Jexe 1968 JOA WARBURTON AND L. G. YOUNG Neutron Activation Procedures for Silver Analysis in Precipitation J. A. Wansurron axp L. G. Younc Desert Research Institue, Univesity of Nevado, Reno (Manuscript received 15 January 1968) ABSTRACT Laboratory techniques have been developed for concentrating and isolating silver fram aqueous samples ‘When these concentrated samples are activated in a thermal neutron Hux of 9X10" n em*see~*quantitative measurements down to 10-* gm masees of silver can be made. When Liter samples of water are used, the lower limit of detection of silver in the sample is about 3X10" gm cm”* concentration. Typical Ag con- centrations being observed in snow collected in the western United States range from this ower limit to 10-4 gm cm, the majority being between 10"? and 10°. The lower limit does not therefore appear to be serious facto in silver determinations in snow collected at ground stations, The system described is @ non- destructive one, the accuracy of measurement using y-ray spectrometry being 1, 2, 10 and 80% for ‘masses of silver 10°, 107, 10-# and 107 gm, respectively. By using a 24sec half-life radioisotope for the Ag determination, the cost of activation and turnaround time on samples is kept to & minimum, Data 433 analysis is computerized and rap 1. Introduction Despite a large number of investigations into both organic and inorganic cloud-sceding agents, silver iodide at present still emerges as the most useful agent for large-scale areal seeding work because of the large numbers of active particles that can be conveniently produced per gram of the component, cipitation for the presence and concentration of the seeding substance, it may be possible to demonstrate the effectiveness of the seeding agent on the production ‘of precipitation, and to find what area is being affected. ‘There are serious meteorological problems associated ferpreting the presence of seeding agents in precipitation, which are not discussed here. The detec- tion of the substance itself in the precipitation is a trace analysis problem of a high order of difficulty ‘this paper, one useful technique is discussed in detail, 2. The problem of sensitivity Ti silver iodide is released for cloud seeding either from airborne or ground-based generators of the usual type, simple calculations indicate an expected. concen- tration in the precipitation of the order of 10- to 10 gm mI. By far the most sensitive way of detect- jing such small, and even smaller, quantities of this substance is by the observation of its ice-nucleating properties. Vonnegut (1949) showed that minute hydro- phobic particles as small as 10 gm could be detected by observing their ice-crystal-producing property. Later, Tsono (1961) demonstrated that colloidal sus- pensions of such particles with masses probably around 10" gm, when injected in suspension into a fog-illed cold chamber, could also generate ice crystals in a similar manner. ‘The success of Isono’s method for detecting the presence of the Agl colloidal particles depended on the extremely low solubility of this chemical in water 2 parts in 10"). By introducing a small excess of iodine into an aqueous solution of silver iodide it has been shown that it is possible to suppress the solubility slightly to about 6 parts in 10°. The major difficulties involved in using this technique have been described by Warburton (1963, 1965). Under the majority of ci cumstances expected in area-type, cloud-seeding experi- ments, the concentration of the seeding agent in the precipitation would be less than this critical value G parts in 10) and hence some form of concentration {is needed before this method of detection can be used. A further complication in using the ice-nucleating property of the silver iodide as the means of analysis is that other insoluble salts, including iodides, are effective in initiating ice-crystal growth. Ton-exchange methods have been employed, not only to concentrate but to isolate the silver ions from solution for analysis purposes. Descriptions of these procedures and the results obtained by using them have been given by Warburton (1965) and by Warburton and Maher (1965). These ion-exchange extraction procedures have led ditectly into the current work in neutron-activation ‘analysis described in this paper. ‘Activation analysis using thermal neutrons provides a highly sensitive means of detecting either silver oF iodine by producing radioisotopes from the natural silver and iodine. This technique, like others, has many apparent limitations but from the point of view of analysis of moderate volume samples of precipitation,434 [ACTIVITY IN OF MAXIMUM OBTAINABLE 7 any JOURNAL OF APPLIED METEOROLOGY Vor 7 my IRBADIATION TIME io. 1, Activity of isotope produced as a function of i it appears to provide advantages over the methods using the ice-nucleating property of the silver iodide. From the point of view of analysis of individual ice crystals and hailstones, other methods such as the “pig tail? technique of Koenig (1960) would appear more readily feasible at this time, although further develop- ment of neutron-activation methods may ultimately make it equally as attractive. Both silver and iodine are highly sensitive to neutron activation analysis. How- cever, in view of the likelihood of a considerably higher natural background of iodine than of silver, it seemed wiser to choose silver as the better analysis element. 3, Choices of method for neutron activation analysis of silver The natural isotopes of silver and their ebundances are Ay! (31.35%) and Ag (48.65%), neither of which is radioactive. When placed in a nuclear reactor and subjected to fluxes of neutrons both of thermal energy (~0.025 eV) and higher (up to 10 MeV), many reactions occur, including (n,y), (nyn'), (0,2n), (n,p) and (na) [see ‘Lukens (1964). ‘Table 1 shows the majority of the isotopic reactions for silver which can and do occur in a reactor flux together with the more sensitive y-ray emissions accompanying such reactions. The half-lives (74) of the isotopes produced are given ia column 4. ‘Many of these isotopic reactions also involve other emissions such as B~ particles, but these are not included. for the purpose of this discussion as the detection system is concerned principally with 7-ray scintillation spectrometry. sation time in half-lives. The probabilities of these reactions occurring and the consequent sensitivities vary considerably, in fact by many orders of magnitude, The factors affecting these reactions include the neutron absorption cross section of the atom for the reaction concemed, the neutron ffux available for the reaction, the activation time and the half-life of the isotope produced. ‘The decision on which reaction to use for the analysis, ‘obviously depends on the specific problem. From the point of view of analysis at the most sensitive levels for aqueous samples collected in weather modification work, the choice would appear to be between the two (n,7) reactions for the Ag isotope of silver. Let us consider these specifically. ‘Tate 1. Isotopic reactions for silver. Primary Target Product, led : r energy fzotope Reaction —_aotope site (MeV) Ag (np) As 23 min 0.63 * na Sorm 44 sec 0.093 (man) Ag Rbdays St 2imin OL (op) Page 021 me) Rh "4 inOSt ma a 253 days 0.66 fe kee Th om) Ose Gay AE min as op i ‘amin 019 ae 136 oss (na) Rbe 22h 0.515 Raw 30sec ostJoxe 1968 Joa. a. Ag (ngy) Age This reaction is the one which produces the long: (253 day) isomer of Ag", the metastable state. This is ‘4 thermal neutron reaction and the thermal neutron absorption cross section for the reaction is about 3.2 barns (1 barn= 10 cm). Fig. 1 illustrates the activity ‘of an isotope produced (as « per cent of the maximum obtainable) as a function of the irradiation time in half-lives. It can be seen from this figure that activation for one half-life produces about $0% of the maximum activity obtainable. This particular reaction (r= 253 -days) is impractical. For realistic activation times, the per cent activity produced will be approximately lin- ‘early related to the activation time as a fraction of the halflife Fig. 2 shows the decay scheme for Agi#™. This scheme involves the emission of many y-rays with different energies, some emitted in coincidence, opening the way to highly sensitive 7-7 coincidence counting methods which tend to offset the disadvantages of long half-life and relatively long irradiation times. It is also possible ‘to use post-irradiation radiochemistry for separating the silver from