOGRAPHY CONNECTIONS (1H) Brinckman, F. E.; Jewett, K. L.; Iverson, W. P.; Irgoiic, K. J.; Ehrhardt, K. C.; Stockton, R. A. J. Chromatogr. 1980, 797, 31. (2H) Chan, L. Foronslc S o . Int. 1981, 78, 57. (3H) Coe, M.; Cruz, R.; Van Loon, J. C. Anal. Chim. Acta 1980, 720,171. (4H) Cruz, R. B.; Lorouso, C.; George, S.; Thomassen, Y.; Kinrade, J. D.; Butler, L. R. P.; Lye, J.; Van Loon, J. C. Spectrochim. Acta, Part B 1980, 358, 775. (5H) De Jonghe, W.; Chakraborti, D.; Adams, F. Anal. Chlm. Acta 1980, 775,89. (6H) De Jonghe, MI. R. A.; Chakraborti, D.; Adams, F. C. Anal. Chem. 1980, 52, 1974. (7H) Folestad, S.; Josefsson, B. J. Chromatogr. 1981, 203, 173. (8H) Hahn, M. H.; Muiligan, K. J.; Jackson, M. E.; Caruso, J. A. Anal. Chim. Acta 1980, 778, 115. (9H) Iadevala, R.; Aharonson, N.; Woolson, E. A. J. Assoc. Off. Anal. Chem. 1980, 63,742. (lOH) Korophak, J. A.; Coleman, G. N. Anal. Chem. 1980, 52, 1252. (11H) Messman, J. D.; Rains, T. C. Anal. Chem. 1981, 53, 1632. (12H) Ricci, G. R: SheDard, L. S.: Coiovos. G.: Hester. N. E. Anal. Chem. 1981, 53,610. (13H) Suzuki, K. 7'. Anal. 13iochem. 1980, 102,31. (14H) Thorburn Burns, D.; Giockllng, F.; Harriott, M. Analyst (London) 1981, 706. 921. (15H)-'ktareiii, P.; Mascherpa, A. Anal. Chem. 1981, 53, 1466. (16H) Van Loon, J. C. Am. Lab. (Fairfield, Conrr.) 1981, 73,47. (17H) Vickrey, T. M.; Howlell, H. E.; Harrison, G. V.; Ramelow, G. J. Anal. Chem. 1980, 5 2 , 1743. (18H) Woolson, E. A.; Aharonson, N. J. Assoc. Off. Anal. Chem. 1980, 63, 523. ATOMIC FLUORESCENCE SPECTROMETRY (11) Azad, J.; Kirkbright, G. F.; Snook, R. D. Analyst (London) 1980, 705, 79. (21) Bolshov, M. A.; Zyblri, A. V.; Koioshnikov, V. G.; Vasnetsov, M. V. Spectrochim. Acta, Part B 1981, 368,345.
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Surface Analysis: X-ray Photoelectron Spectroscopy, Auger Electron Spectroscopy, and Secondary Ion Mass Spectrometry Noel H. Turner and Richard J. Colton" Chemistry Divisbn, Naval Research Laboratory, Washington, D.C. 20375
The present review is on the subject of surface analysis and includes the fields of X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), and secondary ion mass spectrometry (SIMS) for the period of 1979-1981. This review will cover the literature abstracted in Chemical Abstracts between September 3, 1979, and November 2,1981 (plus some important articles that have appeared in the latter part of 1981). The reviews of XPS, AES, and SIMS are written as separate sections for the reader's convenience. XPS, AES, and SINE are the most widely used techniques in surface analysis anld are often used in combination. Although XPS (and U P S ) and AES have been covered by earlier
Fundamental Reviews in Analytical Chemistry ( l a ) SIMS , is only mentioned briefly in the Application Reviews on Surface Characterization (6). Considering the importance of surface analysis in today's technology, we thought that XPS, AES, and SIMS should be included in one review. This review, although lengthy, is not an all-inclusive(2 year) bibliography of XPS, AES, or SIMS. We have tried to select the most important papers in each field that (in our opinion) will advance the "state of the art" of XPS, AES, and SIMS. We also decided to omit some topics such as the use of synchrotron radiation in XPS, for example, and to limit or ignore a large number of papers on applications in order to keep this
This article not subject to US. Copyright. Published 1982 by the American Chemical Society
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