Fisher, R. A,, Brodale, G. E., J . Chem. Phys. 37, 2952 (1962). (19D) Hellwege, K. H., Schembs, W., Schneider, B., 2. Physik. 167, 477-86 (1962). (20D) Hutchison, C. A,, Tsang, T., Weinstock, B., J . Chem. Phys. 37, 555 (1962). (21D) Hyman, H. H., “Noble Gas Compounds,” The Vniversity of Chicago Press, Chicago (1963). f22D) Johannesen. R. B.. Candela, G. A., ‘ Inorg. Chem. 2, 67 (1.963). (23D) Kachi, S., Tabitda, T., Goto, Y., Kogyo Kagabu Zasshi 65, 1753 (1963). (24D) Knox, K., Gineberg, A . P., Inorg. Chem. I , 945 (1962). (25D) Leask, M. J. M , Roberts, L. E . J., Walter, A. J., Wolf, W. P., J . Chem. SOC.4788 (1963). (26D) Legrold, S., :Rare Earth Res. Seminar, Lake Arrowhead, Calif., 142 (1960). (27D) Locher, P. R., Gorter, C. J., Physica 28, 797 (19fi2). (28D) Maginn, R. E., Manustyrskyj, S., Dubeck. M.. J . Am. Chem. SOC.85, 672 (1963). ’ (29D) Sheppard, J. C., Wheelweight, E. J., J . Phys. Chem. 67, 1568 (1963). (30D) Slivnik, J., Brcic, B., I‘olavsek, B.. Smale. S.. Frlec. B., Zeml.iic, S., Anzur, A:, Veksli, ‘Z., Croat. Chem. Acta 34, 187 (1962). (31D) Stevenson, R., Can. J . Phys. 40, 1385 (1962). l32D) Trzebiatowska. B. Jezowska-, ‘ Wojciechowski, W.; Bull. Acad. Polon. Sci., Ser. Sci. Chim. 9, 685-791, 693-8, 699-704 (1961). (33D) Trzebiatowski, W.,and Suki, W., Bull. Acad. Polon. Sci., Ser. Sci. Chim. 10, 399 (1962): Trzebiatowski, W., Troc, R., LecrejewicG, J., Ibid., p. 395. (34D) White, J. A., Williams, H. J.,
Sherwood, R. C., Phys. Rev. 128, 581 (1900). 135D) Woodhead. J. L.. Fletcher. J. M.. ‘ AL’Energy Res.’ Esta6. (Gt. Brii.) Rept: R 4295, (1962). (36D) Zanowick, R. L., Dissertation Abstr. 23, 857 (1962). (37D) Zelentsov. V. V.. Dokladv Akad. S S S R i39, iiio-ii (1961). ~
Applications
(1E) Ackerman, E., Brill, A. S., Biophys. Acta. 56 (3), 397 (1962). (2E) Bliumenfeld, L. A., Benderskii, V. A., Biofizika (Trans. English) 6, 4 (1961). (3E) Bottei, R . S., Laubengayer, A. W., J . Phys. Chem. 66, 1448 (1962). (4E) Burgess, J. H., Rhodes, R. S., Mandel, M., Edelstein, A. S., J . Appl. Phys. 33, Suppl. 3, 1352 (1962). (5E) Chernyakovskii, F. P., Machtina, K. A , , Musabekor, Yu. J., Zh. Fiz. Khim. 36, 865 (1962). (6E) Duffy, W., J . Chem. Phys. 36, 490 (1962). (7E) Ehrenberg, A , , Anders, A., Yonetani, T., Acta Chem. Scand. 15 (5), 1071-81 (1961). (8E) Felgentreu, I., paper in “Structure and Biological Function of Proteins,” p. 77-9, H . Kirsch, ed., Gustav Fischer, Jena, Germany, 1962. (9E) Francois, H., Bull. SOC. Chim. France, 506-19 (1962). llOE) French, C. M., Pritchard, R., Arch. Biochem. Biophys. 93 (3), 598 (1961). 1E) Haberditzl, W., Havermann, R., Gelgentren, I., Z. Phys. Chem. (Leipzig) 218, 354 (1961). 2E) Havemann, R., Haberditzl, W., Mader, K. H., Ibid., p. 71 (1962).
(13E) Havemann, R., Haberditzl, W., Rabe, G., Ibid., p. 417 (1961). (14E) Hazama. Y.. Hazama. K.. Ehren‘ berg, L., Radliatibn Bot. 3 (1) 7 (1963). (15E) Heit, M. L., Ryan, D. E., Anal. Chim. dcta 29, 524 (1963). (16E) Karimor, Yu. S., Schchegoler, I. F., Dokl. Akad. Nauk SSSR 146, 1370 (1962)
(17E) Lelgrand, D. G., J . Poly Sci. 60, S71 (1962). (18E) Lumry, R., Solbakken, A., Sullivan, J.. Rverson, L. H., J . Am. Chem. Soc. 84, la2 (1962). ’ f19E) Malmstrom. B. G.. Broman. L.. ‘ Mosbach, R., fihrenberg, A., Anders; A,, J . M o l . RioE. 5 (4), 450 (1962). (20E) Mayr, G., Rabboti, G. C., Experientia 13,252 (1957). (21E) Mulay, L. N., Fox, M. E., J . Am. Chem. SOC.84. 1308 (1962). and J . Chem. Phys. 38; 760 (1963). (22E) Okumura, K., J . Phys. SOC.Japan 18, 69 (1963). (23E) Pacault, P., Poquet, E., Compt. Rend. 255, 2106 (1962). (24E) Sager, W. F., Fatiadi, A,, Parks, P. C.. White. D. G.. Perros. T. P..’ J . Inorg. Nucl. Chem. 25, 187 (1963). (25E) Senftle, F . E., Thorpe, A. N., I S A Transactions 2 (2), 117, (1963); Suture 190, 410 (1961). (26E) Somoilova, 0. P., Blyumenfeld, L. A , , Biofizika (Trans. English) 6 ( l ) , 14 (1961). (27E)‘Sriraman, S., Sabesan, R., Trans. Farad. SOC.58, 1080 (1962). (28E) Liu, Tung Rfing, Hua Hsueh Tung Pao, No. 7, 34. 1962 (29E) Wallman, J. C., Cunningham, B. B., Calvin, M., Sci. 113, 55 (1951). (30E) Ward, R. L., J . Chem. Phys. 38, 2558 (1963). (31E) Woernley, D. L., Arch. Biochem. Biophys., 50, 199 (1954); Ibid., 54, 378 (1955).