other interfering radioactive elements. The combination of these factors and others has shown that it is possible to detect down to 10-* gm of silver with relative ease by using this particular reaction for the analysis 3B, Agi (nj7) Agr? This also is a thermal nentron reaction. ‘The half-life of this isotope of silver (Ag!) is 24 sec. Reference to Fig. 1 shows that it is possible to reach saturation for this reaction after activation for about 3 min, However, again the investigator must choose the most advantageous activation time, considering such things as other elements present in the sample, The thermal neutron absorption cross section for this reaction is high (113 barns). Fig. 2 also shows the decay scheme of Ag", The short half-life of Ag makes the use of postactivation radiochemistry difficult but pre-activation chemistry can, in many ways, make up for this. Again the com- bination of these many factors enables an investigator to detect down to 10-* gm of silver with a reasonable amount of effort In summary, there are two relatively clearcut ways to proceed in sensitive analysis for silver. Bach method hhas merits and disadvantages which balance one another to the point where the readily attainable sensitivities are alike (around one nanogram). For some field experi- ments where atmospheric contaminants may be more plentiful, one approach may be more suitable; for different field experiments, the other approach may be better. ‘The remainder of this paper will be concerned with the laboratory and activation procedures used by the authors in analyzing for silver using the 24-sec hall-life WARBURTON AND L, G, YOUNG Aged io, 2, Radioactive decay schemes for radioisotopes Ree anes isotope Ag" obtained from the reaction Ag” (ny) Ag’, Tt also includes results of activation of snow samples using this specific nuclear reaction. 4, Pre-activation procedures Since the halflife of the isotope of silver under study is short, isolation and concentration of silver is carried out prior to activation. Ton-exchange processes are used to do this. A 0.5-gm of Amberlite CG120 (Na) resin is used in the analysis of each sample Equivalent resins of other manufacturers are indistinguishable in perform- ance from the one presently in use, The resin is 200 mesh grade and is bedded down in the usual manner into @ column 0.7 cm in diameter and about 2 cm in depth. The ion-exchange resin is regenerated from the sodium (Nat) form to a saturated NH form using NHANOs in aqueous solution, It is essential that the * fons be removed to a considerable extent, as this clement can cause strong interferences in the subsequent activation process. It is well known that the Nat content of rain water is usually high compared with other elements and since the NH¢ ion is higher on the sensitivity scale than a number of other cations includ- ing Na*, K+ and H+, the regeneration to the NH¢+ form is done at least partially to overcome the problem of the resin taking up these ions from precipitation samples. a. Collection of Ag* on resin ‘The rain or melted hail or snow sample is dripped slowly through the column at a rate of about 5-10 em? min". The pHT of the sample is first adjusted to about 3 by the addition of acetic acid. The manner in which ‘Ag* ions in solution undergo exchange on the resin, the efficiences of collections and the ionic distribution on the columns have been outlined in an earlier paper by ‘Warburton (1965). The collection efficiencies for silver of these strong sulphonated polystyrene resins is as high (90%) after regeneration into the NH¢* form, as was the case for the H* form of the resin, After exhaustion of the Ag* ions from solution on to the resin, it may be removed when desired at any later time. This is ofELUATE VOLUME (rt) Fi, 3. Percentage elution of Ag* by 0.1 NHCNS from jon-exehange colums leaded with 10-©10- gm quantities af ipncercinna am 4 particular value in field operations where it may be necessary to remain in the field for some days and storage and carrying of samples (particularly rain- ‘water) can become a serious problem. 