(786G) W. Koehler and R. Radeglia, 2.Chem., 9,467 (1969). (7870) Y. Arata and T. Fukumi, Mol. Phys., 19, 135 (1970). (7880) W. Koehler and ,Re Radeglia, 2. Phys. Chem. (Leiptzg), 243, 127 (1970). (789G) J. Homer, M. H. Everdell, E. J. Hartland, and C. J. Jackson, J . Chem. SOC,A , 1970, 1111.
(79OG) Yu. I. Neronov, Z.Kh. Rakhimov, and G. M. Drabkin, Zh. Strukt. Khim., 10,589 (1969). (791G) J. F. Hinton and C. E. Westerman, Spectrochim. Acta, Part A, 26, 1387 (1970). (7920) R. G. Anderson and M. C. R. Symons, Trans. Faraday SOC.,65, 2550 (1969). (7930) 0. Gillber La Force, J. C. Eriksson, and P. &wall, Nord. Symp.
Gtaenae$adekemi, Foztryk Foredrag, Srd, I1 OA7).I \----
(7940) O. F. Beerukov and A. N. POtanin, Dokl. Akud. Nauk SSSR, 192, 353 (1970). (795Gj J. E. Gordon, J. C. Robertson, and R. L. Thorne, J . Phys. Chem., 74, 957 (1970). (796G) P. A. Arrington, A. Clouse, D.
Doddrell, R. B. Dunlap, and E. H. Cordes, ibid., p 665.
Nucleonics W . S. lyon, E. Ricci, and H . H. Ross, Analytical Chemistry Division, Oak Ridge National laboratory, Oak Ridge, Tenn. 37830
T
HE ANALYTICAL BALANCE has continued its swing toward application during the past two years and nucleonics has swung along with it. Thus we again find a smaller number of papers describing new or innovative techniques. The total overall number of papers, however, appears still to be growing. The economic pinch that cut off a number of nuclear projects has resulted in a diminution of research effort in almost every laboratory, and loss of employment to some of our colleagues. In these difficult times, radiochemists and activation analysts have broadened their horizons and narrowed their sights: techniques previously restricted to the nuclear industry are increasingly being applied to highly practical problems concerned with the environment, while a t the same time attention has been focused to immediate specific solutions rather than long term research. Fortunately there is indeed a large reservoir of expertise on which to draw, but we anticipate the outflow to be greater than the replenishment for some time to come. Thus we find our review more present-time and application-oriented than in the past. While the words nuclear chemist, nuclear physicist, and theoretician may not be completely “out,” analytical chemistry is definitely “in” and the activation analyst finds a new interest in his work-and new colleagues alongside him-from a section of the scientific community that in the past eschewed analytical work. We shall all be strengthened and benefited by this association. 4 s usual Table I lists books, articles, reviews, etc., not discussed in the text. Also, as usual, we wish to call attention to Isotopes and Radiation Technologyan excellent source of review articles
NOTEADDED IN PROOF: We have just learned that lack of funding will force
Isotopes and Radiation Technology t o cease
publication with Volume 9, No. 4 (1972). 438 R
*
and current information on all phases of nuclear applications.’ The American Society for Testing and Materials has slowly been adding radiochemical material to its published methods; these include both procedures for testing radioactive materials as well as methods for utilizing radioactive tracers or isotope procedures. Finally, a long overdue statement of appreciation needs to be made t o the International Atomic Energy Agency. This Vienna-based organization has sponsored innumerable panels and conferences covering every aspect of atomic energy from agriculture (application) to zygote (effect cf radiation on). The many publications resulting from these gatherings provide probably the best and most complete documentation of current nuclear research and technology available. Papers from many of these IAEA publications are mentioned in the text below and Table I. These IAEA volumes form a large part of the reservoir of information on which the analytical radiochemist now draws. I n the four official languages of the Agency, we say, “Thanks.” ABSOLUTE MEASUREMENT A N D STANDARDIZATION
The dissatisfactions and uncertainties associated with many of the presently available so-called radioactive standards were articulated in the National Academy of Science special publication “National Uses and Needs for Standard Radioactive Materials” (123). The report, prepared after months of interv i e w and consultations with representatives of all segments of the nuclear industry makes a, number of recommendaticns, the most important of which is that the U.S.Bureau of Standards be funded to perform research and services necessary for providing and promoting use of standards of from 1-370 accuracy. Implementation of these recommendations by the
ANALYTICAL CHEMISTRY, VOL. 44, NO. 5, APRIL 1972
