Nucleonics W. S. Lyon, E. Ricci, and H. H. Ross Analytical Chemistry Division, Oak Ridge National Laboratory,’ Oak Ridge, Tenn. 37830
The maturation of a field is often presaged by a decline in innovative papers and confirmed by an increase in textbooks and reviews. During the past two years, the decline in number of good papers has become precipitous; concurrently, the quantity and quality of books, reviews, and bibliographies has greatly increased. In previous Nucleonics reports, we attempted to set up (somewhat arbitrarily) specific criteria for selecting publications to be included in the written text. Our basic guide was that a paper should exhibit something new or unusual in the conceptual sense. Clearly, a large number of excellent articles on applied analytical procedures were thus eliminated, but the policy did serve to keep Nucleonics within reasonable size limitations. During the past two years, we find that papers meeting our original standard are all but non-existent. However, if we relax this standard only slightly to include new and useful analytical procedures utilizing isotope techniques, the number of papers to be reviewed in a critical way would be unmanageable. Therefore, in the spirit of conservation so popular (and necessary!) today we present a much abbreviated-but not, we hope, neglectful review. What we lack in quantity in this report is made up for by the quality of material found in our expanded tables. A glance a t Table I will show the reader a number of excellent books and chapters in books that more than adequately fill the needs of neophytes and oldtimers alike. 1 Operated by Union Carbide Corporation for the U.S. Atomic Energy Commission.
Table I1 lists reviews and bibliographies covering many aspects of the nuclear-radiochemical field. Readers desiring information on specific techniques, access to application-type papers, or lists of references will find plenty to occupy their hands here. Table 111, Proceedings, can be used in conjunction with Table I1 as a source of recent good work in Nucleonics. As we have emphasized before, perhaps the best source of current on-going research in our field is conference talks and proceedings; remarkably little redundancy is found in the oral presentations (67). Finally, in Table IV, we index some useful compilations, tables of data, and similar information. Use of references such as those of Table IV can often save hours of searching handbooks, “encyclopedias,” and literature publications. Some readers may accuse us of slighting the analytical radiochemical side of this review and favoring activation analysis. There is partial truth in this charge, but like some of our now departed political leaders we will merely plead nolo-contendere and throw ourselves upon the mercy of the court. There is still much unfinished business for the nuclear scientist: the energy crisis is reviving demand for nuclear reactors of many types; these demands include better measurement techniques and more thorough radiochemical information. The food shortage and population explosion offer the radioisotope chemist an opportunity to contribute to a better quality of life through understanding and improvement of life processes. Medical research relies heavily upon tracer techniques; who can believe that we have reached the limit in these applications? One could
Table I. Books Radiochemical Analysis Ref. (
99)
56) 124) 74
I
90)
1125) 11121 136) 132) 173) 169)
Title
CommentQ
Gamma Ray Spectroscopy. . . Instrumentation in Applied Nuclear Chemistry Isotope Dilution Anal. Measurement of Low-Level Radioactivity Modern Analytical Chem. Nuclear Analytical Chemistry. I. Introduction Nuclear Milestones Physical Methods of Chemistry Practical Measuring Techniques for B Radiation Principles of Radiochemistry Radiochemistry
Complete practical coverage (111P) Covers detectors and hardware Gen. rev. of tech. and applications ICRU pub. Undergrad. text describes rad. chem. anal. Basic principles of nucl. physics and chem. Speeches of G. T. Seaborg Chap. on -,-ray spec. Wide range of detection tech. discussed Gen. text Subjects includ. trans-curium elements, nucl. chem., and Moessbauer spec. IMA) Design and use of large scale facilities Several chap. of anal. interest Theory, applications t o law and insurance Can serve as gen. text Rev.: includes procedure for ions and organic compds. (153 R) Chapters on isotope methods, tracer tech., radchem. sep., nucl. radiation. (MA) Topics include nucl. and radiochem. anal. (MA)
(27) Radioisotope Engineering 3) Radioisotopes in Medical Diagnosis 11) Radioisotope Instruments. Part 1 Radioisotope Laboratory Technique (3rd ed.) 29 ) ( 7 1 ) Radiometric Titration
‘
154) 1110)
Treatise on Analytical Chemistry. Part I, Vol. 9 Vistas in Analytical Chemistry
Nuclear and Atomic Activation Analysis Ref.
(42) 162) 19) (23) I
a
136) ‘54)
Title
Comment
Activation Analysis Advances in Activation Analysis Modern Analytical Techniques for Metals and Alloys Neutron Activation Analysis Physical Methods of Chemistry. Pt. I11 D Treatise on Analytical Chemistry. Part I, Vol. 9
State-of-the-art summaries Vol. I1 (MA) Chap. (130 R ) Exhaustive treatment (656 P) Rev. chap. (53 P) Chap. emphasizes basic principles
P = No. of Pages. R = N o . of References. MA = Multiple Authors.
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431 R
Table 11. Bibliographies and Reviews Radiochemical Analysis Ref.
Topic
Comment’
(116)
Source material for radiochemistry
(114) (82)
Radioisotopes in anal. Radiochemistry Environmental anal. Analysis of drugs Analysis of radiopharmaceuticals . Electrochemical anal. Tracers
Recent refs. to books, revs. and journals: wide range of sub. (117 P) Rev., indust. applications 1132 R) Rev. of lit. pub. July 69-Aug. 71 (131 P) Gen. anal., med., use of labeled cmpds. 16 P) Many nucl. techs. covered (8 P) Criteria for assessment discussed 14 P) Applications and techs. 16 P) Very extensive 136 P)
General
163)
(72) (47) 143) (140) Methods and Techniques Ref.