8. Bhuion of Ag* from ion-exchange resin The removal of the silver from the ion-exchange column is now done differently from that described in earlier papers. In order to analyze for silver by an ice crystal nucleation process, it was considered necessary to remove the silver from the ion-exchange resin with a soluble salt having an anionic radicle which also gave a soluble silver salt. As a result Ba(NOs)2 was used. This problem no longer exists and the requirement now is to use a soluble salt which will give highly insoluble silver salt and yet not introduce elements which have sensitive activation products, Ammonium thiocyanate is being used for this purpose. A number of the first samples submitted for activation were blanks together with samples of chemicals being used in the laboratory Procedures. Stall quantities of silver were detected in some of these. This contamination was finally traced to the NHCSN in which small quantities of Ag (pre- sumably in the form of AgS) were present. A silver-free source of sulphur was located and NA,CSN made from JOURNAL OF APPLIED METEOROLOGY Vouume 7 ‘Tans 2. Collection and elution effciences for frst § ml of elute for various exchange column loadings. 0.5 M HNO, regeneration Exchange column Collection Elution oa eficeney ——_efiieney (em Ag) © (2) iF 95 8 a 93 87 ioe cy a 10 -410°6 gm Nat 95 8 10-4 10-¢ gm Net 95 82 I 95 5 1 95 3 io" 95 0 10 9s 8 ios 86 83 io o a 10" 95 a 10» % a 10-4.10-* gm Nat 93, 2» 1010-8 gm Na o aS 0.8 A NHANOs regeneration 10 93 7 0 30 8 10-5410" Net 93 7 10-10" Nav 98 i 107 2 ct 107 98 3 it. No further contamination from this source has occurred. ‘Table 2 shows results obtained for the percentage yield in the first 5 ml of eluate when eluting Agtont from 0.5-gm columns of CG120 (NH,*) and CG120 (H+) over the range of column loadings from 10-* to 307 gm of silver. The results represent an improvement in elution efficiency by a factor of 10 at the 10-® gm level and a factor of 200 at the 10~® gm level over the values obtained using 0.05M Ba(NO,)s solution, The flow rates used here did not exceed 0.5 om! min~!, For ‘most efficient operation, it is desirable to remove most of the excess uid from above the surface of the column bed before adding the NH.CNS. This can be introduced. along the wall of the glass tube containing the ion- exchange column with a hypodermic syringe without disturbing the surface beads of the resin column. The NHCNS is added slowly to allow as much contact time with the resin as possible prior to the eluate being collected, ‘Most of the Agt is removed in the first 5 ml volume of eluate, the average percentage yield in this and successive 5 ml volumes of eluate being given in Fig. 3 for column loadings between 10-* and 10-® gm. In a number of tests, microgram quantities of sodium (Na+ ions) were added to the samples before the ion-exchange collection. In the cases where the resins have been regenerated with nitric acid (H), the sodium was collected in the resin and subsequently appeared in the dluate with the silver. When NHNOs regeneration occurred, no detectable sodium appeared in the eluate with the silver ions, NHNO, regeneration is now used exclusively for field sample testing. All of these dataJose 1968 J. A. WARBURTON ‘were obtained from monitoring experiments using aqueous Ag!" NOs of specific activity 3 Ci gm and counting in a well-type NaI(T?) scintillation counter with 512 channel analyzers The first S ml of eluate from each sample are collected fon a small piece (15 mg) of Parafilm plastic stretched cover the top of a small beaker. After evaporation to Gryness in a sealed drying unit the sample is sealed off and placed in a polyvial “rabbit” for subsequent activa tion. The “rabbits” are chosen to suit the fast transfer vacuum system for transporting samples in and out of the reactor core. 5, Neutron activation procedures a. Isolope production When atoms of an element are bombarded with a flux of neutrons, some of these atoms capture neutrons in their nucleus and are converted to another isotope of the element. In general, these newly produced isotopes are radioactive and decay by emission of some other particles or radiation. ‘At a time dé after the commencement of irradiation, the number of atoms 1V of the isotope resulting from the nuclear reaction is given by aN=dNy-\Nal, a where Ne is the number of atoms of the new radio- nuclide produced by the irradiation and the second term on the