federal government will immeasurably benefit all users of radionuclides. Embellishments, modifications, and variations of the classic 4rp-7 coincidence counting technique for absolute disintegration rate determinations continue to appear. 4rp-y anticoincidence counting has been shown by Japanese workers (79) to give useful results for measuring nuclides with complex decay schemes. Another group of Japanese has derived a new correction method for the 4rp-7 coincidence absolute measurement of nuclides emitting soft (12). The conversior? electrons resulting correction formulas were applied to the absolute measurement of l*oTb and to the mixed 140Ba-140La activity. The disintegration rate obtained was found to have an uncertainty of no more than 1%. d number of other papers have appeared which present theoretical treatments, lengthy calculations involving many correction factors, and/or minor changes in preparation, and measurement of samples. For the analytical radiochemist, such refineinents appear to go beyond the realm of praci icality. Closely related to standardization is the problem of purity and integrity of radioactive compounds. Labeled compounds in particular have come under scrutiny (%), especially selfdecomposition. I n one survey, for example, an unacceptable level of impurities was indicated by 70% of the respondents (55). The report of the Panel on Analytical Control of Radiopharmaceuticals (7) provides much information on this problem. The term “trace colloids” has been suggested in discussing some of these problems (19). The stability of 7 commonly used radionuclides in sealed glass ampoules was studied and recommendations made as to the suitability of each as standards ( 7 7 ) . The obverse of the self-degradation situation is one where radiation from a solution to be mea-
s u r d for some nonradioactive property affects the measuring device. Studies of these effects have been sparse, but one recent paper indicates the cumulative effect of gamma radiation on electrodes to be probably minor up to at least lo7 rad (88). MEASUREMENT IMPROVEMENTS
Gamma-ray spectrometry continues to be the most powerful tool available to the analytical radiochemist; often it is applied without prior chemical separation to samples containing many different radionuclides. Ge(Li) detectors have largely replaced NaI(T1) for this type of multielement determination. Most of the papers appearing in the current literature cite data obtained from Ge(Li) spectroscopy, and only a few results utilizing NaI(T1) crystals as primary detectors were noted. Of course, NaI has not disappeared-it is used in well type detectors for routine counting, whole body counters, anti-coincidence arrangements, and other special assemblies-but the more complex problems of the ‘90’s demand the sophistication of solid state detectors, large memory analyzers, and computer data processing. Of this latter we can say little; each worker continues to be “an island unto himself,” developing his own program or modifying another’s. Such procedures are obviously inefficient, timeconsuming, and frustrating, yet the very complexity of the overall problem (different size detectors, different analyzers, different computers) militates against any uniform treatment such as was established with NaI; meanwhile, the situation cries for some sort of standardization or unification. Perhaps work such as that at Idaho Falls (58) will eventually lead to such a conclusion; these workers discuss a method to determine relative detection efficiency and linearity of a Ge(Li) spectrometer by using but three radioactive sources: %e, **Br, and W o . The problem of attempting to measure small photopeaks in the presence of large backgrounds continues to engage the attention of investigators. A French group (61) has described an interesting spectrometer that can operate simultaneously in three modes: low energy gamma-ray spectrometer (30-500 KeV), Compton spectrometer or “duode” (0.3-4 MeV), and pair spectrometer (>2 MeV). A possible tool for some special assays is a Si detector system in which internal conversion electrons are observed in coincidence with fluorescent X-rays subsequent to them (72). The authors claim suppression cf almost all pulses produced in the detector by beta and gamma rays. T o obtain greater efficiency, a group in Australia has operated
three
Ge(Li) detectors in
parallel
(96). For measurement of low gamma activities, a Ge(Li) well type detector has been studied (69). An everpresent danger in the use of lithiumdrifted germanium detectors is the unexpected loss of liquid nitrogen from the cryostat. An alarm circuit has been developed (137) for warning against excess leakage current in the detector due to inherent detector failure, vacuum failure, or loss of cooling. A promising detector for use in examination of chromatograms or other radioactive samples in which a two-dimensional analysis is required has been reported (24-96). By inserting a very high resistance collector in an otherwise conventional detector, the rise time of any pulse therefrom is made position sensitive but energy independent. The rise time, and therefor the position, is accurately determined by means of pulse shaping and timing. A British patent (169) describes a new method and device for producing a multicolored photographic record of the concentration and distribution of radioisotopes using scintillation scanning. The device includes a t least two sources of light, each of a different cclor, and a discriminator for selectively energizing the light sources in accordance with the amplitude of the output signal of the pulse-rate measuring device. As an area is scanned by a scintillation probe, the color-sensitive photographic film is scanned by various combinations of colored light, thus producing a multicolored record of the isotope distribution. Another scintillation device is based on delay-line time conversion for improved resolution of low-energy gamma emitters (63). Signals from the photomultipliers are fed to appropriate intermediate taps of a delay line