Nucleonics G. W . leddicotte, Nuclear Division, Union Carbide Co., Tuxedo, N. Y
A
is presented of the fundamental developments in nuclear methods of analysis for the period from late 1961 to late 1963. It continues to be a rapidly expanding field and the wide diversity in publication media and in the number of analysts reporting results has brought about a marked increme in the number of papers (over 1760) contained in this review. Thus, it has been difficult to attain as complete ccverage as in the prior review (920). A1 though no serious attempt has been made to curtail a n y area of contribution, some omissions will be evident. Minimal coverage has been given to the reports on nuclear data, instrumentation, and general items such as report5 on conferences. The major portion of this review is concerned with applications of radioisotopes as tracers. Sections on activation analysis, isotope dilution and radiometric methods, separation procedures, and the use of radioisotopes as sources and as tracers in developing analytical GENERAL RE VIE^
methods are presented. I n addition, significant information about investigations in age determinations, radiochemistry measurement, and the use of computer-integrated programs to reduce data from such measurements to a n accurate and reliable form is given. The format of this review follows closely t h a t of the prior one (920). General references, survey papers, arid the like are given a t the beginning of each section. Specific references to radioisotope applications are cited either in the text in each section or in one of the tables. M a n y problems are being solved through the use of nucleonic methods. The ITS;\EC has emphasized their usefulness by providing periodic bibliographies on the use of radioisotopes in world industry (1653, 1654). Individual writers have provided excellent source books. Clark (309), in particular, has edited a major encyclopedia on many areas of radiation measurements and applications. Books by
Chase and Rabinowitz (276), Yesmelanov (1171), O’Kelley (1225), Taylor (1.596),Lindner (962), Overman ( l y l ) , and Peterson and Wymer (1272) give practical information on scientific investigations in such varied fields as instrumentation, radiochemistry, and autoradiography. Other books and articles give information on the production of radioisotopes by either nuclear reactors or charged-particle accelerators (78, 161, 600, 229, 270, 459, 61fi, 687, 843, 1056, 1059-1061, 1169, 1130, 1323, 1405, 1452, 1507, 1.545, 1609, 1635). Hara (616) and others (50, 64, 205, 397, 428, 579, 686, 740, 988, 989, 1025, 104.9, 1061, 1075, 1087, 1187, 1391, 1475, 1682, 1687) report on the applications of radioisotopes and nucleonic methods in such areas as exchange reactions and chemical reaction mechanisms in chemical analysis and technology, and in biology, agriculture, and indus-
try. Specific books by Slater (1528) and Dzhelepov and Peker (398) contain VOL. 36, NO. 5, APRIL 1964
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tabular lists of gamma rays emitted by radioactive nuclides. Other reports show gamma-ray spectra (1221) and the growth and decay patterns of many irradiated nuclides (140, 426). In the special field of age-determination of terrestrial and extraterrestrial materials, many excellent articles have appeared. The complete proceedings (688) of the 1962 Symposium on Radioactive Dating reflect the present status of radioactive dating. The scope of this technique has been broadened and ita use extended by several of the above papers. Olsson and Karlen (1229) discussed the problems they encountered in measuring the half life of CI4 by absolute measurement of 8-decaying gases. Oeschiger (1200) reviews the radioisotopes of interest in radioactive dating and discusses the types of lowlevel counting devices required for their measurement. H e also describes experiments involving the analysis of the residual background of low-level gas counters. Other authors have reviewed the general subject (155, 330, 685, 692, 958, 1118, 1119, 1138, 1280, 1338, 1339, 1447). Price and Walker (1319) have studied the age of minerals by measurement of the fission products formed in the irradiation of uranium. The age of iron meteorites and terrestrial molybdenites has been determined by measurement of the R e and Os content by neutron activation analysis (648). Other dating studies have been made on pitchblende (879), basalt lava (1428), uraninites (541), carbonate deposits (1605), sea water (155), natural waters (544, 1600), rocks, soils, ores, river and marine sediments (SSO), ferromanganese nodules (1181), the stratosphere (1138), meteorites (452), and distilled spirits (1320). These studies involve radiochemical and radiometric methods; gamma spectrometry and alpha- and beta-counting techniques have been used to complete the analyses. I n another special-interest area, nucleonic techniques using a pulsed beam of 14-m.e.v. neutrons as a n activation source are being studied as a means of determining the composition of the surface of the moon and other planets. Schrader et a1 (1465),Fite et al. (457), Lee and his associates (926),and Martina and Carlson (1024) report on their activities in this area.
RADIOACTIVITY MEASUREMENTS
Several books and review articles describe the general methods and equipment currently being used to detect and measure radiation (34, 44, 67, 68, 88,171,209, 214,440,4XZj528,552,560, 744, 760, 840, 857, 927, 932, 983, 9x5, 1083,1116,1197,1260,1277,1278,1301, 1310,1314,1358,1367,1378-1382,l4O8,
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ANALYTICAL CHEMISTRY
1 ~ 0 9 , 1 ~ 7 ~ , 1 5 1 9 , 1 5 ~ 3 , 1 5 8 3 , 11604, 599, 1686, 1690, 1703, 1718, 1732, 1735). Each of these sources discusses the properties of specific types of radiation detectors and gives examples of practical applications of these detectors, and the counting and measurement techniques used in radioactivity problems in research and in industry. Bruno (221, 222) reports on beta and gamma spectrometry techniques and Bastin-Scoffier (112) and Roach and Walker (1384) report on methods of alpha spectroscopy. Abson (3) surveys scintillation and gas ionization detectors. -4rmbruster and Specht (79) report on scintillation spectrometry uses. Berenyi and Biro (143) report on the technique of beta scintillation spectrometry. Other reports on scintillation counting techniques have been made (60, 681, 930, 933, 1134, 1236, 1248, 1245, 1587, 160X, 1690). Blonde1 (167) describes differential gaseous counting methods to measure the contamination of counter filling gases. Methods that can be used to determine the efficiency of and to calibrate a counter have been reviewed (1309, 1670). Standardization procedures, based 8-7 coincidence counting, for pure b e t s emitters by use of suitable i3-y emitting radionuclides ( S C ~Co60, ~ , BrS2, etc.) are reported (559). Other reports on radionuclide standardization and the storage of standard sources have been made (607, 645, 651 , 658, 674, 784, 898, 1089, 1149, 1169, 1451, 1601, 1760). Gold and aluminum absorbers have been used by Daddi and D ' h g e l o (346) to identify beta emitters. Artem'ev (83), Fleishman (460), and others (36, 460, 977) report on statistical processes in counting. Developments in counting equipment include a miniature counting tube that can be cooled (1314). Several studies have been made of the dead-time of a detector (93, 224, 493, 894). Cove11 (336) and Fite (455) use an automatic drift control device on a multichannel spectrometer. Reports on methods to increase the efficiency of scintillation counters have been made by Ankenbrandt and Lent (62, 63) and Anderson and Berlman (59). Graber (562) has been able to predict the resolving power of scintillation counters by studying the characteristics of the photomultiplier tube. Methods to eliminate self-absorption and self-scattering in S36(1705) in P3*, Ca45,C14 (945),and in thick-layer preparations of Y90,91Sr89,90, Cel41 Ce144, Pr144 (134) have been described. Bosch and Caracoche (182) use A1 and Be plates to reduce the backscatter effects of x-ray spectra recorded by a scintillation spectrometer. Techniques for sampling and preparing samples for counting have also