right-hand side of the equation gives the number of atoms which have decayed in time df, Sub- stituting for Ne we have dN = fnodt~Nodt, @ sano acre aren a see asasiaion rr AND L. G. YOUNG 437 Standord Ag Activation Gr tot ‘Gin Ag Activated ic. 4, Net counts in 066 MeV --ray photopeak of Agi as a Tincion of mass of cee Atuveeas P where fis the fax of neutrons em” sec“, w the number of atoms bombarded, © the neutron capture cross section in barns, ¢ the neutron irradiation time in seconds, and \ @ decay constant, i.e., X= (In2)(r4)%, where ry is the halflife. ‘At any time 1 after irradiation, the number or radio- active atoms present is then given by wef fw IL ro = ae ae TIME AFTER IRRADIATION (mine Fic. 5. Vatiation with time after iradiation of Ag*/Ag™ activity ratio,438 JOURNAL OF APPLIED METEOROLOGY Voveme 7 wy a i wt 2 2 SRR, Ew Ew “ . : ane : ain : a w w Co EY ey Os os ee 12 15 te ai 2427 30 ENERGY (Me) ENERGY (Hav) w we we 2 z Et Biot egy stan \ bd we oes oa op? aa) aa a7 a0 oes ob oh WS ea an ay a0 ENERGY (MeV) ENEROY (Mev) Fi, 6. y-ray spectra for activated samples of 10°F, 10-* and 10-* gm masses of silver. (3) ind Calculations are made for silver and other elements in the sample after some prior knowledge reveals which other substances are present. A compromise is ulti- mately reached in which the maximum available sensitivity is obtained for the silver by controlling the various parameters carefully. Under the present circum- stances, in which most of the interferences have been removed, the following procedures have been adopted. (i) Activation is in a flux of 4.3% 10" neutrons emt sec~!, the normal TRIGA Mark I reactor flux of thermal neutrons when operating at a power of 250 kW. (ii) Activation is for a period of two half-lives, vis., 48 sec for the Ag". (Most of the other isotopes at present appearing in the y-ray spectra have longer half-lives and it would be a disadvantage to activate for greater than this time.) ii) ‘The activated sample is transferred in a time less than 2 sec from the core of the reactor to the counting room. (iv) The sample is removed from the polyvial in which it was activated and transferred into a similar unactivated polyvial. (v) Approximately one half-life after the end of irradiation, the saruple is counted by one of two methods for period 0.3 min live-time. It is either (a) placed 0.5 inch above 3 inchX:3 inch solid NaI(T) scintillation crystal, or (b) placed in a well of 3 inchX3 inch well- type Nal(T?) scintillation crystal.Joxe 1968 J. A. WARBURTON One of the principal reasons for delaying the start of counting for Ag is to allow specific isotopes to decay. One of these isotopes (N") is produced from large quantities of oxygen in the polythene wrappers. This isotope has almost completely decayed after 25 sec. If the dead time of the multi-channel analyzer exceeds 50%, it is necessary to wait even longer for the overall activities to decrease before counting begins. Large dead times in excess of 30% can lead to serious gain shifts in the amplifiers and a general broadening of hotopeaks in the y-ray spectra. b, The need and use of standards Some portions of the analysis procedures are chemical, some physical. In both, the reactions and measurements proceed with varying degrees of efficiency. In order to monitor these efliciencies and limitations in. measure- ‘ment, the use of standards is imperative, Such standards enable accurate quantitative data to be obtained for precipitation samples collected from field experiments. As there are several steps in the handling of a pre- cipitation sample through to the point where it is activated and then counted, itis important to know the correction factors which must be used to convert the apparent values of Ag content to the actual values for the precipitation samples studied. This is achieved by monitoring the several steps using a trace quantity of Agi NO, which, at a maximum, would constitute no more than 5% of the lowest detectable amount of Ag in the precipitation. The Ag isolation procedures can therefore be interrupted at any point and monitored. Even after the neutron activation stage, the sample can be returned to the pre-chemical laboratory and mea- sured again, as essentially no new Ag’ is produced in the 48-sec