so that the delay times are proportional to the coordinates of the photomultipliers on the crystal. A block diagram and performance parameters are given. By using a pair of gas flow proportional counters, one operated as a tritiated standard counter, it has been shown possible to correct for the plateau-shifting effect of impurities in the flow gas (109). The principal advantage of the standard counter over a counter using an external source is that the pulse-height spectrum more closely mirrors that of tritium in the gas phase. A new type of proportional counter has been described that can be used to locate the position of impact of a charged particle (155). The counter uses a resistive electrode; charge amplitude is used to localize the ionizing event. I n our 1968 Review, we presented an interesting analytical technique utilizing a “track-etch” method. Since that time, new analytical applications of the method have appeared. For example,
T a b l e 1.
Books, Reviews, and Bibliographies
General : (60,4O, 65,81, 113 ) Gases as tracers: (141,1?‘6) Radiochemistry: (91,93,118,168) Standards: general (17) methods (76,114) Nuclearmethods: (43,73,142, 144,146) Low level, radiorelease: (64,110) Neutron protection, safeguards, dosimetry: (16,37,~40,164) Activation analysis: Books: general ( l 4 , 8 7 ,96,143) gamma-ray s ectrometry (1,46) Reviews and biiliographies general (61,67,10S, 108, i64) non-neutron (106,118) neutron generators and space app. (64, 106,160, 139, 171,181) pollution (70,107) forensic (104) oceanography (106) archaeology (69,170) medicine (177) Aids : gamma-ray energies and spectra (13, 65,
r4,114,1sa)
neutron-capture gamma rays (160,161) second-order interference (130, 131)
solid state track detectors have been used to detect minute concentrations of uranium in water (48). A known volume of liquid is placed on a trackdetecting material and evaporated. The residue is covered with a second detector and irradiated in a known thermal flux t o induce fission reactions. Then the detector is etched and the tracks produced are counted. The number of tracks is a direct measure of the uranium content. A conference a t Clermont-Ferrand, France, in 1969 covered applications of ,nuclear tracks and volume 2 of the proceedings is available covering 39 papers of general interest (71). An invention purported to improve the statistical counting accuracy of a sample has been noted (138). Sample rotation during measurement appears to be primarily responsible for the increased accuracy. Standard test procedures for GeigerMueller counters are presented in a note published by the IEEE (4). Specifications for test conditions, counter parameters, and test equipment are given, and pulse characteristics are defined. A book on nuclear electronics for radiation detectors and signal processing has been published (86). Survey chapters (general) on instruments for radiation detsction and measurement have also been noted (66,184). The increasing concern regarding environmental pollution and nuclear safety is reflected in the increasing literature of low-level radioactivity measurements and fissionable material assay. Although most of the papers treating the former subject can hardly be called
ANALYTICAL CHEMISTRY, VOL. 44, NO. 5, APRIL 1972
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new since they reflect primarily improvement in counting techniques or modified chemical separations, this does not mean that the subject is essentially closed; the demand for ever lower radionuclide release will challenge the radiochemist to further sharpen his techniques. An excellent discussion from the British point of view has appeared (49), the overall U.S. problem approached in an article in Nuelear Safety (60),and the revised (1971) APHA “Standard Methods for the Examination of Water and Wastewater” (167) indicates present status of liquid waste m y . Fissionable material inventory, bumup analysis, isotopic Pu and U determinations are not new, and techniques have been developing over many years. What is new, of course, is the urgency of the demand for safeguards type measurements. The problems have been aired a t a number of meetings; the Karlsruhe conference proceedings (50) give an excellent picture of the problems and present solutions. LIQUID SCINTILLATION COUNTING
The technique of liquid scintillation counting continues to show growth on a broad front. For a general view of the field, the reader is referred to the proceedings of two important meetings that have appeared in hardback form. The proceedings of the symposium on the current status of liquid scintillation counting (19) consists of a number of review papers that attempt to bring into focus the recent trends in liquid scintillation counting technology. However, some previously unpublished work is also presented. The proceedings of the international conference on organic scintillators and liquid scintillation counting (67) is somewhat different in that most of the contributions are new. These two books complement each other very nicely. A general review of the liquid scintillation technique (71 references) has a Lso appeared (66). A great deal of work has been observed in the study of “gelling” systems for counting aqueous samples. The characteristics of twelve polyethoxylated surfactants were compared in a toluene scintillator system for counting aqueous tritium samples (la)). The effects of micellization and solubilization of water by nonionics are discussed. It was observed that surfactant compounds exhibiting simple I R and NMR spectra produce less quenching and have a higher tritium counting efficiency. In spite of the usefulness of gel systems, some difficulties have been observed. One investigator indicates the problem he experienced when employing a commercial “ready t o use” gel scintillator for tritium labeled thymidine samples (23). I t was determined that the solubilizing properties of the scintillator 440R