been described (125, 177, 191, 220, 494, 844,1045,1191,1268,l459,1495, 1509, 1511, 1541, 1626, 1639, 1645). Special equipment items-lead shields (401, 1246), scanhing devices for paper chromatograms (471, 1052,1121, 1122, 1275, 1276, 1288, 1392, 1461, I479, l717), measurement cells (1571), sample changers (327, 439)-have also been described. Descriptions have also been given of total absorption scintillation spectrometers (187, 1572), a portable 2 a flow counter for alpha and beta measurements (332), a G-M counter that uses mercury vapor (188),a portable transistorized G-M Counter (997), a bulk photoconductivity detector for gamma measurements ( $ l o ) , portable gamma spectrometers (411, 477), a large plastic scintillator (1044, 1332), a low-background, high-efficiency G-M counter (647), and a large-volume methane counter (1454). May and Hess (1040) and Pijck (1290) report on the background radioactivity to be found in radiation detection devices and equipment. Markichev (101.4) reports on the contributions of cosmic radiations to counter backgrounds. Solid-State Detectors. Many workers now find t h a t semiconductor detectors are superior to ionization chambers a n d scintillation counters in many spectroscopy analyses. This has resulted in a n increased use of such detectors. Many articles review the characteristics and performances of semiconductor detectors (224, 294, 412, 41 3, 475, 552, 600, 615, 689, 7r4, 802, 824, 870, 885, 998, 1030, 1109, 1140, 1182, 1333, 1426, 1565, 1526, 1594, 1595). Other authors have reported more specifically on the use of p-i-n type detectors (53, 715, 736, 824,1046, 1406, 1518, 1716), and lithium-drifted diodes in beta and gamma spectrometry (165, 305, 1708). Alpha and high energy particles also are being analyzed by the use of semiconductor devices (166,319,1435,1496). Fox and Borowski (476) report on the use of a guard ring for silicon surface barrier detectors in beta spectrometry. Inskeep (683) describes his work with 0.1 micron thick p-type silicon particle detectors. Bosch and his colleagues (183) also have used solid state detectors in the beta spectroscopy of %a7, Cs137, Aul98, and Pba3. Gold-silicon surface barrier detectors have been used in alpha spectroscopy (306). .A p-n junction silicon detector has been used as a Pu air monitor (1281). U2" and U235 have been determined simultaneously in liquid samples by use of semiconductor detectors (554). Liquid Scintillators. M a n y references have appeared on the use of liquid scintillation counters for beta radionuclides. Reviews of t h e principles of liquid scintillation counting
and the equipment utsed have been made by Ball (loo), BerlInan (147), Brooke and Schayes (206),I h m e r c et al. (391), Faissner (455, 436) Hellstroem (639), Horrocks (669), Jeffay and Alvarez (729), Klumpar and Majerova (822), Luedke (980), Rapkin (1346), Teshima ( 15Y6), To kunaga ( I 611) , Ueyanagi (f631), and Zutshi (1767). Studies on the efficiency of liquid scintillation counters have been made by Benson and Maute (137), Bush (238), Fodor (463), Giffin and hi:: colleagues (517), Kobayashi and Hayakawa (826), and Kohegyi et al. (837). Cs13' and Cd"' sources have been used as external sources to determine the efficiency of liquid scintillation counters (652, 903). Berlman (149) and his associates (148) explain the a- and ,$'-pulse shapes obtained in liquid scir;.tillation counting. Color quenching of the scintillators has also been studied (351, 357, 381, 1303, 1445, 1666). Many different liquid scintillator and solvent mixtures hrtve been used in liquid scintillation ccunters. These include p-, 0-, m-oligophenylenetoluene (427, 11 62), p-terph,:nyl-toluene (467, 832, 1606), PPO-toluene (530, 1072, 1383), POPOP-tolu,sne (530), PPOand POPOP-dioxme-ethanol-xylene (426), polyvinyl-toluene (106), diphenyloxazole-toluene (31I , 732,1279,1606), Hyamine 10X-methanol-toluene (1053), Triton X-lOO-toluene (1063), p cymene-toluene (772),and cyclohexaneeoluene (54). Napht'halene (628, 827), dioxane (628), and toluene+!thyl alcohol-ethylene glycol-HNOa (1438) have also been used as sclvents for the organic scintillators. Gels in ether or toluene (530, 1398) :and poly-2,4,5-trimethylstyrene film scintillators (154) and substrate paperc, (1501) have also been used. Liquid scintillat,icNn counting has been ' specifically used by Jones and Monk (737), Kohegyi (837), Leclipteur ( Q 1 4 ) ,and Tamers and Bibron (1586) to determine H3. Othl3r analysts have used it to determine :H3 in bacteria (73, 632), glucose (168),wool (384), urine (444, 1146), and other biological materials (444, 611, 1228, I J Z l , 1455, 1497). Other studies'(561, 611, 623, 746, 799, 1276, 1305, 1406, 11799) are also reported. Reports on the use of liquid scintillation counting to determine CI4 include those by Nathan et al. (1153), Leger and Tamers (931), Cuypers et al. (343), and Bloom (16.3). The C14 content of wool (384) and other biological materials (122h',1321, 1455, 1497) has been measured tly liquid scintillation counting. S t r h s of lens paper placed in a liquid scsintillator mixture has been used to determine C14 in urine ( 1 710). Filter paper-liquid scintillatorsolvent mixtures have been used to measure C14-labeled gluconates (163).
Other examples of C14 determinations by liquid scintillation counting are reported (127, 468,542, 729, 7-46,828, 832, 569,1184,1228,1271,1276,1305,1468, 1474, 1481, 1497, 1583, 1725, 1764). Liquid scintillation counting has also been used to determine sulfur-35 (382, 384, 468, 553, 729, 746), chlorine36 (&%), calcium-45 (251, 468,1438), iron-55, -59 (732), nickel-63 (530), and plutonium-239 (1616). Crystal Scintillators. Monaghan (1099) reviews recent developments in alkali halide scintillation crystals. NaI (Tl) crystals have been standardized by use of calibrated Sc46and CoB0sources
(419). Other 4 7r counters have been described by Hawliczek (629), and others (986, 1627). Bernard (141) describes the first liquid ionization chambers. Miscellaneous. Furuta (4991) described a gamma detector composed of a dielectric scatterer and a Pbabsorber. CdS crystals have been used as y-ray detectors (1754). Plastic scintillators and an ion chamber have been used to measure SrsO-YgO(287). A plastic well-type counter has been used to analyze C O ~ Coao, ~ , Fesg, Cr", and I 131 (326). Erbe and Franz (424) and Gebauhr (202). (502) discuss the advantages of using halogen counters over Geiger counters. Flanagan (458) showed that bremTownley et al. (1619) report on the use strahling caused photomultiplier fatigue of a long counting changer with an in scintillation crystal counters. Reelectrically charged stainless steel wire ports on the efficiency of NaI (1223, to measure FP gases. 