Emission Spectrometry Marvin Margoshes, Digilab, Inc., P.O. Box 2047, Silver Spring, Md. 20902 Bourdon F. Scribner, National Bureau o f Standards, Washington, D. C. 20234
T
is the eleventh in a series; it covers primarily publications during 1968 and 1969, with the addition of some significant publications from earlier years which came to our attention after the last review (16A) was written. As has been the practice in earlier reviews, most attention is devoted to contributions of basic importance with less emphasis on applications. The reader may refer to reviews published in this journal in alternate years for information on the developments in emission spectroscopy in individual applied fields. We noted last year the increasing difficulty of isolating flame techniques from other areas of spectrometric analysis. Xevertheless, the sheer number of publications on flame techniques including atomic absorption and atomic fluorescence as well as emission, reflects a general interest in this specific subject and has made it advisable to devote a separate review to it. We trust that this arrangement will be more satisfactory to the reader than the single review article attempting to encompass too large and too active a n area. HIS REVIEW
BOOKS AND REVIEWS
ii new volume of “Spectrochemical Abstracts” (MA) covers the years 1967 and 1968. It abstracts 470 publications in emission spectrometry, flame emission and absorption, and X-ray spectrometry; clearly this is not an inclusive list, but only selected references. Another way to keep up with recent developments is provided by the publications from the XI11 (10A) and XIV (9A) Colloquia Spectroscopicum Internationale. The proceedings from these two conferences both include the principal invited papers, and thus provide a valuable summary of current developments. The Proceedings of the X I V Colloquim also includes many contributed papers, and it is questionable whether it might have been better to have these published instead in journals. The same comment applies to other publications resulting from conferences, such as “Developments in Applied Spectroscopy” ( 4 A ) . Such books contain some papers of importance and interest, but they are mixed in with others of questionable value. The review process in journal publication is a n effective and proven screening method. The opposite extreme is represented by the ASTM publication “Methods for Emission Spectrochemical Analysis,” 398R
now in its fifth edition (2A). The material included in this volume has all been carefully screened, resulting in a publication of great value to the practicing analytical spectroscopist. I n addition to reliable information on methods of analysis, the spectroscopist requires more fundamental data, such as energy levels of atoms and the wavelengths and relative intensities of lines. Moore (2OA) has compiled a bibliography on the analysis of atomic spectra; all elements from hydrogen to einsteinium are included in four sections. Wavelength tables and atlases are also invaluable. An atlas for grating spectrographs has been published by Kalinin, et al. (15A); in this case the language barrier should be unimportant, the major difficulty being in obtaining the publication. Two books have also appeared on the theory of atomic spectra, by Hindmarsh (1SA) and by Shore and hlenzel (%’A), On a more day-to-day-practical basis, May (17A) has published a group of “Spectroscopic Tricks,” all of which previously appeared in Applied Spectroscopy. This book serves to collect them in a form which is more convenient for ready reference. Only one new textbook on spectrometric analysis in English is known to us. Dawson and Heaton (7A) have written a brief text on the analysis of clinical materials. It may be useful to those just entering this particular field, but unfortunately it does not reflect the latest instrumentation and techniques. I n contrast, at least three texts have been published in Russia. These include one by Atovmyan and Borod’ko (SA) on spectroscopic and X-ray diffraction analysis, and one by Nagibina and Prokof’ev ( H A ) on spectral apparatus and technology. Zaidel and Shreider (S4A) have written a text on vacuum ultraviolet spectroscopy. A Polish book by Dobrowolski and Bondaruk (8A) covers the analysis of gases and metals by spectrometric techniques. We may hope that a t least some of these works will become available in English. Several review articles of more or less general interest have also appeared, and these again serve a useful purpose for those new to the field or striving to keep abreast. Yoakum (SIA, 33A) has written two general reviews, emphasizing recent studies. Addink (1A) has contributed a chapter on optical and X-ray spectroscopy to the proceedings of a conference on trace anal-
ANALYTICAL CHEMISTRY, VOL. 42, NO. 5, APRIL 1970
ysis, and Grant (11A) has also contributed to a similar volume. Discussions of emission spectrometry, with some additional material on sparksource mass spectrometry, have been written by Kaiser (144) and Nicholls (22A). The history of spectrometric analysis in the Soviet Union in the past half-century was surveyed by Belyaev, Ivantsov, and Karyakin (5A). Historical reviews were also prepared by Strock (SOA) for the dc arc and by Walters (S1A) for the spark. The latter is also an excellent survey of the state of our present knowledge of the spark source. Much of this knowledge comes from time-resolved spectrometry, and Minami (29.4) has reviewed that subject. The particular subject of vacuum ultraviolet spectrometry has been ably summarized by Milazzo and Cecchetti (18A) and by Romand and Vodar (25A), all of whom are well known for their contributions in this field, Pinta (24A) and Specker (29-4) have surveyed methods of trace analysis, including spectrometric methods, and Burmistrov (6A) has discussed the improvement in the sensitivity of spectrometric analysis between 1937 and 1960. Particular applications of trace analysis have not been neglected. Pepper (2SA) reviewed the determination of impurities in uranium, and Hickey (12A) described instrumental methods, including spectrometric, for water analysis. Along with much of analytical chemistry, the teaching of spectroscopy has suffered in recent years. Considerable attention is now being devoted to this whole subject, and Schulz (26A) has discussed a method of teaching spectroscopy which is said to be simple and efficient, certainly desirable criteria. SPECTRAL DESCRIPTIONS AND
CLASSIFICATIONS
Continued interest in the phenomena occurring in plasmas of various origins has stimulated further work in the description and classification of atomic spectra. For an overall view of the literature on the subject, the extensive bibliography by Moore (ZOA), mentioned, earlier, should be consulted. Much of the effort in measuring new spectral wavelengths involves the spectra of stripped atoms with observations in the vacuum ultraviolet. Although this region of the spectrum is not extensively applied in spectrochemical analysis, the compilation of atomic
emission wavelengths below 2000 A by Kelly (25B),will be of interest. For the spectra of analytical interest, largely of the neutral atom and lower states of ionization, a number of contributions have been made and these will be considered. New lines have been reported in the spectrum of singly-ionized argon by Soroka, Kustanovich, and Polak (45B). An extensive series of measurements in the spectra of Ca I and Ca I1 have been made by Risberg (41B). The observations $overed the range from 1950-30,000 A and new wavelengths and energy levels are reported. The classification of C1 I has been extended by Radziemski and Kaufman (S8B) by new wavelength measureqents in the region from 950 to 12,000 A. New energy levels have been reported by Blaise and Van Kleef (ZB) for the spectrum of Gd I1 based upon observations of the Zeeman effect. The term systems of Ga I and I n I have been extended by new wavelength measurements in the infrared by Johansson and Litzen (24B). A use of the dc arc for differentiation between Ho I and Ho I1 lines has been reported by Held (ZOB) in which the spectrum assignments correspond well to results obtained with the electrodeless discharge and spark excitation. Calculation of energy levels for La 11, Ce I, P r IV, E u 11, and Gd have been reported by Eryomin and Maryakhina (I5B). An extensive remeasurement of the arc spectrum of lead has been published by Wood and Andrew (62B); the new grating and interferometric measurements spa? the spectral region of 1977 to 12,561 A and many new energy levels are reported. Persson (S6B) has extended the term analysis and new identifications of Ne I1 in the vacuum ultraviolet. Measurements in the spectrum of 0 I by Eriksson and Isberg ( I @ ) , have improved the term assignments in the spectrum. Sugar (46B) has reported on the third spectrum of praseodymium in the vacuum ultraviolet. Reader and Davis (S9B) have published new measurements and term assignments in the spectrum of Pm I and the classification of 714 spectral lines. Measurements in the spectrum of Pa I by Richards, Stephen, and Wise (40B),showed the extreme complexity of spectra of the heavy elements; some 14,000 lines were recorded and about half of these were classified. Continuing work on the spectrum of Tc I and Tc 11, Bozman, Meggers, and Corliss (4B) report measurements in the range of 2000 to 9000 A. Assignments were made of 3300 lines to neutral atoms and 1200 lines to ions. Zalubas (5SB) has reviewed the present state of term analysis of the first spectrum of T h I showing that energy levels totaling 268 even and 255 odd have
been found. I n other work on T h I, improved values for energy levels and wavelengths have been given by Valero (47B) The thorium spectrum, which serves well for secondary standard w a v e lengths for complex spectra, is now one of the most thoroughly measured of the complex spectra. I n a continuation of observations on the spectrum of W I, Laun and Corliss (SOB) report extensive observations in the region between 2000 and 10,500 A with 6800 spectral lines of which 5500 are classified. Additional new even levels and classified lines for W I were later reported by Corliss (9B). Contributions to our knowledge of spectral descriptions and energy levels continue to appear from the work of the late William F. Meggers. The term analysis of Yb 11, reported by Meggers ( S I B ) , provided the most complete interpretation of a complex rare earth spectrum known to that date-1967. More than 5000 Yb I1 lines are listed, of which 80% are classified and %yo of the total intensity is accounted for. Two new contributions to our knowledge of the spectrum of zinc are reported. Johansson and Contreras (2SB) measured 45 lines of the Zn erc spectrum between 3000 and 25,000 A to improve term designations. Crooker and Dick (I2B) reported improved wavelength measurements and new energy levels for Zn I1 and Zn IV. Other areas of interest, particularly in defining line intensities, are transition probabilities or oscillator strengths. A supplement to their bibliography on atomic transition probabilities was published in 1968 by Glennon and Wiese (18B). (An extension of this bibliography, covering the period January 1916 through June 1969, is to appear early in 1970.) A critical compilation of data on atomic transition probabilities has been extended for the elements sodium through calcium by Wiese, Smith, and Miles (50B). This compilation includes transition probabilities for about 5000 spectral lines of the second ten elements in the periodic system and involves critical evaluation. I n related work, de Galan, Smith, and Winefordner (I7B) have considered electronic partition functions of atoms and ions between 1500 and 7000 OK. Extensive new measurements on atomic transition probabilities for light elements by means of the shock tube have been reported by Miller (S2B). Included are transition probabilities for visible lines of C I, S I, S 11, P I, P 11, Si I, and Si 11. I n a later report, Miller ( S S B ) considers transition probabilities for C I, 0 I, Ne I, A1 11, Si I, Si 11, P I, P 11,S I, S 11,and C1 I. Transition probabilities for Ar I are given by Corliss and Shumaker (10B) and by Verolainen and Osherovich (48B). Shumaker and Popenoe (44B)reported arc I
measurements of some argon I1 optical transition probabilities. Oscillator strengths are given for Ba I1 lines by Von Specht (49B). Excitation temperature functions have been reported for C I, C 11, and C I11 by Petrakiev and Voros (S7B). For Cr I and Cr 11, gf values were determined from shock-tube measurements by Wolnik, Berthel, Larson, and Carnevale (61B). Also, for chromium, gf values have been reported for Cr I and Cr I1 by Byard ( 5 B ) . Relative oscillator strengths have been measured in a copper spectrum by Alekseev and (1B). Komarovskii, Vereshchagina Penkin, and Shabanova (28B) applied Rozhdestvenskii’s method to determine oscillator strengths of 49 E u I lines. A homogeneous set of intensity-related data on oscillator strengths has been calculated for 3288 spectral lines of Fe I bycorlissand Tech (11B). Measurements of oscillator strengths for Fe I were made by Peach (S5B) using a low noise photo-electric scanning system. Huber and Tobey (21B) have reported gf values for Fe I, Cr I, and Cr I1 lines. These results show disagreements with gf values of Corliss and others based on arc measurements for lines which have an upper excitation potential exceeding 48,000 cm-1, Oscillator strengths for the resonance lines of krypton and xenon are reported by Griffin and Hutcherson (19B). Using a cascade arc operated a t atmospheric pressure in Ar, oscillator strengths were measured for lines of Si I and Si I1 by Schulz (4SB). Forbrich, Marlow, and Bershader (16B) give measurements of the sodium D-line absolute oscillator strengths by the hook method. Using tables of relative line intensities previously published, Corliss (8B) derived relative oscillator strengths for lines of T b I. Other measurements in rare earth spectra include oscillator strengths for spectral lines of Tu I and Yb I by Komarovskii and Penkin (27B) using the hook method. Shocktube measurements of absolute gf values for neutral and singly ionized titanium were made by Boni (SB). Using an arc, absolute probabilities for tungsten transition lines were reported by Kirsanova (26B). Increasing use is being made of isotopic shifts in atomic and molecular spectra for isotopic analysis. Some of these applications are given a t the end of this review. For a comprehensive survey of basic information in this field, reference should be made to the bibliography by Moore (20.4). Some typical contributions in this field will be listed here. Champeau and Gerstenkorn (7B) measured isotope shifts for four natural isotopes of cerium. Shifts in the dysprosium spectrum were measured by Pacheva and Abadzhieva (%@).