are not sufficient to bring all incorporated aHinto a detectable form; dissolution of the sample in a strong base before using the gel scintillator is recommended Also noted were two patents for new gel materials. Ethylated nonyl phenol and ethoxylated dodecyl phenol are used in a xylene base (94) and low molecular weight polyenes (18) such as polyethylene have also been described. I n the constant search for more efficient fluorescent solutes, some new prospects have turned up. A study was made of a family of aromatic nitriles (178) such as 9,10-anthracenediacarbonitrile. Although nene of the compounds examined surpassed p-terphenyl or PPO, the author suggests that other members of the family might prove promising. Tri-a-naphthylboron has been tested in both liquid and plastic media (58). Spectral characteristics and concentration effects were examined. Recent patents describe the use of 2-aryl indoles (68) and some novel oxadiazole derivatives (127)as organic scintillators. Despite the wide diversity of fluorescent solutes studied for liquid counting, the 5 or 6 “standard” fluors appear to be well entrenched in the majority of a p plications noted during this review period. Some degree of progress has been made on the ever-present problem of standardization and quench correction. The direct atsolute measurement of the activity of pure 6 emitters has been described (83). The method is based on the coincidence and singles counting of the sample in a dual phototube system and appears essentially identical to a procedure published over 10 years ago (66). I t is mentioned here since a minor controversy exists over the theoretical basis of this technique and the validity of the results obtained. The lack of readily available standards for some isotopes in a nonquenching form has led investigators to use 14C as a secondary or substitute standard; lachexadecane has been used to standardize samples (35) and l4C-to1uene has been substituted for lzQI (151). In both studies, the carbon-14 standards proved acceptable for work of moderate precision under a variety of conditions. Quench correction techniques have been studied extensively for conventional liquid scintillation counting but have not been rigorously applied to Cerenkov methods. We note, however, that the channels ratio procedure was found to be most accurate when applied to counting of 44Kin biological samples (116). Items of general interest include the use of a tin-loaded liquid scintillator to count iodine-125 with a 55% efficiency (11). A modified coucting vial is used that separates the sample from the scintillator. The liquid scintillation counting characteristics of a new RCA photomultiplier tube, type C31 OOOD,
ANALYTICAL CHEMISTRY, VOL. 44, NO. 5, APRIL 1972
were studied in detail (84). This tube used gallium phosphide for the first dynode which increases the multiplication factor from 3 to 40. The tritium energy spectrum was examined in terms of shape and distribution. An autumatic system for preparing tritiated biological samples has been designed (156). An operator drops a sample capsule in a furnace and collects the combustion products in scintillation solvent, ready for counting, a t the rate of one sample every 3 minutes. The present state of application of liquid scintillation counting is reflected in the results of a questionnaire circulated to 127 laboratories (165). On the average, 1400 samples are measured per month. Thirty-seven per cent are *H, 41% 14C, 16% others, and 6% double labeled samples. Quench correction is mainly responsible for the total average error of 3~6.1%; the internal standard method is considered the most accurate of 7 different procedures. Many other application results are tabulated. RADIOCHEMICAL SEPARATIONS AND ANALYTICAL PROCEDURES UTILIZING RADIOISOTOPE TECHNiQUES
On the basis of our previous reviews, we were not surprised to find little that is conceptually new or unique in the areas of radiochemical separations or radioisotope analytical procedures. This is not to say that work is not being done in these areas but the vast majority of the papers that we have reviewed appear to be variations on the themes of isotope dilution and exchange, radiorelease, and kryptonate chemistry. The following discussion represents a cross-section of radioisotope separation and application techniques that appear interesting but it should not be construed as being i omplete or necessarily new. Machine separations of large numbers of radionuclides remain an attractive objective for the radiochemical laboratory. An ion-exchange and chromatographic separation method has been developed that is suitable for the simultaneous determination of up to 40 elements (156). The unit is automated and requires a separation time of five minutes for four samples. If the number of elements to be determined is reduced, separation time can also be reduced without instrument modification. The performance characteristics of an automatic analyzer for tritium in urine have been described (133). The standard error in estimating the correct concentration from the AutoAnalyzer was shown to be +lZ% a t the 10 pCi/liter level. A new liquid-liquid extraction method has been developed for the separation of cerium(1V) from berkelium(IV) and other elements (116). A quaternary ammonium nitrate in xylene is used to extract the cerium from a solu-