irradiation time used for the determination of the Agi, As an example, if 10-7 gm of Ag is present in the sample, Eq. (3) shows that on the average, only 10* atoms of ‘this Ag are converted to Ag™™ via the reaction Ag (nyy) Ag" in the 48-sec period. Analysis procedures at the reactor are considerably simplified by the activation of known standards of Ag at the same time. There are possibilities that changes ‘occur from batch to batch in such things as thermal neutron flux, transfer times, counting geometry of spectrometer, and times between irradiation and count- ing. If known standard samples are irradiated at the same time as the unknown samples, most, if not all, of these variables can be eliminated from the calculations. Fig. 4 shows results obtained from activation on a number of different occasions, of nominally equal standards of 10-7, 10-6 and 10? gm of silver, and measured in the ‘two counting configurations. The diagram plots corrected net counts in the silver photo- peak as a function of the mass of silver activated. The counting efficiency of the y-ray spectrometer ‘used for these measurements is affected by a number of factors. These include the size of the NaI(P0) crystal AND L. 439 G. YOUNG gai i COUNT /MNAT END OF 08 MN, ACTVAION a i Enenor cas) vse of Tic. 7. Reduction in y-ray speci Background Dy "Mavi ‘of Emm thick plastic Parafiim ‘membrane plastic, sheeting, a used, the counting geometry of this crystal, the type of lead shield used, the laboratory radioactive background, and the emission energies of the y-ray’ or energetic 6's being detected. Known activities of Cs-137 (0.662 MeV) and cobalt-60 (1.17 and 1.33 MeV) gamma energies are usually used for the purpose of calibration of the linearity of the amplifiers and for the determination of efficiency and optimization of counting geometry. If the total mass of silver present in the sample being activated is less than 10 gm, counting can usually. commence within 25 sec after activation ends. The activity of the Ag isotope at the end of activation is approximately thirteen times that of the Ag (pro- duced by the reaction Ag (nx) Agi. Standard samples of silver over the range of 107-10? gm are activated in the same batch with the unknown precipi- tation samples. As a result, a direct comparison of the ‘unknown with the standard can be made without any further concern for the Ag'* contribution to the activity being counted. i, however, the total mass of silver present in the sample exceeds 10~* gm (which it has in some of the snow samples analyzed), the activity of the sample after activation can be so great that it becomes neces- sary to wait several minutes before counting can hegin. ‘This is because of the large dead times produced in the counting equipment. Fig. 5 shows the ratio of the activity of Ag®™ to Ag" as a function of time after ieradiation. It illustrates how this ratio changes and why direct comparisons with the 10-710 gm standards are no longer valid for the silver mass determination. In these cases, it becomes necessary to perform separate calculations based on the activity of the 2.3-min half-life ope Agi as well as that of the Ag!®. Examples of440 JOURNAL OF APPLIED METEOROLOGY Vouume 7 ry wt w pave 3 3 i Eat f 8 8 oe w ww @ 03 66 op 12 Wo 18 a) a4 27 a0 O03 Ge op 1h WS we a) as ay a0 ENERGY (MeV) ENERGY (Mev) a rr es a i 3 Eat = 8 g ow oe w w 0 03 06 op 12 15 18 21 24 27 30 ENERGY (Mev) 0 03 os a9 12 15 is a) 24 27 30 ENERGY (Mev) Fic, & pray spscten of precipitation sample extracts for three areas of western United States, Masses of Ag ~3X10~ gm. the spectra obtained from 10~?, 10% and 10 gm standard samples are presented in Fig 6. Some time was spent in finding a suitable plastic material in which to place the sample for activation. A number of substances were tested for chemical content, sealing properties and plasticity. A thin commercial plastic sheeting was used for a while, but Parafilm was finally chosen for regular use. Figs. 7a and 7b demon- strate the reduction in background for the 7-ray spectra achieved with the better plastic material in which the samples are activated. The principal photopeaks occur at 13. and 1.8 MeV and are due to Na and AF, respectively. The overall reduction in intensity through- out the whole spectrum of 6b is essentially due to decrease in the mass of plastic activated. The major portion of the background, i.., the energy range O-1 MeV, is probably Compton scatter from the Na* and AB.” Hence, this reduction in background results principally from a reduction in sodium and aluminum in the plastic. Fig. 6a is produced from activation of mm plastic sheet, and Fig, 6b is that obtained from similar activation of about 15 mg of Parafiim plastic. 