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Relative isotope shifts in the spectra of erbium and ytterbium were measured by Chaiko (6B) using highly enriched isotopes to obtain high precision. Further work in the rare earths was reported by Koniordos and Winkler (S9B) for isotopic shifts in Eu I1 and E u I11 and b y Saksena et al. (45%) for 143Nd, Hyperfine structures for some levels of the isotopes l71Yb and 17aYbwere given by Duong, Gerstenkorn and Luc (ISB). Isotope shifts for X e I lines of several Xe isotopes were measured by Jackson and Coulombe (22B). INSTRUMENTATION
The development of spectrometric equipment during the important period 1918-68 was reviewed by Learner (SOC), who discussed theory and hardware and also briefly projected future trends. Namioka (4SC) discussed the theory of the concave grating in spectrographs and monochromators. Spectral instrumentation for plasma diagnostics was described by Lochte-Holtgreven and Richter (SSC) and also by Lincke (S2C) who placed emphasis on vacuum ultraviolet spectrometry. Moenke (39C) discussed spectroscopic equipment manufactured by Zeiss-Jena, and Petrakiev (48C) covered a variety of spectral instruments made and used in the East European nations. Davies and Stiff (16C) described gratings recently ruled in Australia. The continued interest in spectrometer design comes, in part a t least, from the need to improve performance, and the renewed emphasis in recent years on the Czerny-Turner type of grating mount arises from the possibilities for minimizing aberrations. Allemand (8C) described coma correction in this type of instrument, and Reader (58C) compared analytic theory and ray tracing in the design of Czerny-Turner spectrographs. After having designed and constructed a spectrograph, it becomes necessary to determine its performance. Feautrier and Schneider (,%'IC)gave experimental techniques for measuring the instrumental profile of a spectrograph, taking into account the finite slit widths and the effects of the microphotometer. A specific discussion of slit functions and the influence of changing slit width on spectrometric measurement was presented by de Galan and Winefordner ( 2 4 C ) . Nikonova, Voronich, and Startsev (46C) compared three vacuum spectrometers for the analysis of steels, manufactured in the U.S., Britain, and the U.S.S.R. Kozodon and Malkin (S9C) described an attachment to a spectrograph for the simultaneous photoelectric measurement of several lines, Single-channel spectrometers were designed by Bueckert and Giavino (9C) and by Dale (I5C) whose instru400 R
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ment was intended specifically for the determination of beryllium in liquids. Czakow, Grzelak, and Szymborska (1.42) described an attachment to a prism spectrograph for the visual observation of spectra, with provision for simultaneously exciting and comparing a sample and standard. Baird (4C) was issued a patent on a system for performing such measurements photoelectrically. Beatrice and Glick (5C) constructed a direct-reading polychromator specifically for use with a laser probe source. It incorporates pairs of photomultipliers, recording background and line-plus-background intensities, and provides for oscilloscope display of the signals or for digital readout of line intensity above background. Rlakabe and Hashizume (S6C) obtained a patent on a spectrometer incorporating two or more gratings on a turntable. High-speed scanning spectrometers were designed by Dawson, Ellis, and hlilner (18C) and by Buchhave and Church (8C). Such instruments appear to be attractive for spectrochemical analysis, permitting the measurement of many lines with a single detector. However, the fact that they record data at any one wavelength for only a small fraction of the total measurement time limits the precision of measurement except with the most stable light sources. Other instrumental developments are aimed a t improving spectral resolution. High resolution is obviously important in analyzing complex spectra, but it is also a useful method of improving line-to-background ratios for trace analysis. Callomon and Chandler (1%') constructed a 4-m Czerny-Turner grating spectrograph which gave resolutions of a t least 700,000 over a 50-cm focal curve. Interferometers offer a potential means of improving spectral resolution without extremely large instruments while preserving luminosity to a reasonable degree. Fabry-Perot spectrometers were described by Gagne (2SC) and hIena ( S W ) , and the latter also showed the application of the instrument to the isotopic analysis of uranium. Nguyen, Zhiglinskii, and Turkin (45C) also investigated spectrometric analysis with an interferometer, specifically for the determination of strontium, aluminum, and calcium in quartz sand, and reported improved sensitivity and virtually complete elimination of the effect of interfering lines. Certainly, developments along this line will be watched with interest. Wada and Watanabe (66C) were issued a patent on a system for optical spectrometric observation of the spark source in a mass spectrometer. One may question whether that source is really useful for optical spectrometric analysis, but this will have to be es-
ANALYTICAL CHEMISTRY, VOL. 42, NO. 5, APRIL 1970
tablished experimentally. Along immediately practical lines, Leys ( S I C ) developed a double exit slit system for background correction with a single photomultiplier detector. Pfeiffer (55C) obtained a patent on a system for correcting for temperature-dependent spectral shifts based on forming sets of exit slits, each set corresponding to a particular temperature, on a quartz carrier whose position is adjusted automatically by monitoring one temperature-sensitive line. A method of spectrometry with self-reversed lines was developed by Burridge and Scott ( I S C ) . They employed a pair of slits which pass light only from the wings of the line, where the intensity increases linearly with concentration even when the center of the line is self-reversed. An interesting detector was described by Boksenberg ( 7 C ) . h thin insulating layer is placed on a grounded conducting plate, which may be shaped to the focal curve of the spectrometer. Exposure of this plate generates a distribution of charges corresponding to the spectrum, and the charges are read out with a vibrating probe which is scanned a c r o s the plate. Considerable emphasis has also been placed on the detection of extremely lowlevel intensities by both photographic and photoelectric means. Franklin, Horlick, and Rlalmstadt (22C) developed a simple photon counting system, and compared it to other techniques for detecting weak optical signals. Their paper also stresses other advantages of photon counting, including the possibility of making very precise measurements. Alfano and Ockman ( I C ) also compared methods of detecting weak light signals. -4sensitive spectrometer designed by Ness and Hercules (442) combined a largeaperture optical system and a n image intensifier tube before the photographic plate. Petrakiev and coworkers published a number of papers (IOC,19C, 49C-54C) on enhancing the sensitivity of photographic plates by changes in the method of development and other post-exposure treatment. In most spectrometric methods, the detection limit depends less on detection of weak signals as such than on discrimination against background. Gerbatsch and Krasnobaeva (S5C) looked a t this subject from several aspects, including the contrast, sensitivity, and granularity of the emulsion and spreading of the image. Burmistrov, Nedler, and Polyakova ( I I C ) recommended microphotometry with the narrowest possible slits for optimum measurements of weak spectral lines in the presence of a strong background, and found that the detection limit could be improved by a n order of magnitude in this way. On the other hand, Plsko (66C) re-
ported that tests with five photographic emulsions indicated better detection limits were obtained with wider slits on the spectrograph. It appears to be difficult to reconcile these conflicting reports, and presumably the subject is not closed. Time-resolved spectrometry has been used to improve detection limits as well as to research time-dependent processes in sources. Minami, Uchida, and Fujita (382) described a high-speed spectrometer with a photomultiplier gate and signal processing electronics. This instrument was said to give time resolution as short as 10 nsec. Apparatus for photographic time resolution, as described by Boboli and Otrebski (SC), comprises two disks, one of which runs a t a fixed speed and separates spectra in time while the other has a variable speed and generates a trigger for the discharge. For non-repetitive events, Kendall (28C) has improved a mechanical shutter to give microsecond response. Svoboda (63C) proposed parameters for evaluation of photographic emulsions in terms of the absolute and relative sensitivities of analysis, and compared according to this scheme a number of the spectrometric emulsions often used in Europe. Polaroid film is often a convenient emulsion, for fast checks when experimental conditions are changed and for use by students. Scherer and Sakurai (6OC) stressed the latter application, especially with regard to the use of inexpensively constructed spectrographs. An obvious disadavantage in the use of photographic emulsions in the need for tedious microphotometry. Automatic microphotometers are hardly new, one having been used more than 30 years ago in acquiring data for the M I T wavelength tables. The new automatic microphotometers are much improved, and provide data in the form needed for computer processing. One of the newer instruments is described by Steinhaus, Engleman, and Fisher (62C),who use it to locate and measure every line in an emission or absorption spectrum. Helz, Walthall, and Berman (27C) have also constructed an automatic microphotometer, capable of measuring a 10-inch spectrum in less than a minute, and have written computer programs for reduction of the data for spectrochemical analysis. Computers have also, of course, been in use for some time to process data from photoelectric instruments. Although equipment for digital printout in computer format is commerically available, some find it necessary or desirable to construct their own. Digital printouts for spectrometers were described by Theiring, Kramer, and Pepper (64C) and by Farafonov et al. (SOC).