tion containing bromate ion and dilute nitric acid. An interesting and simple method has been noted for the determination of radioruthenium (8.8). A sample solution is placed in a conical flask with small amounts of sulfuric acid, silver nitrate, and potassium periodate. The mouth of the flask is covered with a thin polyethylene film and the flask is heated on a water bath for 2 hours. Radioruthenium is oxidized to the tetroxide, evaporated by steam distillation, and fixed quantitatively to the inner surface of the polyethylene film as a black stain. Contamination ratios of other nuclides is less than 2 X 10-4. A sensitive way of detecting radionuclides on a thinlayer chromatogram is to mix a powdered scintillator with the chromatographic substrate and use @-radioluminescence on photographic film or direct photometric detection. Experiments have been reported that show the technique is feasible and that interference is not caused by the admixture of the powdered scintillators with the substrate (98). A radioisotope derivative procedure has been developed for the determination of epinephrine and norepinephrine (28). High specific activity lz6Iis used to form labeled iodoaminochromes which are isolated by column chromatography, after the addition of inactive codoaminochrome of the sought-for catecholamine. The determination of sulfate ion (2 to 100 pmoles) by replacement of iodate in la1I labeled barium iodate has been described (87). Each determination takes only a few minutes and the precision is *2.5’%. A new radioanalytical method for the assay of 0.1 to 10 pg of arsenic is based on the homogenous reaction between arsenic(111)-diethyldithiocarbamate and labeled arsenic(II1) iodide in carbon tetrachloride (186). The procedure has been applied to the determination of arsenic in sulfuric acid. Iodine has been determined by a radioactive kryptonate procedure (174) and by radioelectrochemical isotope dilution (1.86). A radioactive kryptonate of thallium has also been used for the determination of pH (176). Hydrogen ions react with the surface layer of the kryptonate and release active krypton in amounts proportional to the hydrogen ion concentration of the solution. New and more efficient assay procedures have been developed for uranium and the transuranium elements in process solutions and environmental samples (164). The preparation of mercury derivatives of fluorescein labeled with 197Hg by direct irradiation of the mercuricompound in a reactor has been reported (86). Often tried but almost always unsuccessful in the past, such a technique appears most attractive to chemists studying mercury and other
heavy metal pollution. Another paper (36) describing direct separation and enrichment of the product of a neutron capture event-in this case Ir2Pr from natural Pr loaded onto a faujaaite zeolite-would seem to point the way to isotopic enrichment through simple techniques. Present interests and projected prospects in nucleonics should encourage every radiochemist to remain enthusiastic; the problems of today and tomorrow are truly analytical ones. For those few jaded personalities discontent with the conventional, we can offer these last few items gleaned from the literature as follow-up subject for potential research. Do cosmic phenomena (radiations from outer space) influence the growth of living creatures (180)? A report (80) that the environment can change the half-life of larI could be the source of future environmental research. Two uses of radiochemicals to “overthrow” accepted statistical theories have also appeared: using a radioactive source and counter, a researcher in parapsychology has shown it possible to influence the decay by psychokinesis; (267) another report, presented a t an ACS meeting maintains that “better than statistics” counting results can be consistently obtained in a I4C experiment (8). Finally, having reassured our readers in the last review that on the basis of a French study, there was no evidence of psychological disturbance from working with radioactivity, we must now prepare you for a grimmer prospect. A survey of longevity among scientists shows that persons working with radiation have the lowest life span of all disciplines studied-61.8 years us. 76.7 years for the longest lived group, archeologists (101 ). Unemployed radiochemists may derive some comfort from the fact that they may live longer-if not as satisfactorily-as their more fortunate colleagues. Seriously, these results would appear to warrant study by appropriate professional groups; in fact presentation of this problem to the American Chemical Society might provide a real indication of depth of the latter’s new interest and concern in the welfare of its members. ACTIVATION ANALYSIS