183) 192) (77)
Topic
Comment
110) (120)
Backscattering spectrometry Track etch tech. Trace anal. Trace anal. for solids Mossbauer spectrometry Application of Mossbauer Spec. Radiochem. of Mn Carbon-13 Isotopic gauges Pharmaceuticals and labeled cmpds Isotope X-ray fluorescence Liq. scint. counting Pollution control Transplutonium elements
Ref.
Topic
149)
(118) 131) (1111 1119) 1331
(137) 153) 1351
Survey of theory and applications (11F) 133 R) Rev. 137 R) Rev., many nucl. meth. (62 R) Rev., mainly instrumental (143 R) Rev. 1771 R ) Rev. of applications i n rad. chem. 117 P) New revision ,103 R) Abstract-bibl., author and key word index 1627 R ) Pollution control 13 P) Prep. with short-lived isotopes (1269 R ) Rev. Basic, wide range survey 139 R1 Industrial applications ( 5 P) 2 parts, bibl. 1757 R )
Nuclear and Atomic Activation Analysis Comment
General
f66) (91)
(75) 137) 88)
(68)
Gen. coverage Gen. coverage Trace analysis Forensic analysis Art and archaeology Nucl. and X-ray tech.
Updated 4th issue 1892 P) 1-6200 R) 142 P) (300 R ) Emphasizes NBS programs i l l P) Rev. (91 R ) Includes other nucl. tech. (204 R ) Rev. of tech. at AEC labs (15 P) 126 R )
Californium-252 14-MeV neutrons Ion beam techniques Ion beam techniques Charged particle scattering Biological trace analysis Preconcentration tech.
Annotated bibl. (13 P) Extensive annotated bibl. (295 P) (820 R ) Rev. 1108 R ) Rev. (124 R ) Detailed, some previously unpub. info. 128 P) Rev. includes med. and dentistry (1027 R ) Rev. of meth. (9 P)
Methods and Techniques
1106‘ 1130) 1138) 115) (55)
161) (1051
a F = No. of Figures. P = No. of Pages.
R
= No.
of References.
go on and on, but the point need not be belabored; in the new scheme of things, there is an important role for the nucleonics expert.
R.; DIOCHEMICAL ANALYSIS Analytical Procedures Utilizing Radioisotopes. It would be difficult to identify one or two areas of unusual activity in the application of radioisotopes to analytical procedures. The old stand-by techniques of isotope dilution and exchange, radiometric titrations, radiation absorption and scattering, substoichiometry, elc. are all astir but show little innovative vitality; the main thrust of work in these areas appears to be problem-oriented. However, this is not all bad. For years, radiochemists have extolled the virtues of tracer techniques for a wide variety of analytical problems. Unfortunately, these methods were all but ignored by the general analytical community (save for the biomedical investigators who were more or less forced to use them). This was caused, perhaps, by real or imagined problems of safety or the feeling that isotope teck.niques were too “exotic” for the analytical development laboratory. But, like Kekule’s snake, the head swallows the tail, and it now appears that tracer methodology 432R
has been re-discovered as practice catches up with principle. Mundane problems continue to harass the radioisotope user: losses of radioactivity from solution, or of the solution itself from sealed vials have been studied (127), and errors in the labeling of commercial radionuclides still occur (134). Measurement Techniques. On the basis of published surveys, 14C and 3H are the most extensively used radioisotopes in analytical assay procedures. Thus, continued vigorous activity in the field of liquid scintillation counting technology is both expected and evident. The proceedings of two international conferences have appeared recently and a third is due before the publication of this review. As an over-view, we would say that the field has matured to a state of refinement rather than conceptual development. A great deal of effort is being expended on pushing the technique to lower and lower detection levels for dating and environmental applications. The ever-present problems of standardization, quench correction, and sample preparation continue to be attacked, but only incremental progress has been observed. No substantially improved scintillator fluors or solvents have been introduced during the report period and the performance level
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W. S. Lyon is Head of the Nuclear and Physics Methods Group of the Analytical ,Chemistry Division, Oak Ridge National Laboratory. He has been associated with the nuclear energy field since 1944 and has been at ORNL since 1947. He is a graduate of the University of Virginia and has done graduate work at the University of Tennessee in both chemistry and industrial management, receiving a master’s degree in the latter in 1968. His main interests have been in nuclear measurements, decay scheme studies, and activation analysis. He has published a l m x t 70 papers on these subjects. He is the Editor of “Guide to Activation Analysis” (Van Nostrand, 1964), an associate editor of Radiochemical and Radioana/ytica/ Letters and Regional Editor of the Journal of Radioanalytical Chemistry. He is actively pursuing standardization through committee work in the ASTM, USASI, NCRP, and the APHA. Enzo Ricci has been a Research Staff Member in the Nuclear and Physics Methods Group of the Analyticai Chemistry Division, Oak Ridge National Laboratory, since 1962. Licensee in Chemical Sciences (1952), Ph.D., Chemistry (1954), University of Buenos Aires, Argentina (where he was born); also, M.S.. Physics (1971), University of Tennessee. He has developed methods and facilities for activation analysis by thermal-, fast-. and neutrons as well as charged particles and photons. He has been an IAEA fellow at Atomic Energy of Canada Ltd., Chalk River, 1959-61, Group Leader of the Argentinian AEC Activation Analysis Laboratory, and Professor of Radioisotope Applications, University of Buenos Aires, 1961-62. Author of over thirty journal articles, three book chapters, and one U.S. patent. He has been the Chairman of the Committee on Analytical Applications of Isotopes and Radiation of the American Nuclear Society since 1972, and is also a member of the American Chemical Society and of the Sigma Xi.