12.24, 1681, 1741) and CsI (693, 594) Ely and Ballard (418) report on the crystals have been made. Another application of photosensitive gas countarticle reports on the use of a CaFs ers to scintillation counting. Heimcrystal (1557). Glass scintillators of (636, the S ~ O Z - L ~ Z ~ - M ~ O - A ~ ~ O ~ - K ~ ~buch -C~O Z - 636) reports on the use of scintillating anion exchange resins. As203 type have been used for y-ray Alpha Radioactivity Measurements. detection (57, 174, 713). Murano and Doke (1139) have used a Anthracene crystals in a liquid solvent gridded ionization chamber to measure have been used t o determine H3 and the alpha activity of uranium specimens. C14 being eluted from a liquid chromatoMahnau (996) reports on the use of a graphic column (766,767). pulsed ionization chamber for alpha Attempts have been made to obtain counting. Kawata and Aragaki (777) better energy resolutions from NaI(T1) report on the use of a multiple-wire crystals. For instance, Mathe and spark counter for counting alpha parVoszka (1035) have coated the crystal ticles. ZnS scintillation detectors (82, with a microcrystalline layer. Mota 663,770, 865), emanometers (271, 3 7 4 , (1126)and Verherijke (1681) determined Li-Mg-A1 glasses and Vycor (1655) the efficiency of a 3- X 3-inch NaI (Tl) have been used to measure radon and well-type scintillator crystal. other alphaemitting radionuclides. Anthracene and Plastic ScintilOther methods and counting equipment lators. Rapkin and Gibbs (1347) for measuring alpha radioactivity are report on the use of a n anthracene described by Gusarov et al. (591), crystal-counting apparatus to determine Giffin et al. (617),Ferrari and Rorkowski H3, C", and alpha activities i n flowing (448), and others (230, 248, 976, 1331, streams. Anthracene cells have also 1334, 1384, 1630, 1648, 1649, 1701). been used to measure CI4 and H3 (1467), Beta Radioactivity Measurements. and studies o f the scintillation anisoBeta-ray spectrometry has been used tropy of anthracene a t low temperatures by Cramer and his associates (337) to have been carried out (634). measure the beta decay of Ce144-Pr144, A large size plastic scintillator has AP8, Po, and TI]*. been used in y-counting by Iinuma and Techniques to measure low-level beta Burch (680, 681). radioactivity have been reported (189, Ionization Chambers. T h e use of 388, 915, 929, 1197, 1577, 1578, 1645). ionization chambers in special measHaberer (695) and others (577,678,684) urement problems are described spereport on the use of membrane filters, cifically by Hohle and his colleagues ion exchange resins, etc., to measure (663). Hohle and Zimmerman (664) low-level radioactivity in water. Gelareport on the use of a 4 r ionization tinized scintillators (1398), and a thinchamber of determine the radium equivalents of NaZ2, NaZ4, S C ~Cr61, ~ , CoB0, plate phosphor (255) have been used in beta counting. CUM Zn86 Rb86 Sn113 I131 Cs137 Au19B 1 , 1 7 , > Brown and Watt (210) report on and HgZo3. the intercomparison of 4 A proportional Spherical ionization chambers have counting techniques in the U.K., been used to measure C14, (2060, T l 2 0 4 , Canada, and the ITS. Karosev and Sr898g0,and YgO (1627). Ionization others (768), and Le Gallic (928) have chambers have been used to measure used 4 T counters operating with H3- and C14-labeled compounds (627, methane for beta measurements of Ca45, 1721), Ar4I from a nuclear reactor P3*,and T1204. The use of plastic phosstack (725), Cr61, MnS6, Zn66, Sb124, phors for beta counting is also reC s 1 3 4 , 1 3 7 Ce141 Tm17O Irl92, and Hg205 ported (622). The gross beta activity , VOL. 36, NO. 5 , APRIL 1964
421 R
in urine was determined by Gunter and Smiley (589). G-M COUNTERS. Several studies have been made of the dead-time of a G-M counter (894, 1000, 1096, 1097). Reichel (1353) has reduced the background count of a G-M counter to 3 counts/minute by the use of a simple anticoincidence unit. Hardt and Lutz (617) report that perforated P b fillers improve the energy dependence of a G-M counter. Marxen (1017), and others (111 , 261 , 710, 1150, 1437, 1629) report on the use of Geiger-Mueller counters to measure weak beta radiations. Sato (1.439) reports on the use of a dip counter of the G-M type to monitor aqueous streams for C14, P6, and Srgo-Ygo, A beta-scintillation counting method in which wet filter papers are placed directly on the surface of the photomultiplier tube is used to count C14, Ca44,and P32(818). PROPORTIONAL COUNTERS. Kocharov and Korolev (834), and Smith and Conway (1531) describe the theory and action of proportional counters. Leistner and Diettrich (934), Moscicki (1119), Schulze and Wenzel (1479), Herber (644), Ito and others (709), Mlinko and Szarvas (1085), Nydal (1193), Ono and Morimitsu (1831) and Perkins and MacDonald (1268) report on the use of proportional counting techniques to measure C". Xenonmethane mixtures have been used in a proportional counter to measure x-ray emitting radioisotopes (540, 1150). Eulitz (431), Chmalambus and Goebel (175), Buttlar and Stahl (144), Lee et al. (985) have used a proportional counter to measure H3. Proportional counters have been used to measure (844), C P (955), and Krsa (481). bmardeil and Gonnard ( 3 7 ) , Lerch et al. (942), and Mirianashivili and Burchuladze (1090) have used a highpressure proportional counter for low activity measurements.
Gamma Radioactivity Measurements. M a n y of t h e papers reviewed during this period have used gammar a y scintillation spectrometry t o complete t h e radioactive measurements. Almost all of t h e activation analyses reported in Table I1 a n d t h e radiochemical separations a n d t h e radiotracer applications tabulated in Table I a n d 111, respectively, have used a g a m m a spectrometer to complete t h e analyses. General papers on the use of gamma scintillation spectrometry included those by Owen (1243), Elleman et al. (410), Demidov (363), Caldwell et al. (146), Bruno (112), Gersch (511), Fricke (479), Kinbara (811), De Soete and Hoste (370),and Perry (2270). Gamma scintillation spectrometry has been used in purely instrumental methods to determine U235in U-A1 alloy fuel eIements (151, 290, 317, 335, 670,
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ANALYTICAL CHEMISTRY
6 7 1 , 7 8 9 , 8 6 9 , 9 6 ~987,1168,1191 , , i270, on ,4pplications of Computers to Nuclear and Radiochemistry. De Soete 1656), in uranium carbides and oxides and Hoste (369) and others (1460, 1480, (585), and in solutions (317, 318, 631); 1669,1759, 1763) report on a simplified and Puzs9in ceramic fuels (486). I t has mathematical relationship between also been used to determine cosmicgamma-photopeak resolution and produced .W and NaZZ (1043, 1400); Ce141, Ce14LPr144 R~106, Ru~OG-R~~@, gamma energy. Gaylor (499) presents a similar treatment for fixed time us. C P , and Zrg5-Nbg6in solutions of irfixed count measurements. Koeppe radiated fuels (2001). Gamma radio(836) suggests a mathematical proceactivities found in boreholes drilled in dure to smooth the shape of gamma shales, limestones, and sandstones, actispectra. Fite et al. (456, 467) and vated by a neutron source were also (515, 883) report on the use of a others measured ( 2 4 9 , as were E U ' ~ ~ - E U ' ~ ~ computer-coupled automatic activation mixtures (1133). Mixtures of Fea, analysis system. Dean (355), Tendow Mn", Crbl, and W1*l (1761); Cs134in (1593), Carnahan (249), and Read and alkali salts (1564); in feces (385) Tomnovec (1350) have resolved multiand hormones (1355); T h , U, and K i n component mixtures of gamma radiabasalts (634); T h , U, and K in ocean tions by use of a computer program. bottom cores (783); T h and U in rocks Trombka (1621) and Croall (340) re(169, 670-672) ; radionuclides in water port on the least-squares method of (286, 288, 773, 1331. 