While computers are relatively new, problems with graphite electrodes must qualify as one of the oldest subjects in emission spectrometry. Graphite may now be better than ever, but the requirements on purity are more stringent. A standard purification procedure has been pre-burning, and Skogerboe, Kashuba, and Morrison (61C) developed some modifications of this technique, reducing impurities to a few parts per billion. Haftka and Votava (S6C) purified graphite electrodes by heating in an electron beam refiner. The determination of impurities in purified graphite was reviewed by Maillard and Ades (S5C) who advised ashing as means of concentrating a large sample. After the electrodes, have been purified, it is necessary to keep them clean. Davila (17C) obtained a patent on a procedure for packaging electrodes in graphite cloth prior to purification. The packaged material is then purified and shipped to the user without further wrapping contacting the pure electrodes. The user must also exercise appropriate precautions, and Zil’bershtein and Nikitina (68C) discussed pickup of impurities by electrodes in the laboratory. A new material for electrodes, glassy carbon, was tested by Morita e t al. (4fC), particularly for the analysis of solutions. They found this material to be quite impervious to solutions, and also reported that very little js consumed in the spark. As a result, the impurities in the electrode are of niinor importance, and the same electrodes can be reused more than 100 times. Angeletti and Maurice (SC) developed apparatus for automatic loading of electrodes, which is particularly useful for radioactive samples. Tonea and Pavloschi (65C) developed a technique for melting samples in an alkali metal salt directly on a copper electrode for spectrographic analysis. They tested the technique on a variety of inorganic and organic materials. Electrode loading is not the only problem in analyzing radioactive materials. Roca Adell, Capdevila-Perez, and De la Cruz (53C) described a complete system for handling and analyzing radioactive materials, including plutonium. The laser probe manufactured by Zeiss-Jena was described by MoenkeBlankenburg (4OC); it differs in several respects from the one made in the U.S. A new rotating-disk apparatus, developed by McIntyre and Peck (342) features a variable rotation speed from 30 to 20,000 rpm. Two novel devices for spectrograph illumination were also developed. One, by Zakharov et al. (67C) is a special nozzle which permits a spark source to be safely located only one centimeter from the slit. The other, by Plsko (57C), is a n integrating sphere
around the light source, which is reported to have several advantages. Nagy and Samsoni (48C) developed several variable light filters for spectrometric analysis, including a wedge filter and one which can be used as either a logarithmic filter or a twoor three-step filter. Finally, Nymmik, Saar, and Tiit (47C) investigated penetration of water vapor into vacuum spectrometers and made suggestions for reducing this problem. STANDARDS,
SAMPLES, CALIBRATION, CALCULATION
AND
Since spectrometric analysis is a comparative method, calibration standards remain of crucial interest. Nagda and Paksey (SOD) surveyed steel and cast iron standards and samples from several countries, with particular reference to homogeneity. Kotsis (SSD) described a series of aluminum standards prepared in Hungary and compared them with standards of French, German, and Russian origin. Kashu et al. (1Q D ) prepared Zircaloy standards by electron beam melting, but failed to obtain material of entirely satisfactory homogeneity. The preparation of standard samples of titanium by arc melting of sponge was described by Tsekhanskii and Khramtsov (5SD), who found that two meltings were needed to get reasonable homogeneity. Slate-base standards for analysis of geological materials were made and tested by Schindler (CSD), and Kibisov and Kubasova (210) gave procedures for making standards for a common-matrix method of analysis of samples of diverse composition. The reliance on standard samples can be reduced in a number of ways. One is the well known method of standard additions. Ogneva, Ognev, and Raikhabum (S6D) derived a series of equations to evaluate systematic errors in this procedure, and Masuda and Inouye (S4D) developed improved equations for the simultaneous determination of several elements by standard additions. Other computation procedures, together with the recording of some additional data, also offer a reduced reliance on standards by correcting for matrix effects. Avdeenko, Neuimin, and Furman ( 4 0 ) applied an empirical set of simultaneous equations to convert spectrometer readings to element concentrations. Each equation derives the concentration of a particular element from all of the spectrometer readings rather from one reading only. A more rational approach is to base the correction on measured discharge parameters according to known physical laws. Decker and Eve (1OD) corrected for matrix effects according to measured arc temperature and electron density, with promising
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results. Kubasova and Kibisov (260) applied a similar procedure, but one that was based only on the measured intensity ratio of a V I line t o a V I1 line, While neither method takes into account the effect of sample composition on vaporization, the first is preferable because it treats arc temperature and electron density separately and is therefore theoretically more sound. The same theoretical principles may also be used in selection of data to be recorded, rather than relying on qualitative “rules” for selection of line pairs and operating conditions. Barnett, Fassel, and Kniseley ( 5 0 ) have studied the theoretical relation between element concentrations, source conditions, and line intensities with respect to internal standardization. Their model was a n r-f plasma torch, but the principles are equally applicable to other excitation sources. Such detailed computations are hardly possible in routine applications without a digital computer. There has been much interest in the form of equations to be used in computerfitted analytical functions and in specific algorithms and programs for this purpose. Torok (510) has compiled a literature review of methods of evaluating spectrometric data. Ivanova and Taganov (130) evaluated the accuracies of six mathematical relationships in fitting analytical functions with data from a series of copper-base alloys, and Kerekes-Cseti (200) described a n equation for this purpose having three constants to which physical significance can be attached. Margoshes and Rasberry (320) developed two computer procedures for fitting analytical functions, including provision for choice of the equation to be used and detection and rejection of calibration data which do not conform to the function. One procedure is intended for use with a time-sharing system and it allows the operator to make these judgments. The other procedure is intended for batch-loading systems, and the judgments are programmed. The BASIC language programs for the time-sharing system for this and other computations in emission and X-ray fluorescence spectrochemical analysis have been assembled by Rasberry, Margoshes, and Scribner ( 4 0 0 ) . One advantage of the use of computers to fit analytical functions is that the same data can be used to evaluate errors in the analysis. Margoshes and Rasberry (320) discussed this aspect in their publication, and Kuznetsov, Gede, and Rudenko (270) gave specific attention to this aspect. Ivanova, Taganov, and Taganov (140, 160) investigated the error in instrument calibration and applied the results to the selection of analytical procedures. Other publications were concerned 402 R
with computer-fitting of analytical functions for more or less specific analytical tasks. Johnson et al. (170) developed equations for spectrometric analysis of biological fluids, and Stenger (480) described an analytical procedure and computer program for analysis of coal ash, fly ash, and related materials. A more flexible procedure is that developed by Thompson, Manheim, and Paine (600) for the analysis of diverse materials encountered in oceanographic research. Many papers have also been published on the calibration of photographic emulsions, with or without computers. Several assume a linear emulsion calibration with the Baker-Sampson (Seidel) transform, although Margoshes (310) has pointed out that this transform was not originally claimed to give an entirely linear calibration function and that extensive data exist to demonstrate curvature of the calibration functions. Anderson and Lincoln (20) laid the mathematical foundation for a computer method of emulsion calibration. They started with the Baker-Sampson transform, but mathematical manipulation and the addition of another constant changed its form. The actual computer program was described by Carnevale and Lincoln ( 9 0 ) . Pellet and Ruquet (370) employed a special-purpose computer, a 400-channel amplitude analyzer, for photographic photometry. Other computer programs for microphotometry were given by Boswell, Berman, and Russell ( 7 0 ) and by Margoshes and Rasberry (330). The latter authors investigated the properties of several transforms, and also discussed calibration errors. Krinberg and Smirnova (250) specifically considered errors in photographic photometry, including calibration and other computation steps. Many other studies on photographic emulsions did not specifically include computer programs. A novel procedure described by Jacobsen (160) makes use of data over a wavelength range rather than merely a t a specific wavelength, in order to increase the amount of information available. He found experimentally that an H&D curve a t one wavelength could be mapped onto the curve a t a nearby wavelength by the use of two constants. Rybarova (410) gave an emulsion calibration method said to be much more rapid than earlier techniques. Zimmer (570) compared calibration of different types of emulsions a t various wavelengths and considered the use of gradient filters for this purpose. The Sabattier effect (formation of a positive image onto the negative caused by a short illumination during developing) was reviewed by Weber and Fugas (530), who considered it as a means of increasing the sensitivity of qualitative analysis.
ANALYTICAL CHEMISTRY, VOL. 42, NO. 5, APRIL 1970
The use of line widths for photometry
is well known, but only rarely used. Bril (80) developed a simple function to describe spectral line profiles on photographic emulsions, and Aidarov (10) and Pittwell (380) discussed the merits of line width photometry compared to the usual practices. Other papers were concerned with optinum spectral registration for trace analysis. Doerffel and Demuth (110) gave a procedure for predicting the optimum additional exposure of the emulsion to improve the detection of weak light signals, and Arakel’yan and Maiorov ( 3 0 ) gave a mathematical treatment of photographic and photoelectric methods for detecting faint lines in the presence of background. Many other publications treated more fundamental considerations in trace analysis. Two basic papers by Kaiser (180) on the definition of the limit of detection were made available in English. Svoboda and Gerbatsch (490) also discussed this matter, and suggested that international agreement is needed, and Slavnyi (460, 470) published two papers on the theoretical and practical limits of detection as affected by the particular instruments empolyed. All such treatments of detection limits are, of course, actually signal-to-noise computations and statistical arguments. Photometric errors affecting detection limits were considered by Samadov and Yankovskii (420) and by Kuznetsov, Kuznetsova, and Korshikova (280). Kuznetosva and Raikhbaum (290) discussed detection limits in geochemical analysis, and the specific problem of determining minute amounts of silver in aqueous solutions was covered by Zil’bershtein and Legeza (560). Zil’bershtein (550) also considered the extension of detection limits by the method of running several exposures and counting the fraction which give a visible line. Krinberg (240) discussed matrix effects on detection limits. Detailed statistical studies have also been put to use in analysis a t higher concentrations. Three publications on this subject were by Berenshtein and Fal’kova ( 6 0 ) , Sheinina (440); and Skogerboe (450), all of which were concerned with improvements in the total analytical procedure by statistical analysis of data. Galazka (120) gave a n equation describing analytical accuracy; he concluded that repeatability depends mainly on the reproducibility of current in the source, which is certainly a factor that can be kept under control with proper electronics. Rao, Amin, and Chakravarti (390) described a procedure for controlling curve shifts by exposing a standard along with each group of unknowns. The effect of carbon on the determination of sulfur in steels was studied
by Korotkov and Titovets (d20), who gave a correction formula which was said to bring the spectrographic data in line with the results of chemical analyses. In the end, the quality of spectrographic (or other analytical) methods is controlled by the sampling process. Menting ( 3 5 0 ) was issued a patent on a procedure for preparing solid metal samples by induction heating and cooling with a stream of liquid gas. Another patent was issued to Williams and Du Bois ( 5 4 0 ) for a method of atomizing liquid metals to form a fine powder suitable for analysis by emission spectrometry and other techniques. EXCITATION SOURCES
Considerable interest continues in the development of new and improved excitation sources and in studies of existing light sources. Many of the studies are quite fundamental, although empirical methods continue to be applied. Quite likely the empirical research will be increasingly displaced by work relying on mathematical treatments based on established physical and chemical laws. Petrakiev (128E) reviewed the development of excitation sources for emission spectrometry. A new procedure employs X-ray or electron bombardment to excite atomic spectra of rare earths in solid matrices. Cathoderay excitation vias applied qualitatively and quantitatively by Larach (96E, 97E) and Larach and Shrader (98E), while X-ray excitation was empolyed by DeKalb et al. (@E) and Jaworowski et al. (76E). Excitation in the condensed phase opens new avenues for interelement effects, and Jaworowski and Cosgrove (75E) explored this aspect of the technique. Among the basic studies, Boumans (22E) gave a treatment of the importance of the partition function in the fundamental physical equations. He also tabulated data for approximation of the partition function over normal flame and arc temperatures. Semenov and Terpugova (148E) described diagnosis of plasmas with asymmetric selfreversed spectral lines, and showed how such data could be employed to determine the density of charged particles, plasma temperatures, and other important parameters. Voros et al. (17OE) proposed a method for determining plasma temperatures from broadening of spectral lines of transition metals. The temperatures of laser plumes were studied by Boegershausen and Hoenle (19E), who found that the excitation and ionization temperatures were considerably different. Such findings may indicate a departure from local thermal equilibrium or simply neglect of radial temperature