The budgetary restrictions of this period have reflected necessarily on the volume-and even on the spirit and approach-of the new activation analysis developments. Most efforts were devoted to the refinement of older techniquev or to find new twists for both old and recently developed methods, rather than to uncover striking new techniques. The nuclear microprobe may now be considered a definitely established analytical method for light elements, and
some important difficulties in chargedparticle activation have been solved. But, amazingly, the method that many would have considered an exhausted “old work horse’’-neutron activation analysis-has provided the most interesting surprises during this period. Applications such as %*Cfhave broadened while a t the same time we see a trend toward highly sensitive and accurate multielement analysis. This trend is apparent in all analytical chemistry and reflects the increasing demand for such data in the biomedical, environmental, and space sciences. The challenge the analytical radiochemist faces, therefore, is to provide impensiuely such multielement quality determinations. Developments in neutron activation analysis during this period have aided in meeting this challenge. Nuclear Microprobe. This method capable of measuring impurity depth profiles-almost a curiosity before-is beginning to find regular usage; profiles of oxygen in zirconium (166), and of carbon in steel (31), were determined by proton bombardment. Deuterons were used to determine bulk nitrogen (6), and also nitrogen and carbon (48) in various metallic matrices. A drastic drop in the price of “C-labeled compounds resulted in their increased application in stable tracer experiments. A full “National (Los Symposium on Carbon-13” Alamos, N.M., June 1971) covered this subject. Thus, for the first time proton-reaction analysis was applied to biological samples (148) to determine l*C, lacisotopic abundances, and N/C elemental ratios; a mathematical formulation was also proposed (147), that facilitates this method’s calculations. Research continued on proton scattering methods (&) but, perhaps, the most promising microprobe development is heavy-ion excited X-ray fluorescence. An extremely sensitive method (10-l2 gram), based on this phenomenon, was proposed by Swedish workers (76), and is presently being tried in many laboratories-with particles ranging from protons to argon nuclei-on a number of matrices. Charged Particles and Photons in Steady State. A good number of papers have been published on these methods, which have already reached routine application. We cannot review them here, but credit should be given to such groups as the University of Lyon, France (9),and the Southern Universities Nuclear Institute, South Africa (IO), for their diversified and consistent work in this area; unfortunately, publication has mainly appeared in local reports. Useful innovations were suggested by three other groups, also very active in charged-particle activation. Texas A
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and M workers used time-dependent, variableenergy bombardments to study trace-element distribution in samples (150), while the Berkeley group (University of California) studied oxygen depth profiles in silicon, by aHeactivation analysis (go), and developed reliable oxygen isotopic standards (89). In addition, accelerated tritons were applied for the first time in activation analysis, by the productive group a t the C.N.R.S. (France), to determine oxygen sensitively on metal surfaces (15). Cyclotron beams were pulsed for analytical purposes in England (41), where a timely conference was also held on chemical, metallurgical, and biological applications of these accelerators (5). Progress in photon-activation analysis has continued, slowly but consistently, in the laboratories that first promoted it: C.E.A., Saclay (France) (52) and the National Bureau of Standards (10.2). Other analytical facilities like that a t Gulf General Atomic’s Linac (28),and the recently installed system a t the Oak Ridge Electron Linear Accelerator, complement these installations. Aside from the use of these large machines, an interesting “bootstrap” approach-based on bombardments with an 80-kCi BoCogamma source-has reached detection limits in the milligram region (179). However, despite some advantages over charged-particle activation, the photon technique appears to be limited in its growth by its dependence on expensive accelerators. Neutron Rally. We expressed surprise before, in these reviews, about the seemingly very long half-life of neutron-activation creativity. Not only are we reaffirming this fact today but, moreover, we find reason to credit this classical technique with the most interesting contributions of this period. As always, useful work on specific techniques continued in several laboratories. Though no mention of these will be made, the patient and fruitful dedication of the group a t Ghent University (Belgium) over all these years deserves special recognition; their work may be followed in Analytica Chimica Acta. The previously predicted increase in applications of 25zCf has occurred. The usefulness of these sources in analysis was appraised (146), an activation method for environmental, mineral samples (134) was developed, and a radiative-capture technique for space exploration reported (173). Great interest in these and other neutron sources-e.g., Po-Be for prompt-reaction analysis ($)-has continued, and the subject was exhaustively explored a t a meeting (125). Original work on electrostatic fast-neutron generators keeps appearing in the literature. Methods to determine deuterium in heavy water by recoil (138),and to correct for photon 442R