6. Calculation methods ‘The activated sample, having been placed in the ‘pray spectrometer, is counted for a fixed live-time period, usually 18sec. At the end of counting, the stored information in the multichannel analyzer is printed out on paper tape and on punched cards. These data cards are coded and have been analyzed with aJone 1968 J. A, WARBURTON AND L. G. YOUNG au ’ Ww ” Epa) v ave ‘counts rea MINUTE COUNTS ree MINUTE w a oa 08 oy 12 15 Ye 2) 24 27 30 Cae ae ae Pons ve wt wt Bitte ga = wt dai an : nove a ; Et wn z Ej ei w w a o's 0 of 12 LS 18 2) 24 27 30 tty 03 06 of 12 Ts 18 2) 2% 27 30 ENEHGY (We) ER (ue Fie, 9 say spectra of precipitation sample extracts for four areas of western United States. Masses of Ag ~10-7 sm. PDP-8 digital computer. The analysis involves cor- recting the raw data by subtracting the Compton scatter background, correcting for radioactive decay, ‘These spectra represent detection of silver in the range, 3.7X107 to 1.7X10-* gm. As the volumes of water in the samples are between one and two liters, this comparing with standard activated samples, and finally, represents concentrations of silver between 45X10 determining the silver concentration in the original and 10-! gm mi! precipitation sample. For a 1-2 liter water sample, the minimum detectable concentration, therefore, is around 3X 10~" gm mit, 6. Some silver concentrations in snow from western assuming a typical transter efficiency of 60%. Walted States In each of the spectra presented in Figs. 8, 9 and 10, Approximately 250 snow samples have been collected the number of counts per minute recorded by the from several locations in the western United States, analyzer in each energy interval is plotted as a funetion Some of these are from areas where cloud seeding with of the y-ray energy. Each graph has been corrected so silver iodide has been carried out. that the counting rate plotted is that which would have igs 8, 9 and 10 illustrate typical y-ray spectra for occurred immediately after the 48-sec activation time. activated samples from four of these areas: Southern _A-very large proportion of the samples so far analyzed, Sierra, Calif; Hungry Horse, Mont.; Reno-Mt. Rose, of which those shown (Figs. 8, 9 and 10) are representa. Nev.; Elko, Nev. tive, contain silver in excess of the minimum detectable442 JOURNAL OF we a COUNTS Pee MINUTE al APPLIED METEOROLOGY Vouume 7 ot & a we oo) os 0 19 15 v8 a 24 ay a fen (ne) eee Tee RT Coat w r e Baier ge : SonEya | a & A age ° 2 Ew Nou AI ” Spt 0 03 06 OF 12 15 18 21 24 27 30 a 03 08 of 12 15 18 21 24 27 30 ENERGY (MeV) ENERGY (hv) ia. 10, yay spectra of precipitation sample extracts for four areas of western United States. Masses of Ag ~3X10- gm amount (10~! gm). The highest silver concentration so far detected is around 10-* gm ml with a large majority between 10 and 10-* gm mt, The lower limit of sensitivity, therefore, does not appear at this time to be a serious limiting factor for silver determina- tion in snow samples collected at ground stations in areas where cloud-seeding experiments are in progress. 7, Discussion ‘The procedures described in this paper have been developed in recognition of a need to measure, quanti- tatively, the amount of cloud-seeding material in precipitation, There are potentially several methods of measurement available to the experimenter. Most, if not all, of the methods require concentration to be first carried out. Many problems still exist in the concentration and isolation procedures used here Although monitoring techniques are used to help deter- mine efficiencies, there still exists the implicit assump- tion that these efficiencies are applicable to the silver in the precipitation. This silver could be in any of a number of chemical forms [e.g,, see DePena and Caimi (1967)}). With the