distributions. Hefferlin and McGregor (70E) gave a procedure for establishing radial temperature distributions without the complexity of the Abel inversion. Morozova, Pavlovskaya, and Podmoshenskii (fO7E)made a study of thermal equilibrium in arcs and hollow-cathode discharges. I n the absence of thermal equilibrium, the detailed excitation and de-excitation steps must be considered, and Gilmore, Bauer, and McGowan (66E) prepared a useful review of the present knowledge of these processes. There have been many contrary reports of the effect of atmospheric pressure on line intensities from spectral sources. Nikitina and Gorevaya (220E, I d l E ) joined the ranks of those reporting enhanced sensitivity under certain conditions. They studied the effect of pressure on arc and spark discharges in atmospheres of air, oxygen, and argon, and explained the observed intensity changes on the basis of alterations in sampling and excitation mechanisms. Improvements in precision and sensitivity of analysis are possible by photoelectric recording a t frequencies a t which the source is most stable. Belyaev et al. (13E) reported on detailed studies of the frequencies of fluctuations between 20 and 10,000 Hz for the dc and ac arc, the plasma jet, flames, a hollow-cathode, and an electrodeless discharge. For most sources, the low-frequency noises predominated. Arc Excitation. Although much work has already been done on determination of arc temperatures, several more studies o n this subject have been published. Snelleman (15dE) applied the line-reversal method, often used for flames, to the determination of arc temperatures, reporting an absolute accuracy of *50° a t 6000 O K . Arc temperatures during excitation of several mineral samples were determined by Kupkova (9SE) from CN band intensities, and Grechikhin and Tyunina (65E) measured line profiles for the determination of arc temperatures and electron densities. Milyus et al. (106E) also investigated electron concentrations from line broadenings. A detailed study of arc temperature, voltage, and electric field under the conditions applied in the analysis of uranium was reported by Avni (6E), and Krempl and Schmid (88E) measured temperatures of arcs in argon. Semenova, Sukhanova, and Elizer’eva (150E) reported on the influence of sodium in the sample on arc temperatures and electron densities, while Troshkina (16SE) described theoretical studies of the influence of sample composition on degrees of ionization for several elements. I n another theoretical study, Krinberg (91E , 9dE) investigated the relation between sample composition, arc temperature, and elec-
tron density. Rost (IBOE, 1 4 f E ) considered correction for matrix effects due to changes in plasma temperature and electron density. I n another study, Borovik-Romanova (21E ) investigated the effects of the addition of easily-ionized elements to soil samples being analyzed for lithium. Even more work was reported on the dynamics of sample evaporation and transport in the arc. This is in contrast to the situation a t the time of the last review (16A), when we reported on only a few such studies. Several reports were published on chemical reactions in the arc electrode, including those by Bril (&?E),Chernenko (SYE), Filonov, Proleskovskii, and Pavlyuchenko (53E), Frishberg (54E), Karyakin, Laktionova, and Pavlenko (78E), Lazebnaya, Yudelevich, and Druz (99E), Nickel (118E), Preis (136E), Rautschke and Holdefleiss ( f S 8 E ) , Rautschke and Schindler (139E), and Shipitsyn, Sambueva, and Plastinin (151E). A series of papers by Zolotukhin (182E-184E) was concerned with vaporization from metallic electrodes in pulsed arcs; the studies included measurements of temperatures of anode and cathode spots, and high-speed photographs showing the entry of droplets of molten metal into the discharge. Pllilenina and Rudnevskii (1O4E) related the entry of material from metallic electrodes to the surface tension of the molten metal. Petukh and Yankovskii (13OE) studied the influence of deposits of alkali metal carbonates and ammonium halides on vaporization of metals in the arc. Turko and Korshakevich (I66E) investigated the evaporation of plated metal layers from a third electrode introduced into an arc; they found that there was no evaporation when a potential of less than 40 V was applied between the sample electrode and the cathode, increasing evaporation up to 50 V, and a constant rate above 50 V. Two publications by Naimark reported on arc electrode temperatures (11323) and their relation to sample (114E). Osawa evaporation rates (ld5E) described similar studies for the element gadolinium as the oxide mixed with graphite. The effect of sample composition on vaporization behavior was considered by hbashidze ( I E ) ,Akulovich, Proleskovskii, and Dubovik (2E), and by Filonov, Dubovik, and Pavlyuchenko (52E). Bril and Vinot (29E) reported on a relation between the evaporation of tin from a graphite electrode and the arc potential, while Dzhanibekov and Zagranichnaya (@E) looked into the effect of electrode shape and arc current on sample vaporization. These fundamental studies have many practical ramifications. Boumans and Maessen (ICE) considered first the
ANALYTICAL CHEMISTRY, VOL. 42, NO. 5 , APRIL 1970
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efficiency of material transport from the electrode cavity to the excitation zone, as influenced by several experimental parameters, and then (25E) showed how these factors affected detection limits and precision in the analysis of geological materials. Boumans ( M E ) calculated theoretical intensities for 200 lines of 53 elements a t typical arc temperatures and related the results to the problem of optimizing excitation conditions for trace analysis. Another ramification is evidenced in the brief study reported by Woodriff (177E) on the repulsion of liquid droplets by an arc discharge, which must be considered in the design of excitation sources for solutions. Other work by Decker and Eve (41E, 42E) was concerned with the explication of the mechanisms of the effect of spectroscopic buffers on electrode temperatures, sample evaporation, and other factors. Another sizable group of publications has been on material transport and related phenomena in the arc plasma. The potential complexity of this problem is indicated by the study by Vukanovic and Vukanovic (172E) on demixing of hydrogen isotopes in the arc plasma; this phenomenon is well known to plasma physicists but is less familiar to analytical spectroscopists. Usov, Ivanova, and Tuponogova (167E) examined the distributions of a number of elements in de and ac arcs, observing both cathode and anode layers. More detailed studies include measurements of the lifetime of atoms in the plasma. Such investigations were reported by Malykh and Serd (102E), by Nazarov, Gerasimov, and Milyus (116E), and by Polatbekov and Zhukov (135E). Usov (166E) applied time-resolved spectroscopy to the study of element distributions in the ac arc, with emphasis on the cathode layer. Polatbekov and Zhukov (134E) also studied the radial distribution of sodium atoms in the arc, and Zhukov (180E) investigated the effect of sodium on arc plasma temperatures and the distributions of alkaline earth elements in the arc column. The radial emission intensities are controlled by the atomic (or ionic) distributions and temperature profiles. Studies of radial intensity profiles were made by Ognev (128E) and by Triche (161E). Ovechkin and Sandrigailo (126E) related the dependence of line widths on element concentrations to radial element distributions. Little is known still of chemical processes in the arc plasma. Raikhbaum and Kostyukova (137E) investigated this subject with respect to its effect on intensities of lines of beryllium, zirconium, and sodium, and suggested ways by which additions might be made to the samples to influence chemical reaction equilibria in the arc column. 404 R
A magnetic field can be used to stabilize the arc column, and also to influence element distributions and lifetimes. The mechanism involved is changes in ion trajectories by the applied field. Buyanov and Zamaraev (35E) related the effect of the magnetic field to its influence on diffusion in the plasma, and Buyanov, Zamaraev, and Polyakova (36E) reported improved analytical precision by the use of a magnetic field to induce a more even distribution of material in the arc column. The exact effect of the magnetic field depends on its geometry as well as on other conditions. The use of magnetic fields to enhance detection limits, presumably by increasing residence times of atoms, was reported by Krasnobaeva, Charizanov, and Zadgorska (86E), Lummerzheim and Nickel (101E), Nickel, Leuschacke, and Lummerzheim (119E), Todorovic, Vukanovic, and Georgijevic (160E), and by Vukanovic et al. ( 1 7 l E ) . The use of the magnetic field simply to stabilize the arc column was described by Komarovskii and Stenin (8%) and by Lotrian and Johannin-Gilles (100E). Other techniques for arc stabilization were also investigated. Gordon (58E) developed an arc with a tantalumtipped cathode, burning in argon a t reduced pressure, which is remarkably stable. The current supply for this arc was controlled (59E) by a servo-mechanism monitoring the intensity of one spectral line and varying the arc current to force the intensity fo follow a preset program. Arnal (6.73) reported an improvement in precision in the analysis of plutonium oxide by stabilizing the arc current to a constant value, while Schuringa et al. (147E) found a large improvement in precision through automatic control of the length of the arc gap. Apolitskii (4E) devised a rather complex arc discharge in which an ae arc is superimposed on a dc arc, each arc having its own pair of electrodes. Compared to the ae arc, the new source was claimed to be more stable, to have a higher temperature, and to produce more intense emission lines. Sukhnevich (154E) employed an ac arc in an asbestos cylinder; a downward-flowing air stream served to stabilize the arc and to keep sample vapors in the discharge for a longer time. A de arc in helium was applied by Braman and Dynako (26E) to the sensitive detection of halogens in the effluents from gas chromatographs. Other work was concerned with control of sample introduction. Kantor, Hanna, and Erdey (77E) developed a system for the continuous and simultaneous introduction into the arc of a refractory matrix, such as alumina, and a substance of low boiling point, such as zinc. Means of blowing powders
ANALYTICAL CHEMISTRY, VOL. 42, NO. 5, APRIL 1970
into an arc were given by Batova (12E) and Kuznetsov (94E). Gran’kova and Kiselevskii (64E) employed a high-current arc in helium, along with exposures timed to the e v a p oration times of individual components, to improve detection limits by up to two orders of mangitude. Benko (14E) gave an empirical equation to describe the relation between arc voltage, current, and electrode gap for various samples, and Kuznetsova, Raikhabum, and Malykh (95E) studied the effect of arc current and the electrode spacing on the sensitivity of analysis for several volatile elements in carbon powder and a carbonate ore. Buryak et al. (34E) investigated some matrix effects in arc excitation of solid metal samples as affected by the shapes of counter-electrodes made of graphite and several metals. Spark Excitation. A newlydesigned spark source may be one of the most significant developments in emission spectrometry during the period covered by this review. Walters and Bruhns (175E) described a spark which is triggered by an r-f pulse and which derives its current from a lowvoltage circuit. The method of triggering is said to give very much more reproducible break-down than older techniques, and the use of lowvoltage components for the current supply opens new avenues for shaping of wave forms. Walters (174E) also developed a high-voltage spark power supply with exceptional capabilities in the control of wave forms. Berneron (18E) was issued a patent on a spark source having many different impedances in individual circuits and a rotary spark gap to control the rapid, sequential scanning of the impedance circuits. Kreshkov and Kucharev (89E) studied the application of a rotatingdisk to the visual analysis of organic compounds by observing the intensities of Cz and CN bands. A low-voltage sliding spark was empolyed by Rudnevskii and Prokof’eva (14dE) for the analysis of thin nichrome films. The blowing of dry powders into the spark was investigated by Oleinik (123E), while Muzgin and Lisienko (112E) blew in powders as aqueous suspensions. Daveltshin (38E) employed a condensed spark in vacuum for the excitation of certain metals, but reported relatively poor results with iron electrodes in this spark. The electrodes had to be quite closely spaced to obtain a discharge with a normal high-voltage source. The same technique was applied by Davletshin, Sventitskii, and Taganov (39E) to the determination of sulfur, selenium, chlorine, and tellurium in metals. A unipolar discharge in argon was studied by Startsev, Taganov, and Shlepkova (153E) for
the determination of carbon, p h 0 5 phorus, and sulfur in steels. The addition of materials to the sample surface was the subject of two employed reports. Baskov (11E) powdered oxides or salts on the sample surface to influence favorably the sampling process in the contact-spark procedure of analysis. Barnes ( 9 E ) reported on a study of the effect of a liquid layer on the sample in point-toplane excitation. A large group of papers was concerned with the effect of the spark on the surface of the sample. Brewer and Walters (27E) made use of optical microscopy and the electron microprobe in studying the sampling of metals by the first few discharges in a train. Other papers, including those by Barvinko, Borbat, and Dem’yanchuk (IOE), Davletshin and Taganov (QOE), Kashima and Kubota (8OE), and Takahashi (157E), concentrated on the sampling rate as affected by spark parameters and the nature of the sample. Bondarenko (2OE)applied mathematical and experimental techniques in a study of the processes of melting and vaporization a t the spark contact spot. I n other work, the sampling mechanism was investigated in relation to matrix effects. For example, Koch, Dittmann, and Picard (82E) found that, during the initial period of sparking to a steel sample, the spark attacked sulfide inclusions. Similar dendritic etching was reported by Grikit, Galushko, and Chernyshova (68E) when sparking copper-zinc alloys. Dem’yanchuk, Grikit, and Struina (443)described similar studies with copper alloyed with a small amount of silver. Buravlev (S2E) gave the results of studies of sampling in noble gas atmospheres. Other work was also done on controlled atmosphere spark excitation. A report on this subject by Szabo and Toth (155E) was one of a series of publications on the general subject of rotating aluminum samples during excitation. Other work on controlled atmospheres was described by Buravlev et al. ( S S E ) , Goto and Hirokawa (63E), and Kashima and Kubota (79E).