of commercial counting instrumentation appears to have plateaued. Use of Ge(Li) detectors continues to increase; analytical applications of Ge spectroscopy require both energy and efficiency calibration. A number of radionuclides have had their principal y-ray energies measured (41), and several careful efficiency calibrations have been documented (12, 48). Some uncertainties still exist in the shape of the efficiency us. energy curve a t both the high and low end (39). The best compilation of information concerning Ge spectroscopy, associated electronics, and similar data continues to be the IEEE Transactions particularly those papers from the Scintillation and Semiconductor Counter Symposium (121). Polymer grafting (78) has recently been proposed as a method of detecting charged particles. Ionizing radiation induces the formation of a copolymer in a polymer chain, and this new graft polymer can be identified and measured. The technique appears to be potentially superior to that of particle track etching. Another interesting detector is a xenon liquid-filled multiwire proportional counter
(93.
In our odd- or unusual item category we include the findings of unexpected uranium isotope ratios in Gabon (Africa) that seem to indicate the occurrence of a chain nuclear reaction in the distant past (81, 87). The need for some careful nucleonics measurements is certainly indicated here.
NUCLEAR A N D ATOMIC ACTIVATION ANALYSIS In reporting three 1972 international meetings, one of us (63,though stressing the unique capability of neutron activation for sensitive multielement analysis, and the bright hopes of X-ray fluorescence, had to conclude: “Relative to four or five years ago, activation analysis appears not to have progressed in any marked degree. We are performing much the same analyses in much the same way. What innovations there are have come about through better detectors, better data handling, and more sophisticated equipment . . . . But it does not appear that we can
Harley H. Ross is Head of the Instrumentation and Advanced Methodology Group in the Analytical Chemistry Division, Oak Ridge National Laboratory. A native of Illinois, he received his B.S. degree in chemistry from the University of Illinois in Urbana. His graduate work was carried out at Wayne State University, Detroit, where he received his M.S. in 1958 and Ph.D. in analytical radiochemistry in 1960. I n June 1960, Dr. Ross joined the staff of the Special Training Division of the Oak Ridge institute of Nuclear Studies (now ORAU), where he was a lecturer in the Institute’s courses in the techniques of using radioisotopes. In 1962 he left the Institute to accept a position in the Nuclear Radiochemical Group at ORNL, which he held until 1972. Although Dr. Ross is no longer involved directly with the nucleonics activities of the Analytical Chemistry Division, he continues to maintain an interest and a research effort in both liquid scintillation spectroscopy and the application of radioisotopes to the solution of analytical problems. in 1967 he was given an iR-100 award for the development of the radioisotopic light source photometer.
hope for any great improvements now or in the immediate future . . . . (The above innovations) are really not advances and it is the lack of advances t h a t concerns many activation analysts.” Rather than a pessimistic forecast, this was meant to point out that except for the bright prospects of analytical X-ray fluorescence, one does not seem to envisage future exciting virgin avenues as in the past, when charged-particle, photon, and prompt activation analysis began. Indeed, efforts during this period have concentrat,ed on the “nitty-gritty” details, to crystalize specific applications in each of the broad branches. Thus, scarcity of avant garde papers contrasts with an enormous affluence of publications reporting specific techniques. Consequently, by keeping our early avowed policy of reporting only new advances, we find ourselves with little to discuss. We will still single out-in an admittedly arbitrary manner-the very few, most striking developments of this period, and will leave the long list of valuable, specific accomplishments to the many reviews and bibliographies mentioned in our tables. Many of these accomplishments were also reported a t activation analysis meetings-more numerous this time than ever. The International Conference on Modern Trends in Activation Analysis-the dean of them all-was held a t Saclay, in conjunction with the CNRS one week after the (GlasInternational Colloquium (63, gow) Second International Conference on Forensic Activation Analysis (67). Aside from the numerous specialized conferences listed in Table 111, applications of 252Cf were reported a t an American Nuclear Society meeting held a t the University of Texas (Austin, 1972). An outstanding exception to the settled trends of this period was the rapid progress in X-ray fluorescence analysis, which was only incipient a t the time of our last review. We will thus scan this development in detail. X-Ray Fluorescence. Important recent refinements in the manufacture of semiconductor detectors-particularly Si(Li)-revitalized this old technique. For many decades, physics-oriented analysts have measured X-ray excited X-ray fluorescence with wave-length dispersive detectors for elemental determinations, by slowly scanning the fluo-
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Table 111. Proceedings Radiochemical Analysis Location
Topic
Liq. scint. counting Liq. scint. counting Nuclear data Nuclear data Labeled compounds Radiochemistry Applications of X- and gamma-rays Training in the nucl. field Inner shell ionization phenomena Radioactivity in the environment Contaminants in food Radioactivity in nuclear spectroscopy X-Ray analysis Soils and plant relationships Dosimetry techniques Radioisotopes Topic
U. of Salford, Eng. 13 papers, some rev. 1140 P) 5 sections, wide range of topics (337 P) Brighton, Eng. 36 papers, with discuss. (294 P) Canterbury, Eng. IAEA conf. Paris Marianske-Lame, Czech. 2 Vol., 32 papers 38 papers (330 P) Mexico City 33 papers, some rev. (474 P) Boston Basic and adv. training of chemists and engiRome neers (239 P) X-Rays, theory and application, 4 vol. Atlanta IAEA, 76 papers (980 P) Nuremberg IAEA conf. Vienna Theory and exper., Vol. 1 (590 P ) ; Vol. 2 (929 Nashville P) Current development, 45 papers Denver Current development, 45 papers Vienna IAEA, agric., industr. and med. Vienna Sev. papers in English Tokyo
Location Nuclear and Atomic Activation Analysis
Geo-cosmo chemistry Life sciences Environmental analysis Charged particle anal. Lunar analysis Industrial measurement and control a
Comments"
Kjeller, Norway Bled, Yugoslavia Columbia, Mo. Namur, Belgium Houston, Texas Guildford, Eng.