1484, l476), and analyzing y-spectra. Ishimatsu (700) geochemicals (334); K40 in soils (592); and Rand (1345) describe a response K40, Rb", P8, and Th232 (366, matrix which converts spectral d a t a into 608, 849); CslS7in CosOmixtures (197); IT,Ra, T h , and K in granite rocks (335, incident photon spectra. Blanchard (164) reports on the use of 366, 1436, 1578) and soils and water a computer program to test and reduce (414-4i6); Cs13' in foods (1730) and radioactivity data obtained from a dust (724),and Pa231 in uraninites (1555) liquid scintillation counter. Dingus and Sraoin bones (13i7) were also deterand Stewart (380) have used a commined by gamma spectrometry. Owen puter program to calculate the effi(12.44) reports on the use of y-spectromciences of various sized well-type N a I etry to measure the burnup of irradi(Tl) crystals. Decay d a t a and the ated fuel elements. resolution of the individual components Low energy y-rays have been measin a radionuclide mixture has been calured by means of a n internal G-M culated by use of a computer program counter (1092). ZnS scintillations have (1101). been used by Jackson (714) to measure Busuoli U236 on fuel element surfaces. and associates ($40) describe the fabriRADIOCHEMICAL SEPARATIONS cation and use of a Compton scintillation counter. McNeill and Green M a n y reports have been made on (1051) report on the variations in the radiochemical separation techniques. characteristics of y-spectra when the Analytical techniques based upon prethickness of the radioactive source is cipitation, volatility, electrolysis, solvent a1tered. extraction, ion exchange resins, paper The gray-wedge method has been chromatography, etc., have been used used by Hollstein and Muenzel (666) in either carrier or carrier-free separato determine the energy and the intions for individual radionuclides or for tensity of y-rays. Monoenergetic xthe separation of groups of radionuradiation has been measured on a scinclides. tillation spectrometer (655). De (354) describes the theoretical Coincidence methods of radioactivity and practical aspects of liquid-liquid measurements have been made by extraction and ion exchange processes Frosch and his associates (484) and used, and surveys the analytical proceothers (223, 353, 484, 7776, 1239, i7627, dures used in radiochemical analyses of 1683, l6.94). Kantele (762) describes a at least 50 of the elements. Other rehigh-frequency sum-peak coincidence ports on the use of solvent extraction spectrometer, and other analysts (866, techniques in radiochemistry have been 1527) describe techniques and equipmade by Morrison and Freiser (1116), ment to measure beta-gamma coinciZefirov and Senyavin ( I 761), Wilson dences with a spectrometer. Ce14'et al. (1719), Marcus (IOIO), MartyPrl44 (674); CoEo(131); Ru1OS ( 5 0 9 ) ; nenko (1026), Ueyanagi and Chang and U in ores (1683) have also been (1632) and others (234, 23.5, 706, 1751). determined by coincidence methods. Clark (308) has used diethyl ether, Radioactivity Measurement Data di-isopropyl ether, and tri-n-butyl phosReduction. Many more analysts are phate to extract Fe, R u , T a , and other using computer-integrated approaches elemental salts. Ishimori and his asto reduce and statistically test radiosociates (703) report on the extraction activity measurement data obtained behavior of 60 inorganic ions, chiefly as by the y-scintillation counting. O'Kelradiochemical species, in the system of ley (i226) has edited and issued all of tri-n-octyl phosphine oxide (TOPO)the papers given a t the 1962 Symposium
HCI and "03. ;Smith (1540) summarizes the extraction coefficients for the distribution of Pu(III), Pu(IV), and Pu(V1) in aqueous-organic systems. Saisho (1422) reports on the solvent extraction of T h arid U nitrates with diphosphonate esters. Fission products have been separated from beryllium b y extracting the Be-dibenzoylmethane complex with CHCl3 or butyl acetate (1606). Mciustafa (1127) used T B P and T O P 0 to extract fission products from acid solution. Seki (14861488) reports on the solvent extraction of the fluoride complexes of thorium. Burger (233), Cerrai and Testa (264), Lock and Martin (968), Makens and Bush (999), Olander (1227), Siddall (1516), Keder (180), Morris (1114), Maeck and others (992), Ochsenfeld and Krawczynski (1196), Seleborg (1489, 1490), and I:,himori et al. (704, 705), and others (192, 193,589,442,461, 489, 723, 841, 1054, 1251, 1503, 1605, 1516, 1719, 1755, 1756, 1766) give general information about solvent extraction applic&tions. (Cerrai and Testa (263) and Alfredson and Farrell ( 2 5 ) ,
Radioelement Actinium-228 Antimony-125
Me;hod' P
Barium-140
P
Bismuth-214
P
Bismuth-210
P
v, p
C
P
Bismuth-203, -205 Cadmium-115
E, C
Calcium-45
SE SE
P Carbon-14
GC C B
B
Abrao ( d ) , a n d Alercio et al. (24), Laskorin et al. (900-902), and Zaborenko et a2. (17&), and others (279, 465, 466, ll45,1180,1516,14O2, f 4 2 f , 1434, 1489, 1672, 1673, 1675, 1676) report solvent extractions for uranium and/or thorium, and/or plutonium. Baes (9,5) reviews the dialkylphosphine acid extraction of metallic species. Other authors report on solvent extraction techniques for magnesium-28 and yttrium-90 (900), phosphorus-32 (953), iodine-I31 (960), cesium-137 (341, 769, 913, 1515, 1748), the rare earths (186, 858, 859, 1034, 1293, 1364, 1569), tin-113 (753), and strontium-89, -90 (728), tantalum-181 (28),and niobium-95 (28, 389, 1230). New equipment for liquid-liquid extraction was described by Lindstroem and Flink (964) and Zaborenko (17G). Massart (1032),Marhol (101d ) , Jeanmarie and Michon (728),and others (155, 266,269, 757, 781, 786,1007,1572,137~, 1415,1416 , 1.446, 1715) survey the recent chromatographic methods-cation, anion, inorganic exchange-used to determine the rare earths and the transuranium elements. The adsorption be-
Table 1. Radiochemical Separations Separation from References Radioelement Mill effluents As'", by volatilization as SbHs and pptn. to metal with nascent hydrogen Srw, by EDTA complexing and nitrate, carbonate, and oxalate ppts. Ra, by p tn as n-propyl gaHate Pb2l0,by pptn. as n-propvl gallate Ra, by HC! elution of anion resin Pb, U, Ta, Cu, meteorites; by chemical pptn. In l6, by electrophoresis of KI-HBr solution by T B P extn. from HC1 solution SrgO,by propanol extn. of CXS- complex Srw, FP's; by nitrate and oxalate pptn. Labeled compounds; by liquid scintillation counting Labeled compounds ; by paper chromatography Warburg apparatus; labeled compounds; by liquid scintillation counting Chlorine-36 Tissue as C1402,by liquid scintillation counting
Chromium-51 Cesium-137
SE
Fission products, nitrobenzene extn. of HtO-tetraiodobismuthate solutions
havior of U and T h on strongly basic change resin from ketone, ether, and alcohol media (574, 855, 1178, 1490) and on alumina columns (1201) has also been studied. Samsahl (1432) reports on the anion exchange studies of 32 radioactive trace elements in H2S01 solutions. Seyb (1494) and others (fei7, 665,1032, 1102, 1307,1574, 1597, 1598, 1684, 1693) report on the use of cation exchangers to analyze for all of the fission products. Other ion exchange studies involving Pt chips (1098),irradiated Yb& targets (1867, alkali (40, 992), alkaline ions ( d o ) , and tellurium (1702) have been made. Gas chromatography has been used to separate gaseous fission products (7, 89, 1709). Paulsen (1258) and others (219, 362, 445, 794, 795, 994, 1195, 1261, 1387, 1414, 1685, 1729, 1736, 1742) report on the radiochemical separations used t o analyze radioactive materials. Sugihara (1574) reviews the general aspects of low-level radiochemical analysis. The National Research Council has issued specific monographs on the radio(Test continued on page 426)