There were relatively few papers on time-resolved spectroscopy of sparks. Walters (17SEj studied in detail spectra near the sample surface, obtaining information on the sampling and initial excitation processes. The thesis of Barnes (8E) also reported on time-resolved spectral studies with reference to the ionization processes. Bardocz and Vanyek (7Ej applied time-resolution techniques in order to obtain spark spectra of gas atoms free of the electrode spectrum. Nickel (117E) made use of radioactive isotopes to investigate processes in rotating-disk excitation of solutions, es-
pecially penetration of the solutions into the graphite. I n improving the solution analysis of silicates by the rotating disk technique, Ondrick, Suhr, and Medlin (12QE) found it necessary to weigh each graphite disk individually and to separate them into groups of similar weight. Another method of controlled sample introduction into the spark is to pour or sift the material into the discharge. Herbst and Mannkopff (71E) studied material transport in this technique, and Berezin and Razuvaev (17E) employed this method in the excitation of sulfur and halogens. However, they obtained better results by cementing the samples to rotating-disk electrodes. Berezin, Korpushev, and Razuvaev (15E) reported other work on the determination of sulfur and chlorine, including studies of various atmospheres over a wide pressure range. The effect of the electrode material on low-voltage spark temperatures was investigated by Berezin and Razuvaev (16E). This is one cause of matrix effects. Goryachev (6OE) also reported on matrix effects, in the analysis of copper-zinc alloys, as related to the spark temperature. Grikit et al. (67E) studied matrix effects in magnesium alloys as affected by the capacitance and inductance of the spark power supply. Dryakhlov, Zelinskii, and Rudnevskii (48E) looked into the influence of the counter-electrode material on line intensities and intensity ratios in the analysis of brasses. The effect of spark gap width on line intensities was the subject of a paper by Kondrat’eva (86E). Heat transfer in electrodes was studied mathematically and experimentally by Krauss (87E). Two papers were concerned with the frequency distribution of signals from sparks. Watanson and Chernyak (115E) analyzed the sounds from spark discharges over the frequency range from 18 to 19,000 Hz, and Milenina and Sventitskii (105E) carried out a Fourier analysis of the fluctuations of emission line intensities. Other Excitation Techniques. The hollow-cathode discharge is a well known excitation method which has never been very widely used because of experimental difficulties. Kevertheless, it remains useful for special application. Grimm (69E) developed a new form of hollow-cathode source which can be operated as a glow discharge with very interesting properties. It may be that this source will be used primarily in this latter mode; a pronounced reduction in matrix effects is reported. Pevtsov and Krasil’shchik (131E) described another variant of the hollow-cathode lamp in which the sample is covered with a thin graphite layer in order to separate the vaporization and excitation regions. Pevtsov,
Krasil’shchik, and Lavkina (1S2E) reportedsomeproperties of this source, and Pevtsov, Krasil’shchik, and Yakovleva ( I S S E ) employed chlorination reactions in this source to enhance the vaporization of refractory metals. Fundamental studies of the hollowcathode as a spectral source were described by Semenova et al. (149E), Bueger and Fink (SOE),and Tsukamoto (164E). Zil’bershtein et al. (181E)compared limits of detection in analysis with the hollow-cathode and the carbon arc. Goleb (57E) reviewed applications of hollow-cathode lamps to spectral analysis, with particular emphasis on the isotopic analysis of lithium, uranium, and boron. The use of a high-temperature hollowcathode for the determination of trace elements in steels, high-temperature alloys, and related materials was described by Thornton (159E), and Woodriff, Wheeler, and Ryder (178E) developed a hollow-cathode lamp suitable for use in emission spectrometry. Bueger and Fink (S1E) employed the hollow-cathode lamp in the analysis of liquids, while Dobrosavljevic, Zhiglinskii, and Kholpina (&E) investigated pulsed hollow-cathode emission sources with the help of time-resolution spectrometry. There has been considerable interest in, and confliciting reports on, various forms of radio-frequency excitation sources. The reason for this interest is exemplified by the report of Dickinson and Fassel (45E) on detection limits on an induction-coupled plasma torch. They reported detection limits for many elements to be two to four orders of magnitude superior to the best reported yet by flame emission or absorption techniques. On the other hand, Veillon and Margoshes (168E) reported unfavorable results with a similar (but not identical) plasma torch. They found very complex and severe interelement effects, and ascribed them to departure from local thermal equilibrium. Scholz and Anderson (146E) investigated this specific subject in a plasma torch, and reported the existance of local thermal equilibrium a t pressures of 0.5 and 1 atm. The sources cited above were operated a t frequencies of a few megahertz to some tens of megahertz. Greenfield, Jones, and Berry (66E) were issued a patent on a source of this type, and Hughes and Mavrodineanu (7SE) obtained a patent on a source operated at 2450 MHz. These ultra-high frequency discharges operate a t lower power. Other microwave-frequency sources were described by Hingle, Kirkbright, and Bailey (?‘.$E), Motornenko and Martinyuk (108E), and by Murayama (11OE). The characteristics of sources of this type were reported by Runnels (ICSE), and by Murayama,
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Matsuno, and Yamamoto (111E), who described some studies on matrix effects. Other papers on radio-frequency sources were by Gol’dfarb and Goikhman (56E),Egorova and Perevertun (50E), and Zakharov (179E). Aldous et al. ( S E ) described the design of and some preliminary studies with a n atomic-hydrogen plasma torch. The plasma torches are sensitively affected by the method of introduction of solutions. West (176E) described a n ultrasonic sprayer suitable for use with a plasma torch, and Veillon and Margoshes (169E) described a sample introduction apparatus for this source which converts the solution spray into a dry aerosol. Not all work with r-f plasma has been concerned with the analysis of materials introduced as aerosols. Kleinmann and Svoboda (81E)first evaporated the solution on a graphite disk, which was then placed in a chamber filled with argon. The disk was heated ohmically to evaporate the sample, and the atomic vapor was then excited by a ~O-MHZ,200-W discharge. The plasma jet is a somewhat more established method for the analysis of solutions, and it too exists in several forms making comparison of results from different laboratories rather difficult. Goto, Atsuya, and Suzuki (62E) compared plasma jet and plasma torch excitation of solutions. Not all interest in the plasma jet has been for solution analysis, and Konavko and Urmanbetov (84E) and Krest’yaninov, Shilin, and Teploukhova (90E) described the use of this source for analysis of powdered samples. Jaeger (74E) described studies of temperature and element distributions in a plasma jet, and found an effect of the ionization energy of elements introduced into the plasma on its temperature. This can cause matrix effects, which were investigated for the plasma torch by Schirrmeister (144E, 145E), who reported that the effects observed were not caused by temperature changes. Filimonov and Lavrova (51E) stressed the role of solution droplet vaporization in accounting for matrix effects, and Triche, Butti, and Besombes-Vailhe (162E) also investigated droplet vaporization as well as chemical reactions in the plasma. Goto and Atsuya (61E) and Takeuchi and Katsuno (158E) investigated the influences of several experimental parameters in plasma jet spectrometry and gave detection limits for several elements. Petrakiev and Kyurkchieva (119E) described the properties of a plasma jet operated with a pulsed discharge, which was found to be superior to the dc-operated source. Doerffel et al. (47E) gave some particulars on a modification of the plasma jet called a 406R
0
“cascadestabilized arc,” and Marinkovic and Dimitrijevic (IOSE) described a plasma jet source which was said t o be cooled to a temperature of 3100 OK by addition of potassium chloride to the solutions. This source was said to be relatively free of interferences observed in flames and to be suitable for elements normally determined with flames as well as those which form stable oxides. As with the plasma torch, the method of sample spraying has an important influence on the quality of results obtained with the plasma jet. Owen (127E) compared ultrasonic and pneumatic nebulizers for the plasma jet, finding the former to be particularly superior when concentrated solutions must be handled. Szivek et al. (156E) modified a plasma jet to employ a Zeiss atomizer, and reported a marked improvement in the repeatability of results in the determination of magnesium in blood plasma. Most of the work on plasma jets seems to have been in the direction of making the design more complex. Muntz (109E) has shown that a very simple design is possible; he described a very easily made and used source called a “gas sheathed tubular arc” which may be regarded as a form of plasma jet. TRACE ANALYSIS
Several reviews have appeared on the analysis of pure materials by spectroscopic methods including preconcentration methods. General reviews are by Krasil’shchik and Vainshtein (25F), by Nazarenko and Flyantikova (S6F), and by Pesic (,$OF). The spectrographic determination of trace elements in soils and plants was discussed by Suine (48F). Direct spectral excitation of materials or of samples prepared by simple conversion often serves for high sensitivity trace analysis without chemical separations. Morrison et al. (34F) described the use of the high current dc arc for the analysis of ashed biological materials. Data indicated the possibility of using a single analytical curve for several different types of biological materials. Nash (S5F) established optimum conditions for the direct dc arc determination of rare earths in YzOa. Schramm and Beckert (45F) describe a method of determining traces in very pure tellurium by using tellurium self electrodes with a n interrupted dc arc. For the determination of trace rare earths in GaAs, Wang (55F) found that by selecting the last part of the dc arc burn, detection limits in the parts per billion range could be obtained. Wacehter (54F) described the determination of trace elements in aluminum
ANALYTICAL CHEMISTRY, VOL. 42, NO. 5, APRIL 1970
oxides with a relative standard deviation of 10%. After suitable thermal pretreatment, various preparations of oxides could be analyzed by the same method with few exceptions. Conditions for the determination of trace elements in soils were studied by Rabinovich (4SF) using the dc arc. Karyakin et al. ( d S F ) found that the arcing of small samples in a flow of compressed air for trace analysis showed improved constancy of arc temperature and freedom from contamination from the air. Ecrement ( 1 S F ) studied the use of fluxes in arc spectrography for the determination of trace elements in soils and rocks and found that lithium borate gave 3-10 times greater sensitivity over the KzS04 dilution method. An interesting method for the determination of silver was reported by Woodriff and Siemer (66F). In this method, the silver is plated onto a filament and subsequently evaporated into a stream of helium. The spectrum is excited by a radio-frequency gas discharge resulting in a sensitivity of 2 x ng. The addition of reagents or carriers for spectral excitation to improve the detection limits for trace analysis is well known. Frishberg (16 F ) described a method for determining tellurium in sulfur by using two thermochemical reactions: a reaction of sulfur with 1100~ and of iodine with tellurium to form difficulty volatile MoS2 and volatile tellurium iodide, respectively. Tempelhoff (49F) described the determination of trace elements in high-purity silver halides by using the background as a reference value. Halogenation of materials for increasing the volatility is the subject of several papers. Pevtsov et al. (418’) used chlorination reactions in a hollow cathode for the determination of difficultly volatile elements. Lazebnaya, Moskal’chuk, and Yudelevich (28F), and Yudelevich, Lazebnaya, and Lyandusova (62F) discussed the use of fluorination reactions to increase the sensitivity of detection of trace impurities in alkali metal salts. Nesanelis, Zolotovitskaya, and Shevchenko (STF) determined trace metal impurities in garnets by fractional distillation using Gaz03as a carrier and “Fluoroplast-4” as fluorinating agent. Extensive use is now made of preliminary concentration prior to spectrometric analysis of materials when dealing with materials that are difficult to handle such as sulfur or selenium, or when increased sensitivity is required for trace analysis. The extent of the methods of separation used and the materials analyzed are indicated in Table I where typical systems are listed. Further information on determination of trace elements may be found under Other ilpplications where analyses of specific materials are listed.
LASERS AND MICROANALYSIS
Table 1.