Comments
More than 40 papers 49 papers (672 P) Includes papers on activation tech. Many meth. described Limited number of papers on activation Stresses radiation tech.
P = No. of Pages.
Table IV. Compilations, Tables, M a t h e m a t i c a l T r e a t m e n t s , a n d Aids for Radiochemical, Nuclear, and Atomic Activation, Analysis Ref.
Topic
Comment"
Absorption of X and y radiation Delayed neutrons from fission Resolution of @-emittingnuclides Isotope dilution anal. Double labeling Gamma-ray spectra Cross sections, Q values, sensitivities Gamma rays Low-energy gamma rays Gamma-energies Cross sections Range-energy relationships a
Anal. of binary syst. (MT) Data evaluation iC) Used in liq. scint. (MT) Statistical error (MT) Optimization of counting param. (A,MT) Comput. prog. iC) One tablelelement 189 P). iC,T) From nuclides prod. by photonuclear reactions. (T) From (n,?) reactions. (T) From reactor prod. isotopes. (C) For photoneutrons. I C ) For heavy ions 10-100 MeV 'nucleon (T)
C = Compilations. T = Tables. M T = Mathematical Treatments. A = Aids.
rescence spectrum. The advent of high-resolution semiconductor detectors made it possible to apply gammaspectrometry techniques-already well known to activation analysts-to the simultaneous counting of all X-rays in this spectrum, by what is now called energy dispersive detection. With this breakthrough in detection-enhanced by computer handling of high resolution, complex X-ray spectra-the question of atom excitation itself came under scrutiny. Heavy charged particles were tried and radioisotope sources were improved, to compete with the classical X-ray tube in this task. Protons of 150-400 KeV and of 1.7 MeV were used to probe stainless steel alloy composition (80) and for multielement analysis of aerosol filters ( 5 ) , respectively, while sensitivities for excitation by 1-3 MeV protons (128) and by 16.5-80 MeV a-particles (30) were investigated with regard to different target backings. Even ions as heavy as oxygen (20 MeV) were used successfully to trace lanthanum on the surface of NaCl crystals (107). Excellent sensitivies-3-30 ng/m3 of aerosol contaminants in air-were also reported for radioisotope exciters 434R
(7). Thus, a need developed to establish experimentally which excitation method was the best. This task was taken up quite responsibly and thoroughly by three laboratories in this country (16, 36, 89) while X-ray fluorescence was put in perspective relative to other analytical methods in a survey abroad (52). The conclusions of the comparison, as is usual in analytical chemistry, did not favor one particular excitation technique, but rather pointed out which technique was best for an individual analysis. One must be impressed, however, by the reliability, the low cost and easy maintenance of the X-ray tube-in combination with Si(Li) detection and computer spectrum handling-us. the tedious manufacture, radiation hazard, and decay of the radioactive exciter, or the large investment and demanding maintenance attached to a nuclear particle accelerator. X-Ray excited X-ray fluorescence has been the subject of study a t two national laboratories; LBL has completed an impressive package for trace element determination, particularly in air particulate filters, biological and geological specimens (34), while ORNL devised an original
A N A L Y T I C A L C H E M I S T R Y , VOL. 46, NO. 5, A P R I L 1974
monochromator, that improves analytical sensitivity by reducing the "white" X-radiation originating in the tube (117). Finally, it is perhaps ironic that-after developing the gamma-spectrometry methods that are presently so useful to X-ray workers-activation analysts are only now themselves beginning to recognize the usefulness of X-ray spectrometry in their own field ( 70,76). Other Methods. Because of their striking sensitivity, particular novelty, or opportune development, a few applications are especially noteworthy. For example, a proton-activation method capable of determining nitrogen in water at the 10-6 ppm level (2), and one that determines oxygen in melted sodium (104), thus eliminating target cooling problems by,, following the adage-"If you can't lick 'em, join 'em! A good theoretical treatment for charged-particle prompt reaction analysis (nuclear microprobe) was developed in a thesis ( I 4 ) , and this technique was used to study the still annoying problem of surface interference on charged-particle activation analysis (98). In the always-growing field of photon activation analysis, authors reported, for the first time, sensitivities for bremsstrahlung energies as high as 7 2 MeV (50) and 110 MeV (102). Finally, an array of these newer techniques, involving X- and y-rays as well as a-particles, was used aboard Apollo 15 for analysis of lunar materials, and for remote orbital measurement of lunar radiation ( I ) . The extensive use of 14-MeV neutron generators has, a t last, stirred several studies of systematic irradiation errors in this method (60, 85, 229, 131); these are very belated but, nonetheless, quite welcome. Multielement Analysis. Neutron activation analysis