self-absorption (III), have been published, and the analytical potential of 3 MeV neutrons evaluated (1.2.2). The most interesting developments have occurred in reactor-neutron activation analysis. Here the stage was set by continued research on recent chemical innovations, such as irradiation of frozen samples (SI), substoichiometry (61), and fast removal of radioactive sodium, potassium (172), and phosphorus (165). Good news has come from forensic activation quarters. But the development, most relevant to present time demands on analytical chemistry, has been multielement activation analysis. Forensic and Biomedical Picture. Incipient among activation analysts a t the time of our last review was a healthy attitude that aimed a t avoiding misuses of the method in court. This attitude seems to be catching on. Though the unfortunate “gammaspectrum matching” technique was still used in a couple of cases (158, 168),great efforts were generally made to accumulate massive analytical data, and to interpret them statistically, to provide the courts with scientifically sound evidence for criminal identification. Gulf General Atomic workers published results of comprehensive chemical-statistical studies on paper, paint, bullet lead, and gunshot residues (99). The Aldermaston group-whose classic work on hair samples (1967) set the pattern for such studies-has now investigated 22 elements in each of 540 glass sapples, for the same purpose (60). The heralded IAEA document on method reliability has not yet been published by the international committee of forensic activation analysts; but an excellent exhaustive, and authoritative critical study on evidentiary uses of activation analysis, was published (78). Written by an attorney with a university technological background, this law article should provide a good guide for the legal profession. The increasing emphasis on cancer and other biomedical research has been reflected only slightly in the activation analysis literature. However, interesting applications to the diagnosis of cystic fibrosis (45, I l l ) , and t o traceelement analysis in alkaloid cigarette tobaccos (129) have been reported, as well as epithermal neutron activation of frozen thyroid samples (33). The present role of activation analysis in biomedical and public health research, and some of its novel methods-such as prompt-neutron and proton-reaction analysis-were reviewed in a recent symposium (169). The Environment, the Moon, and Multielement Analysis. Not long ago, activation analysts used to prefer to call themselves nuclear chemists, rather than analytical chemists. Con-
ANALYTICAL CHEMISTRY, VOL. 44, NO. 5, APRIL 1972
temporary concerns about environmental quality, biomedicine, space exploration, and forensic chemistry, have changed this pattern. The progress and the very existence of all these new endeavors rely so heavily on analytical chemistry, that this discipline is no longer considered a technological aid, but it has been called to play a primary role in today’s science. The new prestige has brought a new challenge, however. There is a clear and increasing need, in all the above areas, for multitudes of inexpensive determinations in a large variety of samples. This change finds activation in a fortunate position to answer positively to this challenge. Automated techniques, involving germanium gamma-spectrometry with computerized data-handling of results, allow nondestructive multielement analysis of numerous samples in a relatively short time. Despite the investment in the necessary equipment, the cost per determination has been proved to be low, because of volume and simplicity of operation. Environmental studies, and some renewed interest in geology-sparked by Moon exploration-have opened the doors for the above developments, perhaps the most important of this period. Nondestructive methods were used by different authors t o determine thirtythree ( 4 7 ) , twenty ( I @ ) , and sixteen (136) elements simultaneously in air pollution particulates. Instrumental multitrace methods were also developed for petroleum (162, 163), particularly for the purpose of oil-slick identification (34). The worldwide concern about mercury contamination, resulted in a multitude of articles impossible to list here; however, a revised compilation of radiochemical methods (149) and an interesting study-review on the subject of mercury in the environment (183) were published. Among numerous meetings on environmental subjects, the 1,IEA (Salzburg) Symposium (129), and American Nuclear Society Topical Meeting on Kuclear Methods in Environmental Research (Columbia, Mo., August 23-24, 1971), deserve special mention for their relevancy t o our specialty. Multielement activation analysis was also used to determine 59 elements in rocks (117 ) and 39 in precious minerals (S), while the application of nuclear techniques to mining was reviewed in Poland by an international panel (128). Finally, the importance of these methods in RIoon exploration became quite apparent in the tn o profusely publicized “Apollo Lunar Science Conferences (97,98). Research sponsored by the U.S. Atomic Energy Commission under contract with the Union Carbide Corporation.