The literature on the applications of the laser to emission spectroscopy has become quite extensive and now includes treatment of basic factors involved in the laser volatilization. The fields of application of the laser were reviewed by Moenke-Blankenburg (S5G), by Katsuno et al. (15G), by Petrakev (4WG), by Sakurai and Shimoda (47G), and by Fijn van Draat ( f 4 G ) . Moenke (SWG) reviewed progress in the field of laser analysis and he compared (SSG)observations on electron beam microanalysis and laser micro spectral analysis. Johnson (19G) discussed potential laser applications in the process industries. Apparatus for laser analysis is being improved, as shortcomings of the original equipment became evident. Peppers et al. ( 4 f G ) described a n improved &-switched ruby laser which provides longer-term stability and improved precision. A laser microspectral analyzer, made in Jena, was described by Moenke-Blankenburg (S4G) and applications in various fields are discussed. Trucco (61G) described a laser with cross spark discharge. Recently, a U.S. patent has been granted to Franken et al. ( f 5 G ) which appears to cover the basic use of the laser in microanalysis. A sample cell to be used for laser excitation of highly toxic or radioactive materials has been described by Barton (4G). The cell also provides a means for controlled atmosphere for the analysis. Basic factors involved in the use of lasers for sample volatilization and excitation are receiving increased attention. Piepmeier and Malmstadt (44G) made time- and spatially-resolved spectrometric observations on single and multiple spikes and discuss the development of the plasma and time periods of excitation. Boegershausen and Vesper ( 8 6 ) proposed a simplified model to depict the production of laser plasmas. They studied the behavior of several materials under action of the laser and made temperature measurements showing temperatures of 4900 up to 7900 OK, with those produced by giant pulses up to a temperature of 12,000 O K . I n another detailed study, Afanas’ev et al. ( I G ) studied the gas dynamic processes occurring during the vaporization of a number of solids. The pulse yield, P , thrown out mass, M , and the rate of evaporation were determined. Zhukovskii, Panteleev, and Yankovskii (58G), using plasmas obtained by a laser under regular and quasi-steady generation conditions, concluded that the laser can be used for excitation without the need of additional electrical discharges. Paton and Isenor (4OG) measured the energies and quantities of ions in laserproduced metal plasmas. General agreement was found with existing theory
Methods of Preliminary Concentration for Spectrometric Analysis
Elements determined AS, 16 elements As, Ga, GaAs 10 elements Ba, Sr fluorides 9 elements Bi, Gal In, Sb, T1 Various impurities Fe 31 elements Ga 16 elements GaAs 18 elements Gab 14 elements Ge HF Hf, Zr Hf, Zr HgSe 14 elements In 14 elements InAs 14 elements ,
Methods of separation Ion exchange Evaporation of Br Extraction Extraction Extraction Extraction Evaporation of Br Extraction Evaporation as I or S Ion exchange Extracted Evaporation of HgSe Extraction Evaporation of As as Br, extraction of I n InSb Various elements Extraction NaOH Extraction 17 elements Bi, Co, Nil Sb, T1 Extraction Extraction 7 elements Ir, Pd, Pt, Rh, Ru Ion exchange Extraction As, Bi, Sb Extraction 23 elements Ion exchange 12 elements Crystallization 15 elements Zone refining Sb 19 elements Evaporation of Br Sb 30 elements Evaporation of Se 16 elements Se Low solubility TeOz 22 elements Te Ion exchange Th D Eu,Gd,Sm Extraction Ta. Ti U Electrodeposition on C rod Zn Ag* ’ Precipitation to prepare Biological subCo, Cu, Mn, Zn pure base solution stances Ionexchan e Blood and serum 18 elements Extraction %y F Minerals and ores Rare earths Evaporation or extraction Organic solvents 15 elements of quinolate Rare earth oxides Various elements Chromatography Coprecipitation with Te A Rocks Extraction N%, Ta Rocks Fire assay Pd, Pt, Rh Rocks Coprecipitation Semiconductors Electrodeposition on Cu disk Solution c1, s Coprecipitation Solution Hf, Zr Precipitation with dye Solution In Electrodeposition on C rod Surface water Heavy metals Paper chromatography Pd. P t Waste products Coprecipitation Water 14 elements Matrix
::
Id:
2,
regarding the mean energies of the different ionic species, but the relative abundances display anomalies. The size and shape of craters produced by laser action were studied by Klocke (26G) and the results are compared with theoretical evaporation models which have been developed. I n this investigation, the effect of the reflection of laser light by the evaporating surface has been taken into account. Varsi (5SG)studied the interaction of high intensity laser radiation with metallic surfaces of copper and gold. He proposed a model of the process and demonstrated its validity. I n addition, an experiment was reported for the accurate determination of the yield, that is, the amount of material ablated by the laser radiation. Observations on the application of a Nd laser microprobe, including many details on the phenomena involved, were made by Katsuno, Sunahara, and Morita (14G). Matrix effects in the laser sampled spectrochemical analysis of various alloys were reported by
Cerrai and Trucco (12G, ISG). Effects were attributed to grain size or strain where the electron microprobe showed little variation. Korunchikov and Yankovskii (28G) studied the distribution of intensity in the plasma plume for various chemical elements. The effects of the laser pulse on steel were studied in air and vacuo by Kaporskii et al. (2OG); in vacuo, the central crater is surrounded by a large number of smaller craters. Akhmanova, Kaigorodov, and Karyakin (2G) studied the condensed material produced by a laser plasma from various minerals using infrared spectra. The spectra gave evidence of oxidation and thermal decomposition which occurred in the course of irradiation. Kokora (27G) reported on the distribution of alloying components in the laser radiation-affected zone for steel, and indicated that the action of the laser radiation is analogous to that of electric sparks. The possible use of a single pulse
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laser system for spectral analysis was investigated by Panteleev and Yankovskii (S9G)who indicated that the method could be used to determine metals in alloys. Amounts of elements of 10-9 g or less could be detected. A proposal has been made to improve the action in the laser microspectral analysis by Petrakev, Dimitrov, and Georgieva ( 4 3 3 . Studies on minerals and metal alloys showed that the intensity can be increased up to tenfold depending on the conditions. I n collecting the material vaporized by means of a laser, Putrenko and Yankovskii (45G) report that a carbon tube on the sample provides for more efficient collection of sample. The distribution of alloying elements in some steels in the zone affected by the focused laser radiation is discussed by Rikman, Kokora, and Zhukov (46G). Applications of laser microspectral analysis extend over many fields including biochemistry, metals, nonmetals, and minerals. Glick (17G)has described cytochemical analysis by the laser with a crossed spark discharge. This method was applied to electric spark cross excitation for samples as small as 10-25 pm in diameter by Beatrice, HardingBarlow, and Glick (5G). Application was made to in situ detection of beryllium in biological specimens by Brokeshoulder and Robinson (9G). blicroconcentration gradients on the surface of steel samples were determined by means of the laser microprobe by Webb and Cotterill (550). For the determination of boron, the calibration curve is linear for 10-1000 ppm. A novel application of the laser microprobe is the study of sodium penetration into stainless steel as reported by Sowa (49G). By progressive penetration with a laser through the wall of the stainless steel tube, entry into a sodium-rich region was attended by intensification of the sodium lines. I n a study of spectrographic analysis of nonmetals with the use of a laser, Karyakin, Akhmanova, and Kaigorodov (2dG) stress the importance of adjusting the focusing distance for proper application. Small analytical gaps (2 mm) and high voltages (300 V) for the cross spark discharge result in an increased sensitivity in the combined laser excitation method. I n another area of application, Morris, Askey, and Pardue (36G) demonstrated the feasibility of the laser microprobe for rapid measurement of the isotopic content of uranium. Karyakin, Akhmanova, and Kaigorodov (21G) discussed the use of the laser for the analysis of semiconductor materials. Karyakin et al. (2SG) described the use of the laser for the determination of chromium in ruby. Cerrai and Trucco (11G) used the laser microprobe for sampling for qualitative analysis, and Whitehead and Heady (56G) used it for the excitation of trace elements in powdered materials. 408R
The analysis of minerals with the laser probe is a promising area. Snetsinger and Keil (48G) have studied the reproducibility and detection limits for the estimation of trace elements in minerals and show that detection limits for a number of elements are lower than those generally obtainable with the electron microprobe. The laser probe thus provides a useful supplement to the electron microprobe. Bobrova et al. (7G) described a method for the analysis of minerals using a ruby laser in which individual grains of minerals are analyzed. For the difficult problem of analysis of garnets, Blackburn, Pelletier, and Dennen (SG) described the use of a laser probe including the problem of preparation of standards. Comparison of results with the rock standard W-1 showed good accuracy and reproducibility. The laser is also used as a means of sampling local areas for later analysis by the usual spectrographic method as described by Zhukov, Nikiforova, and Kokora (57G). Although the laser has proved useful for the analysis of a wide variety of materials, the application of microspark emission spectroscopy should not be overlooked. Commercial apparatus is available for this means of analysis and the operator may develop his own equipment as described by Garbini, Mooney, and Schoder (16G). I n this method, a tape is placed on the sample surface and a hole is punctured a t the spot to be analyzed. The sample is excited with a very short spark for spectrographic analysis. A method was proposed by Satanson (37G) to determine the surface osidation of various metals by means of analyzing spectra of short duration discharges on the surface of the oxidized metal. The intensity of the spectral lines obtained for the oxidized surfaces are compared with that for non-oxidized surfaces of the same metal. The intensity shows a dependence on the oxidation of the surface. Local spectral analysis with a spark has been used to study the boundary diffusion of nickel in iron by Krishtal, Mokrov, and Stepanova (SOG). I n a similar application, Krishtal and hlokrov (29G) applied local spectrographic analysis for the study of diffusion in metals. Microspark spectroscopy was used to determine changes in composition a t defect sites on metals by Nikiforova (S8G). Volodina and Kozlova (54G) applied the microspectral method for studying the interaction of solders with metallized coatings on ceramics. For the identification of mineral inclusions, Arnautov (JG) described an apparatus for microspectral analysis in a helium or argon atmosphere. The plasma of the spark discharge comes into contact with the sample. The absolute sensitivity for most elements is reported to be lo-8-10-9 g with a 0.001-mg
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sample. Marzuvanov (S1G) applied a microspectral method to the analysis of mineral grains in polished sections. A report is included on a special atlas and tables compiled for small area spectrographic analytical purposes. The spectrographic determination of oxygen, nitrogen, and hydrogen in steels and alloys has been extended by Buyanov and Fedorova (10G) to local analysis. The area of the sample taken is 0.0007 mm2. Microspectral analysis methods also include the analysis of separated samples. Triche (51G) reported a method involving a selected micrographic attack on the sample. The area, in relief, resulting from the attack is analyzed spectrographically; the method was applied to the study of a Bi-Pb system. For the analysis of samples not exceeding 400 fig, Svoboda and Kleinmann (5OG) describe a high-current impulse argon arc method. Detection limits as low as a nanogram or less are reported. Harvey (18G) has described the procedures for analysis of samples weighing as little as 25-50 pg. OTHER APPLICATIONS