LITERATURE CITED (1) Adler, I . . Trombka, J. I., Gorenstein, P , Anal. Chem., 44 ( 3 ) , 28A (1972). (2) Bankert. S. F.. Bloom. S. D.. Dietrich. F . S . , Nature (London). 242, 270 (1973). (3) Belcher. E. H., Vetter, H . , Ed., "Radioisotopes in Medical Diagnosis," AppletonCentury-Crofts, New York, N.Y.. 1971 (4) Berman. B. L., "Atlas of Photoneutron Cross Sections Obtained with Mono-energetic Photons." UCRL-74,622, University of California, Livermore, Calif., 1973. (5) Bodart, F., Deconninck, G., Hontoy. J.. Wilk. S.. Radiochem. Radioanal. Lett.. 13, 161 (1973). (6) Boltan, N . E., Van Hook, R. I., Fulkerson, W.. Lyon. W. S . . Andren, A W.. Carter, J. A.. Emery, J. F.. "Trace Element Measurements at the Coal-Fired Allen Steam Plant." ORNL-NSF-EP-43, Oak Ridge National Laboratory, Oak Ridge, Tenn., 1973. (7) Bonnet. N. A.. Bazan. F., Camp, D. C., "Elemental Analysis of Air Filter Samples Using X-Ray Fluorescence." UCRL-51388, University of California, Livermore. Calif.. 1973. (8) Brunfelt. A. 0.. Steinnes. E . Ed.. "Activation Analysis in Geochemistry and Cosmochemistry," Proceedings of a Conference Held at Kjeller. Norway. September 7-12, 1970. Universitetsforlaget, Oslo, Norway, 1971. (9) Bunshah. R. E.. Ed.. "Modern Analytical Techniques for Metals and Alloys. Pt. 2." John Wiley and Sons, New York, N.Y., 1970. (10) Cameron, J. F., Meas. Contr., 4, 303 (1971). (11) Cameron. J. F.. Clayton, C. G., "Radioisotope Instruments. Pt. 1 , " Pergamon Press, Oxford, 1971. (12) Campbell, J. L..McNelles. L. A , , Nucl. l n strum. Methods, 98, 433 (1972). (13) "Chemical Nuclear Data: Measurements and Applications." Institution of Civil Engineers, London, 1971 (14) Chemin. J. F.. Roturier. J.. Saboya, B , Petit. G. Y.. Nucl. Insfrum. Methods, 97, 211 (1971). (15) Chu. W. K., Mayer. J. W., Nicolet. M. A,, Buck, T. M., Amsel. G.. Eisen, F., Thin Solid films. 17, 1 (1973) (16) Cooper. J. A . Nucl. Instrum. Methods, 106, 525 (1973). (17) Crook. M. A.. Johnson, P., Scales. B.. Ed..
(18) (19) (20) (21) (22) (23) (241 i
,
(25) (26) (27) (28)
(29)
(30) (31) (32) (33) (34) (35) (36) (37) (38)
faces stiff competition from other methods-such as spark source mass spectrometry and atomic absorption-in the realm of sensitivity. But it still presides over multielement analysis (67), thanks to the Ge(Li) detector, the small computer, and, particularly, the gre& efforts devoted during this period to cost reduction. The main drive has been in the direction of cutting analytical time by automatizing (28, 108, 109, 123) or-more often-eliminating chemical separations altogether, and by simplifying the use of standards. Though the multistandard technique was used (19), nondestructive, reliable methods were also developed, based on only three (22, 64) or even one single (65, 86) comparator. The latter is, in fact, a flux monitor, and the method is called absolute, because it uses first principles-ie., the activation equation-in the calculations. The absolute method-long rejected by activation analysts-appears now more palatable, in view of the more sophisticated counting/computing equipment and the more reliable nuclear data (Table IV) currently available. In this regard, an opportune survey on data needs in activation analysis was conducted (79). And the important effort of the National Bureau of Standards (59) to provide activation analysis standard reference materials (orchard leaves, bovine liver, coal, etc.) has been quite timely and deserves praise. Finally, a glance into the future predicts extensive application of multielement activation analysis in research aimed a t attenuating the "energy crisis," while protecting our environment. This and other analytical methods have already been used to study the balance of trace elements throughout a coal-fired power plant (6).
"Liquid Scintillation Counting," Vol. 2, Heyden &Son Ltd., London, 1972. Dams, R . , Adams, F., J. Radioanal. Chem., 7, 127 (1971). Dams, R.. Rahn, K. A,, Winchester, J. W , Environ. Sci. Technol., 6, 441 (1972). Davies. P. T., Deterding, J. H., Int. J. Appl. Radiat. Isotop., 23, 293 (1972). De Bruin. M., Korthoven, P. J. M , J. Radioanal. Chem., 10, 125 (1972). De Corte, F., Speecke, A,. Hoste. J.. ibid., 3, 205 (1969). De Soete, D . , Gijbeis. R., Hoste. J . , "Neutron Activation Analysis." John Wiley and Sons. NewYork. N.Y.. 1972. "Dosimetrv Techniaues Aoolied to Aariculture, Industry, Biology, and Medicine," International Atomic Energy Agency, Vienna, Austria, 1972. Dyer, A,. Ed., "Liquid Scintillation Counting," Vol. 1, Heyden & Son Ltd.. London, 1971. Dyer, F. F., Bate, L. C., "DecaygarnRadioactive Decay Gamma-Ray Spectra Compilation," ORNL DLC-19, 1972 Eichholz, G. G.. Ed.. "Radioisotope Engineering," Marcel Dekker, New York, N.Y , 1972. Elek. A,, "Use and Automation of Multielement Substoichiometric Extraction of Metal Chelates in Activation Anaiysis" (CONF-721010-69), National Technical Information Service, Springfield, Va.. 1972. Faires, R. A,, Parks, B. H.. "Radioisotope Laboratory Techniques," John Wiley and Sons, NewYork, N.Y.. 1973. Flocchini, R. G., Feeney, P. J., Sommerville, R. J., Cahill. F. A,, Nucl. Insfrum. Methods, 100, 397 (1972). Friedt. J. M . , Danon. J.. Radiochim. Acta, 17, 173 (1972). Galatanu, V., Grecescu, M.. J. Radioanal. Chem., 10, 315 (1972). Gerrard. M., Isotop. Radiat. Technol., 8, 395 (1971). Giauque. R. D . , Goulding, F. S., Jaklevic, J. M.. Pehl, R. H . . Anal. Chem., 45, 671 (1973). Gibson. J. A. B., Lally. A. E.. Analyst (London), 96,681 (1971). Gilfrich. J. V . . Burkhalter, P. G. Birks. L . S . . Anal. Chem., 45, 2002 (1973). Guinn. V. P.. Isotop. Radiat. Techno/., 9, 379 (1972). Hamilton, J. H , Manthuruthil. J. C., Ed., "Radioactivity in Nuclear Spectroscopy."