Method" Separation from References C Rb*"; by acid elution (905) of asbestos-tungstophosphoric acid columns C, P Srw in rainwater and (1623) fallout dusts C, P FP's; by NaOH elution (97'4) of silica gel columns P Rb88: bv ammonium (55. S a l . phosphomolybdate ' 874) -tungstate-chloroplatinate salts P FP's; by tetraphenyl (730, 87S, borate-nitrobenzene 889) extn. Rbse, by cation exchanger and copptn. on tetrapoly acid Srm, Ce144, Zr95, Nb95, Rul06, RE'S; by electrophoresis with acetic acid E Sr90, FP's; by paper electrophoresis with acetic acid C Sea water; by acid elution of asbestosammphosphomolybdate column P Sea water urine, by copptn. on Xi-ferrocyanide Bal@; by paper elecC trophoresis C Irradiated KCl and P32 (1081. and S35; alumina 1082) column adsorption from 0.5N HC1; by elution withO.5N HCl C K40842; by alkaline elu- (1004) tion of alumina column (Continued)
VOL. 36, NO. 5 , APRIL 1964
423 R
Table I. Radiochemical Separations (Continued) Methoda Radioelement Methodo Separation from References SE FP's; by isobutyl methyl ketone extn. C of butylammonium complex SE Phosphorus-32 C Reactor cooling water, corrosion products; C by HC1 elution of anion exchanger A Reactor cooling water; bv vermiculite absorption P Xi, Pd, Ag, Cd, FP's; SE Cobalt-60 A by dithiocarbamate extn. 17 RulQs,Ca13', Srm, Ce144, water; by ring-oven D, c technique U; by chlorination Fission products L) and distillation (mixed) P Plutonium-239 SE U; by alamine-diethylbenzene extn. C Of HYOaHzSO4 Irradiated LiC1, by SE Fluorine-18 T' T B P extn. of HCl, HKO, on HzSOIsolutions P IE Rare earth oxides, by Haf niuni-181 anion exchange SE IE Rare earths, fission products; by elution of Dowex-1 resin SE columns with 0.1M oxalic acid Aq. solutions; by SE C T B P extn. Labeled compounds, GC Hydrogen-3 C as H3-hydrides from liquid scintillation P counting
Radioelement
~
B B B B
B GC SE, P
Iodine-13 1
C C C Manganeee-54
SE P
Molybdenum-99
SE SE
Molybdenum-103 P Neptunium-237, SE -239
E SE
424 R
Lithium metal, aa Hs-hydrides from water Acetylene conversion; by internal gas countmg Tissue; aa H3-hydride, liquid scintillation counting Water; aa H3-butane, gas counting Air and other gases aa Hahydride Beryllium; aa H3-hydride FP's; by extn. with cc14 and pptn. as AgI Te133; by paper chromatography FP's UF4; by acid elution of A1203 column Milk; by acid-alkali elution of Dowex-2 resin Fe66,59. by ether extn. of H c ~solution Corrosion and fission products; by pptn. aa MnO2 and MnOc U FP's; by butyl alcohol extn. Irradiated InllemWSs; by extn. with Michealis buffer solution FP's; by Cr(C(!)g pptn. U, Pu, and fiesion products; extn. by diethyl ether or orthophosphoric acid derivatives Electrodeposition of NpZa7from urine FP's, Pu, Am, Cm, Th, U ; by triiso-
ANALYTICAL CHEMISTRY
c, E P, SE P C
SE Polonium-210
v P C P
E Potassium-42,
C
Protoactinium-231, -233
C, SE
C Rare Earths La140 Ce144 Ce144
C
P C
Separation from References octylamine-xylene extn. from HNOa FP's: by anion ex(774) change Irradiated sulfur bv (3%) . .. toluene Irradiated KCl, Sa, and (1081, CIs6; by alumina col1082) umn adsorption from 0.51v HCl; H 2 0elution Detergent solutions (1453) ZnB5,Fe'@,Sb'24; by (1419, adsorption on peat 1580) column Irradiated S; by dry (1739) distillation of sulfur; paper chromatograph purification Fe+3, & + 3 , and FP's; (1646) by LaF3 copptn. (1647) FP's; by HN03-anion (170, exchange 1714) U,FP's; by anhydrous ( 9 7 9 ) chloride vapor volatilization Arnz4l,by K2Pu(SO4)4 (665,566) pptn. from "03 U, by methyl isobutyl (804, 876, ketone extn. of 877) HPr'Oa U; by CCl4 extn. of (790) cupferrate complex from HC104 or HC1 U: bv HCl-HF elution (872) 'of Dowex-1 resin U,FP's; by "03 (2704) elution of Dowex-1 Transuranic elements; ( 4 3 8 ) by Hz02 pptn. Urine, anion exchange (1434) and electrolysis Aq. solutions; by co- ( 8 4 7 ) pptn. with BiPOa and cupferron extn. Cr, Fe, FP's; by co(1647) pptn. on LaF3 Cr, U, etc.; by "01 (872, elution of Dowex-1 1617) resin Urine, amine-xylene (217) extn. in vacuo sublimation (1) from rocks Uranium concentrates, (1644) by CuS copptn. Bizlo; b HCI, H?1TO3, (833) on H&O e.I ution of cation exchanger Bizlo; by copptn. on (1644) cus Pbal2, by electrodepo(1086) sition Ca46,Kag4;bv ion (469) exchange method ZrS6, Kp237, irradiated (76) Th, U-Th, and BeTh alloy. Elution of resin column with 3.8M HC1, followed by extn. with isobutvl methyl ketone Irradiated T h ; by (508) Dowex-1 exchange Other RE'S, by ammo- (603, nium thiocyanate1740) HC1 elution of cation resin Cs137, Zr95, SrW.Ru106; ( 6 4 0 ) by pptn. as iodate from HCI Solutions RE'S, U ; by paper elec- (682, 480, trophoresis, tartaric, 846) citrate and lactic acid electrolytes
Radioelement La140
Method"
SE SE P SE SE
C
c C Ce14'
SE, P
c Rhenium- 184
SE
Ruthenium-103
A
SE Ruthenium-106
E
SE P
C
Scandium-46
C
Silver-llOm, -111
C SE A
Strontium-90
P
SE P
P P C, p P A
SE
Table 1. Radiochemical Separations (Continued) Radioelement Methoda Separation from References C Other rare earths, T h ; (764) by TUP extn. of SE HXO3 solution Other RE'S; by count- (859) P ercurrent extn. Srw; by copptn. on (835) SE Fe(OH)3 Other RE'S; by T B P (92,860) extn. from HNOZ C solutions Prl43, ?;d147; by count- (14) C ercurrent extn. of Cd and Na chloride SE solutions FP's; by oxalic acid (1706) C Sulfur-35 elution of Ilowex-50 Yb'75, Tni1j0: by huty- (1033) ric acid elution of cation exchanger Yw,Yb175, Srw; byelec- (990, 991) Tellurium-12 5 SE trophoresis sepn. on Pt column A q . s o h . ; by extn. (1018) with nitroethanehexane and .~ pptn. as Tellurium-132 C oxalate FP's, by hydroxyiso- ( 1 726) butvrate elution of Tell~rium-l27~,C cat& exchanger -12P Target; by KOH(697) pyridine extn. Raw water by adsorp(1419 ) C Thallium-240 tion on Multiklon powder Thorium-230 C Sand, water; by CCb (1640) extn. after fusion firm, CsI37, ZrQs,Xbg5, (1510) Pm147,Tc99, and CeI4'; P by paper electrophoresis FP's; by extn. with (599) T B P from HNO3 FP's; by periodate or (77) P persulfate pptn. Srw, Cs137,other FP's; (1510) P by electrophoresis with XaNOa electroC lyte RE'S, Th, Zr, Fe, Ti, (602) Al, Cu; by thioV Tin-113 cyanateHC1 elution of cation resin C Irradiated Pd metal; by ( 2591 ) elution of anion resin Transplutonium with 10.M HC1 Elements Hg, Zn; by dialkyl di- (613) Amgal C thioic complex extn. from HCI Aq. solutions; by rad- (606) iocolloid an pyrites and dust Amz'l SE Srwcontent of skeletal (110, 944) tissues C Irradiated uranium (1478) and FP's; extn. by Il2EHPA-diluted T B P SE Soil, silt, and ash sam- (1399) ples, by pptn. methods SE Sea water, by pptn. (1308) methods FP's; by fuming (676, HNO, and COa and 1366) SE PO4 pptn. Food: by inn exchange ( 6.801 Cranium-236, C plus carrier pptn. -238 Ca46,by pptn. with al- ( 1 78,598) coholic solution of C rhodizonic acid Ym; by adsorption on (814) ammonium salts C Ba, Ca, Na; by di(819, 820) ethylhexyl phosphnric acid-AMSCO extn.
Separation from Yw; by ion exchange
References (823, 1637)
Yw; liquid amalgam (1330) exchange Ca45. P32: bv nitrates (1008) and oxalate pptns. Yw, bone ash; by (467,539, POPOP-toluene extn. 647) of HNO, solutions Y w , milk; by cation (1602) exchanger Yw; by paper electro(1563, phoresis 1662) Milk, by HDEHP(241) toluene extn. Irradiated KCI, P3*, ( 199, C136; by alumina col1081, umn adsorption from 1082, 0.5N HCl; elution 1738) with 0.1N",OH Irradiated antimony (1743) target; by extn. from aqua regia with CHCIZ-. or C C G dithizone Irradiated uranium, ( 1565) FP's, 1 1 3 2 ; by ion exchange Te as tellurate or tel(10) lurite; by electroDhoresis with YaOH electrolyte PbZIO,Bizlo; by paper (1662) electrophoresis 23 common cations, (483) by 0.5M H N 0 3 elution of Dowex-1 resin column Uranium ore concen(15) trates and plant liquors, by copptn. with LaF3 from HZS04 solution Uranium concentrates, ( 1 644) by CUR copptn. Grass, bones; by (537) chemical pptn. C ; by butanol-HCI (8.50-852, elution of Dowex-1 854) resin FP's; by volatilization (568, 670) SblZ4, as SnH4 TelZ7m,by TBPHCI ext,n.