Methods for multielement deterniinations continue to be of interest in view of their efficiency for rapid analysis, Webb and Wordingham (125H) described a dc arc method with LiF buffer for the determination of minor constituents in a wide range of materials. Relative standard deviations of 5-10y0 were obtained a t the 100-ppm level for many elements. Blosser ( 9 H ) described a procedure for combining data from optical and mass spectrometry for complete trace analysis of MgO. Water pollution has been traced over several years by a spectrochemical procedure and the results were reviewed by Kopp and Kroner (66H). The importance of statistical treatment of data for water quality control by spectral methods was stressed by Uman (122H). The methods for introducing liquid samples into a discharge were reviewed by Gusarskii (45H) who concluded that use of an aerosol is to be preferred. Berezin and Korpushev ( 6 H ) reported on methods for determining SI C1, and Br in solutions. Zanzucchi (129H) described direct solution analysis with a new hollow-cathode discharge system. Pevtsov, Krasil’shchik, and Yakovleva (96H), and Zil’bershtein and Nikitina ( 1 S 1 H ) applied hollow-cathode excitation for the analysis of dried residues. Makulov and Zakharova (78H) and Dmitriev et al. ( S S H ) discussed the introduction of the sample as an acid solution on a filter paper into an arc or spark. The analysis of oils was reviewed by Van Rysselberge (123H) and a correlation of emission and atomic absorption
techniques based on results of oil samples by many laboratories was reported by Kittinger and Ellis (62H). Sampling. A large portion of the effort in emission spectrometry involves metal analysis, and problems of sampling continue t o receive attention. Taganov (117H) provided an extensive treatment of spectral analysis of metals with preliminary sampling which has been popular in the U.S.S.R. The goal of direct sampling of molten metals by the excitation source is approached with an apparatus described by Fassel and Dickinson ( S 6 H ) in which ultrasonic energy is used to nebulize the molten metal. Application has been limited to alloys of low melting point. Headridge and Lambert (47H) determined Xi in molten steel under an argon atmosphere with spark excitation. The standard deviation was double that of steel analyzed in solid form. hlelting of millings of steel in a high frequency induction furnace followed by centrifugal casting of the melt was investigated by Kemp (59H) who found advantages for this method. Dickens et al. ( S I H , S d H ) describe a sampling mold for obtaining disks and pins for emission and gas analysis of steel. Kashima and Kubota (57H) investigated means of promoting white solidification of cast iron samples, and Staats (109H) described a two-piece mold for sampling pig iron and cast iron. Metals. Makulov et aZ. ( 7 7 H ) describe a classification scheme of spectral analytical procedures for metals and alloys divided into solid metals, powders, and solutions. For the analysis of alloys by fractional distillation, Tumanov ( l d 1 H ) reported improved stability by forced rotation of the arc anode spot. McKaveney, Baldwin, and Vassilaros (84H) combined classical chemistry and spectrographic methods for the analysis of steels especially for obtaining standards. The determination of gases in metals remains a critical problem. Bruch (15H) reviewed spectrometric methods for the determination of oxygen and nitrogen in metals, and Malamand (80H) reported on analyses for gases and metalloids in steels and refractory alloys using the vacuum ultraviolet. Various escitation methods for the determination of gases in metals were reviewed by Furuya and Kamada (38H). Petrakev and Petkova (95H) describe the use of a high voltage source for determining gases in metals. Skotnikov (107H) attempted to relate the state of combination of nitrogen in the metal to observed intensities. Dickens et al. (SOH) described a new apparatus for simultaneous measurement of oxygen and nitrogen in steel after melting the sample in a tube furnace. Hirokawa and Goto (60H) investigated the determination of nitrogen in
steel with a dc arc observed in the vacuum ultraviolet. The same authors (61H)also studied the use of a lowvoltage spark discharge. Skotnikov (108H)described the determination of nitrogen in steel foils based on heating of the foils and their partial combustion. Determination of oxygen in steel by visual observation of the spectrum was reported by Svet and Kozlova (116H) for the concentration range 0.005 to 0.1% oxygen. Hydrogen was determined in steel by Zolotareva and Bessonova (135”) using a low-voltage discharge from an impulse generator. Grikit et al. (43H) investigated the spectral determination of hydrogen in metallic titanium and Sukhenko, Grigorova, and Lindstrem (1lOH) discussed the determination of hydrogen, oxygen, and nitrogen in titanium alloys. The determination of gases in metals by isotopic methods has received considerable attention; this subject is included in the later section on Isotopic Analysis in this review. For the analysis of steel, Goto and Hirokawa (41H ) reviewed the application of various special instrumental methods including atomic absorption and laser excitation. Manabe and Inokuma ( 8 1 H ) discussed the importance of the control of preliminary treatment of the steel sample for dc arc trace analysis. Nikitina and Gorevaya (87H) found that reduced gas atmosphere pressure improved sensitivity with the ac arc for determination of boron and cerium in steel. The application of the plasma torch to steel analysis was reported by Suzuki (111H) for the determination of aluminum, and the same author (112H) for determination of molybdenum. He reported linear calibration curves over wide ranges. Goto and Atsuya (4OH) described a modification of a plasma jet flame apparatus and applied it to determine aluminum and boron in steels using solutions. Hirokawa and Goto (49H) applied the nitrogen plasma jet flame to the direct excitation of solid metal samples with satisfactory results. As described earlier under Trace Analysis, chemical preconcentration is employed extensively to improve sensitivity of detection. Koch and Ohls (64H) applied this technique to determine 13 trace elements in steel for which a nitric acid solution of the trace elements is atomized into an electrode gap without contacting the graphite electrode surfaces. The factors that affect the spectrometric analysis of steel continue to be investigated. Ohls, Koch, and Becker (90H) showed that effects of inhomogeneity and contamination by sample holders and by the atmosphere were important for determination of sulfur, phosphorus, manganese, and silicon in steel. Koch and Ohls (66H) and Ohls,
Koch, and Becker (91H) showed that considerable improvement in the routine spectrometric analysis of steel resulted from use of a high energy prespark discharge for conditioning the sample surface. Herberg, Holler, and KosterPflugmacher (48H) found that nonmetallic segregates such as sulfides, carbides, or oxides acted preferentially as cathode points in the sparking of steel samples. They recommend increase in discharge energy and decrease in power for the pre-spark period. To minimize the effect of elongated sulfur inclusions in steel Bramhall ( 1 d H ) recommended sectioning of samples to provide surfaces parallel to the direction of mechanical working, otherwise to increase the time of pre-spark. The metallurgical history of high carbon steels was shown by Suzuki (11SH) to considerably affect the spectrometric analysis. Effect of thickness of sheet steel samples was investigated by Buyanov et aZ. (19H) who found that effects were particularly severe for determination of carbon and sulfur. Suzuki and Kambara ( l l 4 H ) studied the effect of graphite and zinc counter electrodes in the analysis of steel and described an improved method for determining silicon and manganese. Effects can serve for practical uses as shown by Bramhall, Haynes, and Willingham (1SH) who described a spectrographic method for measuring the decarbonization of steel. Line selection for the determination of silicon in steel was discussed by Bryan and Runge ( 1 6 H ) , for nickel in steel by Novotny and Oulehla (88H), and for boron in steel by Ono and Fukui (92H). Pruycheva (98H) used a copper counter electrode for determining boron and aluminum in steel by pulsed-arc excitation. The analysis of oxide inclusions in steel was described by Istodor, Dobrescu, and Costin (62H) who separated the inclusions by electrolysis. Improvements in the analysis of nonferrous alloys were reported. Xatocha and Petit ( 8 S H ) described an extensive study of the effect of nitrogen on the spark point-to-plane analysis of aluminum alloys. They reported improvement in precision and reduction of interelement effects by use of the nitrogen shielding. -Matocha (8dH) also described a simple method for preparing briquet electrodes of powder in aluminum caps. Davidson (15H) studied the severe effect of dispersion of silicon particles in aluminum-silicon alloys on excitation and recommended modification of the molten sample in the ladle by addition of a sodium salt flux. The determination of high carbon contents and metallic elements in cobalt alloys by the vacuum spectrometer was described by Malamand (79H). Ferraro Russo (S7H) determined the gold content in gold coatings on brass using
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a solution, dry powder arc method. Dmitriev, Essen, and Boganova (S4H) described a chemical-spectrographic method for determining aluminum and magnesium in nickel-base alloys in which the sample is introduced on a filter paper into the arc. Yudelevich et al. (126H) reported increased sensitivity for the analysis of tin using optimum conditions for cast samples and powdered tin samples. A chemical-spectrographic method was used by Khlystova and Tarasevich (60H) for the determination of tungsten in molybdenum. Vovk et al. (124H) studied the effect of atmosphere composition and the arc discharge on the surface of titanium electrodes; an argon atmosphere is recommended. The analysis of vanadium was investigated by Muzgin et al. (86H) who reported increased sensitivity by volatilization of impurities from the more refractory VzOs in the cathode of the arc. Effects of various atmospheres on the analysis of type metal was reported by Kashima and Kubota (6811)who used a flow of argon through an orifice in the graphite counter electrode. Gabler and Peterson ( S 9 H ) compared five spectrometric methods for the analysis of high-purity zinc and found that direct arcing of metal samples provided best sensitivity. hlilazzo (85H) investigated the use of the hollow-cathode machined from zinc alloys for their analysis. Nonmetals. Spectrometric methods are applied extensively for the analysis of semiconductors, pure elements, rocks and minerals, refractories, biological materials, plants, and gas mixtures. For the analysis of powdered materials, Szarvas, Jr., Papp, and Szarvas (116H) proposed the use of a mixture of 15% resin and 85% carbon mixed 1 : l with the sample and pressed into electrodes. Kirichenko, Khurin, and Fokin (61H) proposed the determination of the type of molecular compound of an element from spectral observation of compounds in an arc; examples are shown for aluminum and magnesium compounds. Kuzina et al. (69H) analyzed aluminum nitride by a Gaz03carrier distillation method. High purity boron was analyzed by Degtyareva and Ostrovskaya (27H) for 32 elements using the arc with Li2C03 or AgCl carrier. The plasma jet was applied by Fagan and Klein ( S 5 H ) to analyze boron tribromide, and they reported standard deviations of 4.60/, for determination of silicon and titanium. Dem’yanchuk and Fushchich ($914) described a method for determining carbon in carbides using the absolute intensity of the C 2296 8 line. For the analysis of powdered slags Trapeznikov and Nikitina (119H) proposed fusion of the sample with flux 410 R