(39) (40)
(41) (42)
(43) (44) (45)
(46)
(47) (48) (49) (50) (51)
(52) (53) (54)
(55) (56)
(57) (58)
Vol. I & Vol. I I , Gordon and Breach Science Publishers, New York. N.Y., 1972. Hansen. J. S . . McGeorge, J. C., Nix, D., Nucl. Instrum. Methods, 106, 365 (1973). Heinrich, K. F. J . , Barrett. C. S., Newkirk. J. B . , Ruud, C. O., Ed., "Advances in X-Ray Analysis." Vol. 15, Plenum Publishing Corp.. New York, N.Y., 1972. Helmer. R. G., Greenwood, R. C., Gehrke, R. J., Nucl. Instrum. Methods, 96, 173 (1971). Hoste. J., Op De Beeck, J., Gijgels, R . , Adams. F., Van Den Winkel. P.. De Soete, D., "Activation Analysis," Chemical Rubber Company, Cleveland, Ohio, 1971 Huertes, V. A , Energ. Nucl. (Madrid), 7, 494 (1970). "Industrial Measurement and Control by Radiation Techniques." Institution of Electrical Engineers, London, 1972. "International Meeting on Chemical Analysis by Charged Particle Bombardment," Namur, Belgium, 1971: Radioanal. Chem.. 12, No. 1 (1972). "Isotope and Radiation in Soil Plant Relationships Including Forestry Proceedings." International Atomic Energy Agency, Vienna, Austria, 1972. Jaffee, M . , Ford, L.. J. Ass. Offic. Ana/. Chem.. 54.879 119711. Jardine.~L.'J.. hiucl. Instrum. Methods, 96, 259 (1971). Kane, P. F., Larrabee, G. B . , Annu. Rev. Mater. Sci.. 2, 33 (1972). Kato, T.. Oka, Y.. Talanta, 19, 515 (1972). Kenna, B. T.. Harrison. P. E., "Neutron Activation Analysis: Tabulation of Cross Sections, Q-Values. Decay Characteristics and Sensitivities." SLA-73-637, Sandia Labs.. Albuquerque. N.M.. 1973. Khol, F.. Radioisofopy, 13, 1085 (1972). Kneip. T. J . , Laurer. G. R.. Ana/. Chem., 44 (14), 57A (1972). Kolthoff, I . M . . Elving, P. J.. Ed., "Treatise on Analytical Chemistry. Part I . Theory and Practice. Vol. 9." John Wiley and Sons, NewYork, N.Y. 1971. Krivan. V , Fresenius' Z. Anal. Chern., 262, 1 (1972). Krugers, J . , Ed., "Instrumentation in Applied Nuclear Chemistry." Plenum Press, NewYork, N.Y., 1973. Kubicek, P.. Mrazek, L., lsotopenpraxis, 8, 343 (1972). Kyrs, M , Kandiyoti, R., Vrana, T . . J. Ra-
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dioanal. Chem., 12, 505 (1972); Kyrs, M., Vrana, T., ibid., 10, 105 (1972). (59) LaFleur, P. D., "Biological Matrix Standard Reference Materials for Trace Element Determinations," CONF-721069-9, 1972. (60) Leal Horta, J. A., Dos Santos, A. N., Anal. Chim. Acta, 63, 359 ( 1 973). (61) Leddicotte, G. W., Methods Biochem. Anal., 19, 345 (1971). (62) Lenihan, J. M. A., Thomson, S. J . , Guinn, V. P., "Advances in Activation Analysis," Vol. II, Academic Press, London, 1972. (63) Lieser, K. H.. Radiochim. Acta, 18, 115 (1972). (64) Linden, R. V. D. Corte, F. D., Hoste, J.. J . Radioanal. Chem., 13, 169 (1973). (65) Linekin, D. M . , Int. J. Appl. Radiat. /sotop., 24, 343 (1973). (66) Lutz, G. J., Boreni, R. J., Maddoxk, R. S., Wing, J.. Ed., "Activation Analysis: A Bibliography Through 1971 ," NBS-TN-467, National Bureau of Standards, Washington, D.C.. 1972 (67) Lyon, W. S . , Anal. Chem., 45 ( 4 ) , 386A 119731 -.-, (68) Lyon. W. S., in "Proceedings of the Interagency Conference on the Environment, October 17-19, 1972, Livermore, California," CONF-72-1002. U S Department of Commerce, Springfield, Va. (69) Maddock, A. G., Ed , "Radiochemistry," Vol. 8 . Butterworths, London, 1972. (70) Mantel, M . , Amiel S . , Anal. Chem., 44, 548 (1972). (71) Mar'yanov. E. M., "Radiometricheskoe Titrovanie," Atomizdat, Moscow, 1971. (72) Maziere, E.. Prod. Probi. Pharm., 27, 20 (1972). (73) McKay. H. A. C., "Principles of Radiochemistry," Butterworths, London, 1971 (74) "Measurement of Low-Levei Radioactivity." ICRU-22 Washington, D.C.. 1972. (75) Meinke, W. W.. Pure Appl. Chem., 34, 93 (1973). (76) Meinke, H., Leszczynski, C.. Weber, M.. Radiochem. Radioanal. Lett., 14, 21 7 (1973). (77) Mitchell, J. W., Anal. Chem., 45 ( 6 ) , 492A (19731, (78) Monn(n. M. M . , Blanford, G. E., Jr., Science, 161, 743 (1973). (79) Munzel, H.. Michaelis, W., "Survey of the Nuclear Data Needs in Activation Analysis," German Rept. KFK 1612, 1973. (80) Musket, R. G., Bauer, W., Appi. Phys. Lett., 20, 41 1 (1972) (81) Neuiily, M.. Bussac. J., Vendryes. G., Compt. Rend., Ser. D , 275, 1847 (1972). (82) Newton, G. W. A,. Gilmore, G. R.. Hemingway, J. D.. "Radiochemistry," Vol. i , Chemical Society, London, 1972. (83) Nicoiet. M.