LITERATURE CITED
(1) Adams, J. A. S., Gasparini, P;:
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T
HIS REVIEW SURVEYS recent d e velopments in quantitative analysis of the elements in organic compounds. It follows the previous review (119) and covers the information and publications which came to the attention of writers during the period from October 1969 to October 1971. After vigorous promotion of automatic CHN analyzers by several manufacturers for about a decade (118), two commercial machines are now entrenched in this country. It is of interest to note that foreign instruments have not penetrated the American market and that American manufacturers are not planning to develop automatic analyzers for the other elements. The users of commercial automatic analyzers still make remarks on their “down time,” which necessitates a stand-by instrument in case of emergency. Research publications that appeared in the past two years seem to concentrate on simultaneous determination of several elements with one weighing, organometallic compounds, and the elements with which it is difficult to get accurate results such as oxygen and fluorine. Automated procedures continue to receive attention. This also accounts for the voluminous literature on electroanalytical and other physicochemical methods of finish, since they are amenable to automation.
CARBON AND HYDROGEN
With the emphasis on automated, rapid procedures, a number of papers
have appeared dealing with this topic. Gel’man (76) analyzed various types of compounds by “wide tube” automatic, dynamic combustion. Sels and Demoen (190) have given details of the mechanical and electrical modifications necessary to convert the Coleman Model 33 Analyzer for the determination of C and H. The same authors (191) later modified their method for use with this instrument t o eliminate systematic errors and to reduce the work of the analyst. Stainless steel absorption tubes were used to ensure rapid temperature equilibration and an automated system for connection and disconnection of the absorption tubes and transfer to the balance was developed. Merz (133) reduced the time for analysis to 8 minutes by passing the combustion gases through a cold trap to freeze out the water and then absorbing the carbon dioxide in alkaline solution. This solution was titrated automatically in a nonaqueous system and the volume of titrant was displayed digitally and printed out. In a separate cell, the water was converted to carbon dioxide and titrated as above. The main disadvantages of the ClercSimon method have been overcome (164) and a more accurate determination of the water content of the combustion gas was obtained by collecting a known volume of the gas a t supraatmospheric pressure instead of in an evacuated apparatus. Bailey and Brown (9) recommended covering the aluminum capsules used with the Perkin-Elmer CHN Analyzer with plat-
inum gauze to avoid damage to the combustion tube. Trutnovsky (223) improved the Heraeus micro combustion apparatus by replacing the power relays in the original circuit with triacs. These relays were short-lived and produced noise when switching. Oda, Ono, and Matsumori (162) modified their double tube system for sample decomposition to allow for a more compact apparatus. Either a conventional or gas chromatographic finish was employed. For carbon dioxide, a spectrophotometric’finish could also be used which involved passing the effluent gas through alkaline alizarin yellow GG and measuring the extinction a t 450 nm. While automated procedures received a great deal of interest, studies continued to be made on the nature of the combustion process and the effect of various tube fillings. Buis and Schroder (24) have shown that it is possible t o obtain correct hydrogen values when using an external absorbent for removal of nitrogen oxides, provided that the whole anhydrone filling of the waterabsorption tube was heated a t 8090 “C. Fildes (63) discussed the role of a wide range of fillings and recommended tungstic oxide, silver tungstate, and permanganate as absorptive and oxidative aids for certain refractory compounds. Pechanac and Horacek (162) studied the catalytic efficiency of cobalt(I1, 111) oxide obtained by thermal decomposition of cobalt(I1) oxalate, Methods for the preparation of both the powdered and solid catalyst were given.
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