(1079)
Cm, Bk, Cf; by rnethanol-HXOa elution of EDTA complexes from anion exchanger C m ; by T O P 0 eutn. from HN03 Ar, Th, P u ; by alcohol-acid elution of aper chromatogram OtEer actinides; by trioctylamine extn. from HCl Other actinides; by inorganic ligand extn. of rarhonate and bicarbonate solutions Cm242, by phosphonate estn. Thorium, by elution from Dowex-50 resin with H?;OI-alcohol Thorium, by elution of Doweu-1 resin with H2S()a-alcohol Thorium, by elution of anion resins with HCI-, HYOT-,
(6Fi4)
VOL. 36, NO. 5 , APRlL 1964
(707) (786) (779) (449, 782, 782) (1264) (8.55) (720) (862)
(Continued )
e
425 R
Radioelement
Method" C
Table I. Radiochemical Separations (Continued) References Radioelement Method" Separation from References Separation from P, SE Pu, Th, Am, soils, water, (771, HpS04-alcohol mixvegetation; by tan1700, tures Thorium, by elution of (1659) nic acid pptn. and iso1767) butyl methyl ketone Dowex-1 resin with ketoneHC1, or extn. -"O. C FP's. oxalate exchanee (673) reactions Urine; Cy TBP extn. (947) Zinc-65 SE In"6, Cr5l, by tri(6011 FP's, by TBP-benzene (550) but oxyethyl p hosZr, Be; by dibutyl (619) hosphoric acid-TBP phate extn. Kerosine Zirconium-95 C Reactor effluents. sea 1973') water; by HC1 elu-97 FP's, T h ; by anion (638) tion of dit,hiazone exchange method saturated cellulose FP's; by thiocyanate (884) acetate column elution of activated C Hfl81; by HCI-acetone(691) carbon column H 2 0 elution of cation Aq. and organic soh(857) exchanger tions; by sulfoxide SE Hf1s1,by TBP-xylene (763) extn. of mineral extns. acids SE Hf1S1,Nb97; by TTA (195, Th, FP's; by liquid (291) extractions from (995) metal extn. mineral acids (496) Thz3',Pazz3,Ybl69, P Nbg6, seaweed, seaLul7'; by cation exwater; by chemical changer (610) PPtn. Other cations; by do- (1667) decyl phosphoric a P = precipitation; TT = volatilization; C = chromatography; acid extn. from GC = gas chromatography; SE = solvent extraction: B = HzS04s o h . combustion; D = distillation; E = electrolysis; A = adsorption. 0
SE SE SE C C
SE
SE C
SE
chemistry of germanium (1013), phosphorus (927), silicon (2135), sodium (525, 91 7 ) , rapid radiochemical separations (831, 881), thallium (21S ) , uranium (324, 6/30), lead (528), silver (2575), distillation techniques (372), rubidium (2136), nickel (GO?), and palladium ( I 008, 1136). Amiel and Yellin (51) also describe rapid radiochemical techniques. Reports on other radiochemical separations have been made by Auerbach (91), Rehounek ( l a g ) , Barnes (202), Kourim et aZ. (867),Kelley (788), Meinke ( 2 057-1 060), and others (262, 994, 1036). Testa (2597) presents a description of the methods used in the analytical chemistry laboratory of CISE for the separation and analysis of many radioelements of interest. DeVoe and Meinke (372) and Parker and Grunditz (2255) describe distillation and volatilization procedures and the apparatus used in the rapid carrier-free separations of radioactive nuclides not isotopic with the target material. Electroanalysis methods to separate radioactive nuclides have been reported (101, 195, 206, 991, 1546). Gorshtein (555) and others (272, 280, 584, 1S02, 1329, 1349, 1589, 1404) report on crystallization and precipitation techniques and Orbe et al (1233) report on amalgam exchange reactions to separate radionuclides. Samsahl (1431) reports on a chemical separation of a t least 15 radioelements by a precipitation method. Schroeder (2470), and Skougstad and Fishman (1524) have compiled a tabulation of the radiochemical methods used to determine radionuclides in mater. Schiffers
426 R
ANALYTICAL CHEMISTRY
(1449) summarizes the methods used to separate Pu. Baurmash et al. (121, f22) describe a separation scheme for use in determining MnSB,FeS9, P32,and S36 in reactor coolants. U(V1) has been separated by means of tridecylamine fluoride extractions (2677). Am242has been extracted from "03, HC104,HCl, HzSO4,and acetic acid solutions with DAMPA-Le., diisoamyl ester methyl phosphoric acid (2754). DAMPA, as well as tributylphosphine oxide (TBPO), has been used to extract uranium (1502). Diethylenetriamine pentacetic acid extractions have been used to determine T h (1316). Jones (738),Nebel (1163), and Overman (2240) discuss analytical methods for the analysis of Pu and U in nuclear materials. Radiochemical separations of P321S35, and (505), radionuclides in blood (532), Cus7 and U235 (1130), radionuclides from aircooled reactors (108.4, reactor materials (1126), waters (500, 504, 743, 807, 1471, 1680), NaZ4, K42, CuM, Moss (970), technetium (792, 794), SrS0(218, 676), ThZz8(218),Am241and PuB9 (176, 11 7 6 ) , Srgo-YrgoCe'44-Pr*44, Pm"' (108, 109, 861), ce'sium-137 (322), and radionuclides in urine (163d), marine organiqms (678), Sb122,124s126 (74), ? V I O ~(75). ~ NpZs7 (230, Sod), and Zrg5 and Hf181 (409) have also been reported. Special reports on the determination of C14 have been made by Genunche (508) and Hamilton and Moreland (609). General information on tritium analyses is given in a number of reports (446, $53,690, 76Y, 1084, 1448, 1600). Table
\
I
I lists many other pertinent radiochemical separations. ACTIVATION ANALYSIS
Many more analysts report on the use of activation analysis techniques to assist them in more difficult analytical problems. Bowen and Gibbons (285) have issued the first complete book on radioactivation analysis. This book gives the theory of the method and describes practical details of the techniques and methods of analysis used to determine 85 of the elements in analysis problems in chemistry, biochemistrv, geochemistry, and metallurgy. Hara (626) and Meinke (1061) report on typical uses of research reactors in pure and applied chemistry research. Included in these reports are general remarks about activation analysis. More review articles on activation analysis applications have appeared during 1962-63. For example, BockWerthmann (172, 17 9 , Schulze and Bock-Werthmann (1477),and the Institute of Nuclear Research of the Hungarian Academy of Sciences (684)have issued extensive bibliographies. Other review articles, appearing in Nucleonics (66, 70) and in dtomics ( 7 l ) ,give much information about the techniques and equipment used in activation analysis and the magnitude of its applications. Review articles were also presented by Baumgaertner (218, 119)) Burrill and Hirschfield (236),C o r k (328),Gebauhr (501), Glubrecht (534), Hoste (673). Hudgens (675), Leddicotte (926, 928, 922), Melnechuk (1065),Morris (1110),
Niese ( l l 7 4 ) , Niesc? a n d Leonhardt (1175), Raleigh (13:37), Sayre (1444), Shiraishi (1508), Trew (1620), Tittle (1607) , Van Eestererl (1663), Wainerdi and DuBeau (1696), Wodkiewicz and Mincewski (17 2 4 , arid others (735, 791, 856, 986, 1520). Other authors protide reviews on the use of activation analysis methods and techniques in specifc problem areas. For example, Aitken (11,12) and Sayre (1443) report their us(’ in authenticating ancient artifacts and in other archaeological applications. Semel (1491) presents the potentials of using activation analysis for trace elements in explosives research, and Hanes (614) evaluates its use to determine trace impurities in chemical products. Gaudin and Ramdohr (497) describe its use in sorting copper ores. Crawford and his associates (338) report on the potentials of using neutron activation analysis in steel production and describe equipment suitable for this application. Fodor (462) and the Isotop Teknesker Laboratory of Swedm (1576) also review similar applications. Girardi and Pauly (627) report ,311 its use in the analysis of nuclear materials. Dibbs (376) and others (69, 531, 757, 946, 966, 1273, I % @ ,1343, lqt’4, 1523, 1589) report o n its potentials for industry. Forensic chemistry applications of activation analysis have been reviewed by Remsberg (1356), Kirk (816),and others (115, 116, 733, 921, $122). Anders (56) a n d Gluck a n d his ahsociates (535) describe activation a r d y s i s tests and equipment that can be used in “onstream” applications. Baird et al. (98) report on the use 0)’ a stable traceractivation analysis technique to evaluate the performance of a reducedpressure backflow prevention value for use on a potable water system. Glubrecht (534) reports on another water study using activation analysis. Although many of the reports cited in this review describe applications involving the use of Cources of thermal neutrons, a number of other papers describe experiments and apparatus for producing other types of nuclear particles to irradiate sample have been reported. X delayed-neutron method has bepn used to determine Lie, 01*,and W7 (45, 49, 50, 450) and 1;235 (396) charged particles have been used to determine many differ’:nt elements (156, $37, 650, 775, 1522, 1623). Techniques with photoneutron reactions (46, 360, 437, 1073, 11 79) , promptgammas (20, 571, 741, 7 @ ) , resonance neutrons (961, 962), 14-m.e.v. neutrons (158, 181, 257, 377, 4J6, 490, 523, 524, 1058, 1062, 1063, lS.L$, 1567), pulsed neutron fields (407, 1094), fast neutrons from a reactor (981, 982, 1581), He3 particles (1015, 1016) and radioisotopicberyllium sources (375,.536, 656, 711, 1568) are also being used.