-A., Mayer. J. W., Mitchell, I . V..Science, 177,841 (1972). (84) "Nuclear Activation Techniques in the Life Science. 1972," International Atomic Energy Agency, Vienna, Austria, 1972. (85) Oblozinsky, P., Ribansky, I . , Radiochem. Radioanal. Lett., 7, 139 (1971). (86) Okada. M., Tamura. N . , "Nondestructive Neutron Activation Analysis for the Determination of Many Elements in a Sample with a Mono-Element Standard." JAERIM-4900, Tokyo, Japan, 1972. (87) "Oklo (Gabon) Fossil Reactor," Energ. Nucl. (Paris), 14, 376 (1972). (88) Perlman. I., Asaro, F.. Michel, H. V., Annu. Rev. Nuci. Sci., 22, 383 (1972) (89) Perry, S. K.. Brady, F. P.. Nucl. Instrum. Methods. 106, 389 (1973). (90) Pickering, W. F., "Modern Analytical Chemistry." Marcel Dekker, New York, N.Y.. 1971 (91) Pierce, T. E.. Selec. Annu. Rev. Anal. Sci., 1, 133 (1971). (92) Piesch, E., GIT (Glas-lnstrum.-Tech.) Fachz. Lab., 16,810 (1972) (93) "Preparation and Trainina of ExDerts in the Nuclear Field. ProceedTngs of the 15th I
436R
Nuclear Congress of Rome, March 12-13, 1970," Comitato Nazionale Energia Nuclear, Rome, Italy, 1971 (CONF-700344). (94) "Proceedings of the International Conference on Inner Shell Ionization Phenomena and Future Applications," Atlanta, Ga.. April 17. 1972 (CONF-720404). (95) "Proceedings of the Japanese Conference on Radioisotopes, No. 10," Tokyo, Japan, November 16, 1971. (96) "Proceedings of the 6th Radiochemical Conference on the Methods of Preparation, Storage, and Control of Labeled Compounds, Marianske Lazne, Czechoslovakia, May 3-8, 1971; Part 1 , Radioisotopy, 12, 491 (1971); Part 2, Radioisotopy, 12,699 (1971). (97) Prunier, J., Ailemand, R . , Laval, M.. Thomas, G., Nucl. instrum. Methods, 109, 257 (1973). (98) Quaglia, L., Weber, G., "Surface Analysis Using Nuclear Reactions to Evaluate the Surface Bulk Material Interference." CONF-721069-34, 1972. (99) Quittner. P., "Gamma-Ray Spectroscopy with Particular Reference to Detector and Computer Evaluation Techniques." Adam Hilger Ltd., London, 1972. (100) "Radiotracer Studies of Chemical Residues in Food and Agriculture." International Atomic Energy Agency, Vienna, Austria, 1972. (101) "Rapid Methods for Measuring Radioactivity in the Environment," International Atomic Energy Agency, Vienna, Austria, 1971. (102) Ricci, E., Trans. Amer. Nucl. SOC., 17. 87 (1973). (103) Richard-Serre, C., "Loss of Energy Per Unit And Range for Heavy Ions-of 10 MeV/Nucleon to 1000 MeV/Nucleon," CERN-72-19, November 1972, Geneva, Switzerland. 104) Roche, M. F.. Ross. L. E., Meyer. R. J . , Trans. Amer. Nuci. SOC..14.617 (19711. 105) Rottschafer, J. M. Boczkowski, R. J , Mark, H. E., Jr., Talanta, 19, 163 (1972). 106) Salazar, E. S.. Vasilik, D. G., "Annotated Bibliography of 252CF,"RFP-1683, National Technical information Service, Springfield, Va., 1972. 107) Saltmarsh. M. J., van der Woude. A,, Ludemarin. C. A.. Appl. Phys. Lett., 21, 64 (1972). 108) Samsahi, K., "Accuracy and Precision Studies of a Radiochemical Multielement Method for Activation Analysis in the Field of Life Sciences." AE-458, National Technical Information Service, Sprinafieid, Va., . 1972. (109) Samsahl. K.. Webster, P. O., Biomqvist, G , "Radiochemical Machine for the Analysis of Cd, Cr. Cu. Mo, and Zn," AE-469, National Technical Information Service, Springfield, Va.. 1973. (110) Sastri, M. N., Ed., "Vistas in Analytical Chemistry," S. Chand and Co. (P) Ltd , New Delhi, India. 1971. (111) Schuman, R. P., "Radiochemistry of Manganese." NAS-NS-3018(Rev.), National Technical Information Service, Springfield. Va., 1971. (112) Seaborg. G. T.. "Nuclear Miiestones," W. H. Freeman and Comoanv. ,~San Francisco. Calif., 1972 ( 1 13) "Second Inter-American Conference on Radiochemistry," Mexico City, Mexico, April 22-25, 1968. Organization de 10s Estados Americanos, Washington. D.C , 1971. (114) Simpson, H.. Rep. Progr. Appl. Chem., 55, 673 (1971). (115) Snipes, M. E . , Lengemann, F. W., lnt. J . Appl. Radiat. Isotop., 22. 513 (1971) ( 1 16) "Source Material for Radiochemistry," NP-19564, National Academy of Sciences, Washington, D.C., 1971 (117) Sparks, C. J.. Jr., Harris, L. A,, "Develop-