(Na2C03plus Na2B407) in the graphite electrode prior to arcing. Trapitsyn (120H) compared the sensitivity of ac and dc arc methods for rare earth determinations and found the ac arc much more sensitive. Effects of rare earth oxides on their impurities in spectrographic analysis were studied by Karyakin, Laktionova, and Pavlenko (56H) who showed shifts of calibration curves for most elements. Osumi el al. (9SH) also studied these effects using solutions; addition of elements having low ionization potentials increased sensitivities. Effects of the matrix on the distillation of refractory elements as chlorides were reported by Pometun, Kopp, and Romaikina (97H). Rare earths are also effectively determined by X-ray stimulated luminescence as discussed by Shand (101H). Kuznetsov and Stakheev (7OH) reviewed mechanization and automation for saving time in the emission spectral analysis of powders. The analysis of airborne dusts for calcium and magnesium was described by Shimozaki (102H). Direct reading determinations of trace elements in silicates was described by Tennant and Sewell (118H) who use automatic background and matrix corrections to attain relative standard deviation of *5%. Shumanis, Fedorenko, and Menaker (10SH) described the determination of 20 elements in sedimentray rocks using arc excitation and a 10-step attenuator a t the spectrograph. The borate fusion technique for the trace analysis of geological materials was examined critically by hfaessen and Boumans (76H) who used X-ray diffraction to observe the effect of fusion conditions in sample preparation. I n the paper the favorable effect of flux addition on the accuracy and precision of spectrometric results is discussed in terms of a model for the exit of analytical elements from the electrode cavity. Luzhnova, Malykh, and Serd (75H) discussed a method for analyzing ores by spectral recording of scintillations, emitted by powder particles flowing into the arc, as a function of time. Livshits (7‘4H) reported an improved assay-spectrographic method for determining gold and platinum elements in rocks. Karyakin, Savinova, and Andreeva (56H) reported that a pulsed vacuum excitation source was effective for the determination of halogens in granites; laser vaporization was not found to be better. For the analysis of refractory oxides, the carrier distillation method continues to serve on a large scale. However, Avni ( 1 H ) described a new method for analyzing U30s, without addition of carrier or chemical treatment, in which the spectrum of the arc near the cathode serves for determination of impurities. It was claimed to be faster and as
ANALYTICAL CHEMISTRY, VOL. 42, NO. 5, APRIL 1970
accurate as other methods in use. Avni (ZH)described a similar technique for determining 35 impurities in T h o z and Z r 0 ~ . I n a later paper on the subject Avni and Boukobza (SH) added carriers to improve sensitivity to determine rare earths. Fluorides or Teflon (Du Pont) in spray form were employed. The same authors ( 4 H ) described the application of their arc cathode region method for the direct determination of 50 trace elements in phosphate rock using calcium metaphosphate as buffer. Several papers have appeared on applications of the carrier-distillation method using various carriers or combinations of carriers to improve sensitivity. For trace analysis of U308,Day, Serin, and Heykoop (26H) used SrF2Ga203 carrier and Kleinmann and Svoboda (63H) used NaCl. Capdevila (2OH) modified conditions for the trace analyses of uranium oxide to improve sensitivity. Capdevila, Roca Adell, and Alvarez (21H) described a method for trace analysis of uranium tetrafluoride in which Y203 is added to convert the uranium tetrafluoride to oxide during the arc excitation, thus reducing the volatilization of uranium. Laib and Lykins ( 7 l H ) described a carrier technique for trace analysis of niobium oxide using a 1:1 mixture of AgCl and AgF. DelGrosso and Landis (28H) reported carrier and other methods for the trace analysis of thorium oxide. The determination of impurities in plutonium was reviewed by Buffereau (18H). Brech ( l 4 H ) compared optical emission and atomic absorption methods for the analysis of plant tissues, and concluded that both are useful but optical emission is advantageous for multielement analyses and for wide ranges of concentrations. Bedrosian, Skogerboe, and Morrison ( 5 H ) described a sensitive and rapid spectral method for the determination of a large number of elements in biological materials using 25-50 mg of dried material for the analysis. Schoenfeld (99H) described the rapid determination of beryllium in urine or lung tissue by an ashing technique and the dc arc, while Hayes, Bisson, and Dennen (46H) employed dehydration of lung tissue and arcing for the beryllium determination. Changes in some parameters in the determination of beryllium in air samples were reported by Gross (44H) to improve the reproducibility and to reduce error. Fundamental discharge conditions for the analysis of gas mixtures were investigated by Bueger, Maierhofer, and Reis (17H) who reported optimum conditions for the determination of a number of gaseous elements. Gran’kova and Kiselevskii (42H) improved a discharge chamber in which the gas is introduced to the electrodes tangentially
to produce a whirlwind effect. The determination of nitrogen in argon and helium continues t o be studied. Korolev, (67H, 6 8 H ) described a double channel gas analyzer with interference filters for determining nitrogen in argon. Perminova ( 9 4 H ) used a high-frequency discharge for determining nitrogen and oxygen in helium. Berezin and Yanovskaya ( 8 H ) investigated three spectral methods for measuring gas pressure; these relate t o changes in spectral line intensities or the continuum as a function of gas pressure. Isotopic methods for determining gases are considered in the following section. ISOTOPIC ANALYSIS
Spectrometric isotopic analysis is applied for determining concentrations of individual isotopes largely in gases, but in favorable cases for elements in solid form as well. Zhiglinskii, Kund, and Khlopina (ISOH) discussed sources of error in spectral analysis of isotopes of strontium with respect t o concentration level and interferometer thickness. Capitini, Ceccaldi, and Leicknam (22H) reported analyses for isotopes of uranium with an accuracy of 2-3% using electrodeless lamps. Shuster and Zabron (104H) determined boron isotopes by aspiration of a solution into a plasma jet discharge and by measuring the intensity of0 1°B and IlB emission lines a t 3451 A. Measurement of isotopic ratios by molecular band heads is a well known principle. Chaney ( 2 S H ) described the determination of boron isotopes by the band heads ‘OB0 and “BO. Ivanova and Fedorov ( 5 S H ) described a general spectroscopic isotopic method for the determination of gases in metals by a dc arc with stable isotopes as internal standards; applications may be made to the determination of nitrogen and oxygen in titanium, niobium, and other metals. Improvement in the hollow-cathode method for analyzing gases in solids was reported by Oganezov, Chikhladze, and Shvangiradze (89H) by making blank corrections. The hollow-cathode served Berezin and Sten’gach ( 7 H ) for determining deuterium in titanium. Determination of isotopes of nitrogen has received much attention. Cook and Goleb (24H) used a n electrodeless discharge with a noble gas as a sustainer for determining 15N. Seiler and Werner (100H) also applied a n electrodeless discharge for this determination. Leicknam et al. (7ZH, 7 S H ) found improved accuracy in the determination of 15N by photoelectric intensity measurement and described their apparatus. Band spectra of Cl60 and C1*0 from a wave discharge were used by Kamada ( 5 4 H ) for measuring the isotope ratio of oxygen in carbon monoxide.
Isotopic equilibration with enriched isotopes is being applied for improved accuracy in the determination of gases. Zakorina et al. (128H) discussed three variations of spectral isotopic determination of gases in metals: high temperature heating of samples with a high frequency generator, hot hollowcathode, and lasers. Shvangiradee, Oganezov, and Chikhladze (106H) applied isotopic equilibration in the hollow-cathode spectral determination of oxygen in metals of widely different melting points, and in silicon (106H). Zakorina (127H) described use of a hollow-cathode method in which there is simultaneous isotopic equilibration and the spectral determination of the equilibrated gas isotopic composition. Borisov, Nemets, and Petrov (10H, 11H) applied high temperature isotopic exchange for the simultaneous determination of hydrogen, oxygen, and nitrogen in gas mixtures and in metals. ACKNOWLEDGMENT
The authors express their appreciation for the valuable contributions of Barbara Pastine, Virginia Stewart, and Charlotte Fleming in literature searching and recording, and of Karen Loraski, assisted by Debra Hull, in the typing of the manuscript. LITERATURE CITED
Books and Reviews (1A) Addink, N. W. H., Nat. Bur. Stand. (U.S.), Monog., 100, 121 (1967). (2A) American- Society for Testing and Materials, ‘‘Methods for Emission Spectrochemical Analysis: General Practices, Nomenclature, Tentative Methods, Suggested Methods,” 5th ed., ASTM, Philadelphia, Pa., 1968. (3A) Atovmyan, L. O., Borod’ko, Yu. G., “Analysis in Chemistry. Spectroscopic and X-Ray Diffraction Methods of Analysis,” Zranie, MOSCOW, 1967. (4A) Baer, W. K., Perkins, A. J., Grove, E. L., eds., “Developments in Applied Spectroscopy, Vol. 6,” Plenum Press, New York, N. Y., 1968. (511) Belyaev, Yu. I., Ivantsov, L. RI., Karyakin, A. V., Z h . Anal. Khim., 22, 1702 (1969). (6A) Burmistrov, M. P., Spektral. Anal. Geol. Geokhim., Mater. Sib. Soveshch. Speklrosk., bnd, (Irkziisk) USSR 1963, 82 (Pub. 1967); C.A., 68, 118969e (1968). (7A) Dawson, J. B., Heaton, F. W., Spectrochemical Analysis of Clinical Material,” (American Lecture Series, Publ. No. 676) Thomas, Springfield, Ill., 1967. (8:) Dobrowolski, K., Bondaruk, F., Spectral Analysis of Gases and Metals,” WNT, Warsaw, Poland, 1967. (9A) Gegus, E., Zimmer, K., eds., “Proceedings of the XIV Colloquium Spectroscopicum Internationale, Vols. I, 11, 111,” Adam Hilger, Ltd., London, 1968. OA) Gillieson, A. H., ed., “XI11 Colloquium Spectroscopicum Internationale, Ottawa, 1967,” Adam Hilger, Ltd., London, 1968. 1A) Grant, C. L., Pum’f. Inorg. Org. Mater., 1969, 11, Marcel Dekker, New York, N. Y.
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I1 Q'lfi7) ,-"-. ,. (65C) Tonea, T., Pavlovsch, G., Rom. Patent 51,325, Oct. 15, 1968. (66C) Wada, Y., Watanabe, E., Ger. Patent 1,277,591, Sept. 12, 1968. (67C) Zakharov, L. S., Aidarov, T. K., Lakhtionova, E. S., Koreeva, T. A., Zh. Prikl. Spektrosk., 9, 189 (1968). (68C) Zil'bershtein, Kh. I., Nikitina, 0. N., Zh. Anal. Khim., 23, 26 (1968). Standards, Samples, Calibration, and Calculation (1D) Aidarov, T. K., Zh. Prikl. Spektrosk., 9,719 (1968). (2D) Anderson, J. W., Lincoln, A. J., Appl. Spectrosc., 22, 753 (1968). (3D) Arskel'yan, N. A., Maiorov, I. A,, Zh. Prikl. Spectrosk., 7, 308 (1967).
(4D) Avdeenko, V. P., Neuimin, Yu. A., Furman, Kh. M., Zavod. Lab., 34, 965 I,-~--,. 1 968). (5D) .Barnett, W. B., Fassel, V. A., Kniselev, R. N., Spectrochim. Acta, 23B (lo), 643.( 1968); (6D) Berenshtein, L. E., Fal’kova, 0. B.,
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Yn. TI.. Nauch. Tr.. Zrkutsk. Cos. NaucK-fssled. Znst. Redk. Tsvet. Metal., 1968 (17), 80; C.A., 71, 56262v (1969). (30D) Magda, K., Paksy, L., Magy. K e m . Foly., 73,250 (1967). (31D) Margoshes, M., A p p l . Opt., 8, 818
(1969). , (32D) Margoshes, M., Rasberry, S. D., ANAL.CHEM.,41, 1163 (1969). (33D) Margoshes, M., Rasberry, S. D., Spectrochzm. Acta, 24B (9), 497 (1969). (34D) Masuda, I., Inouye, T., A p p l . Spectrosc., 22, 749 (1968). (35D) Mentinz, H., Ger. Patent 1,281,185 . . Oct. 24, 1968;’3pp. (36D) Ogneva, E. Ya., Ognev, V. R., Raikhbaum, Ya. D., Zavod. Lab., 34, 1450 (1968). (37D) Pellet,. J., Ruquet, D., Method. Phys. Anal., 5, 3 (1969). (38D) Pittwell, L. R., Can. Spectrosc., 13, 17 (1968). (39D) .Rae, V. N., Amin, A. G., Chakravarti, B. N., Trans. Indian Znst. Metals, 20 (June), 118 (1967). \ - - -
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(17E) Berezin, I. A., Razuvaev, V. A., Z h . Prikl. Spektrosk., 8, 915 (1968). ( B E ) Berneron, R., U.S. Patent 3,308,339, March 7, 1967. (19E) Boegershausen, W., Hoenle, K., Spectrochim. Acta, 24B, 71 (1969). (20E) Bondarenko, B. F., Zavod. Lab., 34, 161 (1968). (21E) Borovik-Romanova, T. F., Zh. Anal. Kh,im., 24, 974 (1969). (22E) Boumans, P. W. J. M., Spectrochim. Acta, 23B, 559 (1968). (23E) Ibid., p 805. (24E) Boumans, P. W. J. M., Maessen, F. J. M. J., ibid., 24B, 585 (1969). (25E) Zbid., p 611. (26E) Braman, R. S., Dynako, A., ANAL. CHEM.,40,95 (1968). (27E) Brewer, S. W., Jr., Walters, J. P., ibid., p 1980. (28E) Bril, J., Spectrochim. Acta, 23B, 375 (1968). (29E) Bril, J., Vinot, J., C. R. Acad. Sci., Paris, Ser. A , B 264, 999 (1967). (30E) Bueger, P. A,, Fink, W., Fresenius’ 2. Anal. Chem., 244, 121 (1969). (31E) Zbid., p 314. (32E) Buravlev, Yu. &I., Z h . Prikl. Spektrosk., 6, 583 (1967). (33E) Buravlev, Yu. M., Grikit, I. A., Ryabova, S. I., Mil’ko, V. I., Sb. T r . Vses. Nauch..-Zssled. Proekt. Znst. Titana,
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