Other experimenters have directed their activities to essentially the sole use of very short-lived radionuclide species--e.g., 5s Br7$m, 17s Se7’m, 10s Fm- to complete a n activation analysis. Loos (%’I), Chinaglia et al. (292, 293), Mitteilungen (1093), Guinn (686, 687), Gibbons and Simpson (516), Anders (55), Albert et al. (18), Baker (QQ), Okada (1205-22), Peck and Pierce (1284), Kramer et al. (871), Kamemoto et al. ( r i g ) , and Bate et al. (116) have issued reports on this activation analysis application area. The use of rapid radiochemical techniques is gaining prominence in some laboratories (811 , 871, 1057, 1357). Other papers review chemical analysis procedures used in activation analysis. For instance, Jones (735) and Franks and Gilpin (478) cite the use of chemical techniques in activation analysis. General information is also presented for the analysis of uranium fuels ( Z S I ) , Ta and N b (316, 417, 839), oxygen (114, 940), germanium, selenium, silicon, thorium, and silica (1088), textiles (81), dusts (1956, I S @ ) , terphenyls and plastics (90,1259), paper chromatograms (1385, 1386, 1562)) C , 0, Al, Si content of coal (1023), beryllium (99), aluminum, iron, and zirconium (17, 18), sulfur (181), rubber (181), meteorites (243, 312), ocean bottom cores (387), lunar surfaces (597, 1071, 1622), sodium glutamate (981), and the C, 0, N content of metals (16). West (1713) reports that activation analysis is a sensitive analytical method for inorganic microchemistry requirements. Albert and Gaittet (91) report on the use of a microchemical scheme for the determination of at least 45 induced radioelements in neutron-irradiated samples. Similar chemical schemes are used by others (368, 373, 472, 473, 1222, 1520, 1564, 1753). Technical problems concerned with self-shielding, flux depression, and moderators have been considered by Morzek ( I 117 ), Reynolds and Mullins (1362), Gilat and Gurfinkel (519, 520)) Hoegdah1 (659), De Pangher and others (367),and Durham (393). Doege (383) and Kenna and Kenna (793) describe a simplified mathematical method to interpret activation analysis sensitivity data. Graphical representations of the induced radioactivity have been presented by Okada (1216). Kamemoto and Yamagishi (758) performed a unique experiment to determine the yield of the carrier added to the postirradiation separation of aluminum-28 from irradiated metal specimens.
ACTIVATION ANALYSIS APPLICATIONS
M a n y new reports on activation analysis applications in the fields of metallurgy, geochemistry, and biochem-
istry have appeared during this review period. Articles from these areas are specifically cited in Table 11. I n addition, Table I1 includes reports on miscellaneous applications areas. USE OF RADIOACTIVE TRACERS IN ANALYTICAL CHEMISTRY
The use of radioactive-labeled materials or a measurement of a material’s natural radioactivity still remains a very useful way to answer analytical requirements. Reynolds and Leddicotte (1361) review the radiotracers, techniques, and analytical methods employed in typical organic and inorganic applications. Such techniques, involving isotope dilution, radiometric titrations, and the use of radiotracers for procedure development are of much value in analytical chemistry. Special reports have been made by Ruzicka (1410) and Reiler (1712) on the use of isotope dilution techniques in analytical chemistry. Radioactive tracers have been used in radiometric methods to determine the elemental species distribution between solid and liquid phases of thoria and urania slurries (581) and the volatilization of inorganic chlorides in dry-ashing techniques (558). Iodine-125 has been used as a radiographic source (582). Millicurie amounts of beta radioactivity have been used to determine the ash content of coal (1022, 1023), the properties of coal and coke (347),and the thickness of deposits on metal surfaces (1028). Radioisotope-excited x-ray sources have found much use in composition determinations (28, 399, 420-423, 1636). Other reports on radioisotope-excited sources have also been published (258, 409, 433 1758). Beta and alpha sources have been used to measure sediment denqities (495, 1099). Gamma-ray sources have been used to measure the moisture content of soils (590, 1164, 1190) and the sulfur content of hydrocarbons (1401). Keutron sources, using alpha radioactivities mixed with beryllium powder, have been used to determine soil m o b ture (454, 1048, 1068, 1172, 1249, 1661, 1731), the water content of sintered iron (878), and the C / H ratios of organics (1618, 1691). Other uSes of neutron or radiation sources have been reviewed by Anderson et al. (58) and Fisher (454). Weisz and Klockow (1712) and Ottendorfer and Weka (1237) report semiquantitative autoradiography techniques to estimate Co60, CsI3’, Zr”, SrgO,CeI4‘, and Rulo6in a variety of materials. Other authors report on similar autoradiography techniques (194> 3.56, 448, YV95,965, 1318). Table I11 tabulates many other uses of radioactive tracers in analytical (ahemistry. iill of the reports cited in this table have originated during this review period. VOL. 36, NO. 5, APRIL 1964
427 R
Element Aluminum
Antimony
Argon
Arsenic
Barium Beryllium
Analyzed in Minerals Rocks Meteorites Diamonds Graphite Terphenyl Sea sediments Metals Lead Terphenyl Silicon GaAs Platinum Selenium Zirconium Lithium compounds Steel Blood Air Meteorites Potassium minerals Biological materials Silicon Selenium Lithium salts Graphite Platinum Phosphorus Steel Eye tissue Gunpowder residues Solutions Ores Minerals
Boron
Bromine
Bismuth Cadmium
Calcium
Carbon Cesium Cerium Chlorine
C hroniium
428 R
Concentrates Solutions Be0 CaFz Minerals
Table II. Activaticm Analysis Appliccitions ConcenAnajyzed Concentrationo Method* References Element in trationa 1-l0Yc NL, (597, 1365) Aq. solutions 15 l-lOCl, xr) (597, 1365) Steel > 1y0 10 NI) 1597) 0 01 Beryllium 10-100 0 1 Granites 3-22 0 001-5 Silicon Cobalt 103
(25