A N A L Y T I C A L CHEMISTRY, V O L . 46, NO. 5 , A P R I L 1974
,
I
I
ment of High Sensitivity X-Ray Fluorescence for Analysis of Toxic Heavy Elements," CONF-721134-1, h ational Technical Information Service, Springfield, Va., 1972. 118) Stevens, J. G., Travis, J. C., DeVoe, J. R.. Anal. Chem., 44,384R (1972). 119) Stringham, W. S., Comp. "Carbon-13: A Selected Abstract Bibliography," MLM1913, National Technical Information Service, Springfield, Va., 1972. (120) Stuber, C. E., "Transplutonium Elements," TID-3317(Suppl. 3), National Technical Information Service, Springfield, Va., 1972. (121) "13th Scintillation and Semiconductor Counter Symposium." Washington, D.C., 1972, / € € E , Trans. Nod. Sci.; NS-19, No. 3 (1972). (122) "Nuclear Data in Science and Technology, VOls. I , 11," International Atomic Energy Agency, Vienna, Austria, 1973. (123) Tjoe, P. S., de Goeij. J. J. M., Houtman, J. P. W., "Automated Chemical Separations in Routine Activation Analysis," CONF-721010-68, National Technical Information Service, Springfield, Va., 1972. (124) Toelgyessy, J., Braun, T., Kyrs, M., "Isotope Dilution Analysis," Pergamon Press, Oxford, 1972. (125) Toelgyessy, J., Varga, S.. Krivan, V.. "Nuclear Analytical Chemistry. l . introduction to Nuclear Analytical Chemistry." University Park Press, Baltimore, Md., 1971 (126) Tomlinson, L., "Delayed Neutrons From Fission: A Compilation and Evaluation of Experimental Data," AERE-R-6993, National Technical Information Service, Springfield, Va., 1972. (127) Tuck, A. G., McNair, A,. lnt. J. Appl. Radiat. Isotop., 23, 395 (1972). (128) Umbarger, C. J., Bearse. R. C., Close, D . A . , Malanify J. J., "Sensitivity and Detectability Limits for Elemental Anaiysis by Proton-Induced X-Ray Fluorescence with a 3 MV Van de Graaff." LA-DC-72-1069. -- -National Technical Information Service, Springfield, Va.. 1972 (129) Vandecastaele, C., Van Grieken, R., Gijbels, R.. Speeke. A,. Anal. Chim. Acta, 34, 187 (1973). (130) Van Grieken, R., Hoste, J . , "Annotated Bibliography on 14-MeV Neutron Activation Analysis," EURISOTOP-65, National Technical Information Service, Springfield, Va.. 1972. (131) Van Grieken, R.. Speecks. A,, Hoste, J . , J. Radioanal. Chem., 16, 225 (1973). (132) Venverloo, L. A. J., "Practical Measuring Techniques for B Radiation." Macmillan. London, 1971. (133) Vogt. J. R., Ed., "Nuclear Methods in Environmental Research," University of Missouri, Columbia, Mo.. 1971 (134) Von Korff, R . W.. Nature (London), 238, 347 (1972). (135) Watkins. C., Ed., "Third Lunar Science Conference, Houston, 10-13 January 1972." (Proceedings), Lunar Science Institute, Houston, Texas. (136) Weissberger. A,, Ed.. "Physical Methods of Chemistry, Pt. IIID," John Wiley and Sons, New York, N.Y., 1972. (137) Wolf, A. P.. Christman, D. R., Fowler, J. S., Lambrecht, R. M., "Synthesis of Radiopharmaceuticals and Labeled Compounds Utilizing Short-Lived Isotopes," BNL-17682; CONF-730309-7, National Technical Information Service, Springfield, Va.. 1972. 138) Wolicki, E. A,, "Nuclear and Ion Beam Techniques for Surface and Near-Surface Analysis." NRL-7477, 1972. 139) Ziegler. C. A,, Ed., "Applications of Low Energy X- and Gamma Rays," Gordon and Breach, Science Publishers, New York. N.Y., 1971. 140) Zmijewska. W.. Chem. Anal. (Warsaw). 17, 179 (1972).
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