silver present in such low concentra- tions (10-* to 10- gm mi, this problem exists more for less independently of the method of detection employed, be it neutron activation or some other procedure ‘The system developed is a nondestructive one using thermal neutron activation. The data, in the form ofJone 1968 A, WARBURTON ‘y-ray spectra obtained by scintillation spectrometry, have been programmed for rapid computer analysis. ‘The turn-around time for the silver determination in snow samples from field experiments, is approximately cone week. Measurement of the radioactivity is a statisti process. Every measurement, therefore, has stat errors associated with it, Since the random events bei measured are occurring together with other random events originating in other places (the laboratory radio- active background), the accuracy of determination varies with the total mass of element being measured, In the experimental configuration described earlier, the standard errors due to this cause for total masses of 10-, 10-7, 10° and 10-* gm are, respectively, 1, 2, 10 and 80%, approximately. Silver is being detected in a large proportion of the samples analyzed. ‘The 1966-1967 winter season. was used to gather, at the ground, a relatively large number cof samples from a variety of geographical regions. Some of these samples were collected from areas where seeding with Agl had been occurring, others where it presumably had not. A more detailed description of neutron activation analysis results of hail, rain, and snow collected from two areas in the western United States, is given in a comparison paper in this Journar. (Warburton and Young, 1968). From the data so far analyzed, there is no doubt that the working analytical technique described will measure ‘quantitatively the minute concentration of the seeding ‘element in precipitation samples. Of course, the presence offrelatively large concentrations of silver in the pre- cipitation does not imply that the silver iodide had anything to do with the precipitation mechanism, What ‘can be deduced at this time is that the silver iodide aerosol reached the general area where the sample was obtained. It now remains to devise ad fioc experiments to resolve some of the underlying meteorological problems. AND L. G. YOUNG 443 Acknowledgments. The authors would like to thank Mr. David James for his care and precision in the handling of precipitation samples through the several pre-chemistry phases of the work, Two graduate students in Atmospheric Physics, Mr. Maarten Pranger and Mr. Harvey Hansen and a Physics undergraduate, Mr. Larry Franks, were re- sponsible for considerable portions of the computer pro- gramming and the data analysis. We would also like to express appreciation of the continued interest and support of Prof. Wendell A. Mordy during the per- formance of this work. ‘Tis work was supported by the U.S. Department of the Interior, Bureau of Reclamation, under the terms ‘of Contract No. 1406-D-5410, 1966, and No. 1406-D- 53995, 1967. REFERENCES DePena, R. G., and E, A. Caimi, 1967: Hygrascopicity. and chemical composition of silver Jodide smoke used in cloud seeding experiments. J. Aims. Sci, 24, 383-386, Teono, K., 1961; Some reaulis of cloud seeding experiments with Use of silver iodide ground generators. Proc. Intern. Cloud Physics Conj., CSLRO, Australia, I. U. G. G. Monoge. 16 Koenig, [, R., 1960: The chemi ion of silver iodide ce mudlel: A laboratory. inary eld study. J Meteor V1, 426-434, Lakens, Hf) R.’ Jr, 1964: Usiization of reactor fast_neuttons for activation analysis. Annual Rept,, No, GA-S073, General Dynamics Corp. 104 pp. Vonnegut, B. J.. 1949; Nucleation of supercooled water clouds by silver iodide smokes. Chem. Rev, 44, 277-289. Warburton, J. A., 1968: The detection of silver in rainwater from loud seeding experiments in Australia, J. Appl. Meteor. 2, 569-573. 1965: The detection of silver in rainwater: Further develop- ments of technique. J. Appl. Mclor., 4, 563-368. ~— and C.'T. Maher, 1068: The detection of silver in rainwater: ‘Analysis of precipitation collected from cloud seeding experiments. J. Appl. Meteor, 4, 860-568 = and L. G. Young, 1968: Neutron activation measurements ‘of silver in precipitation from locations in western North America. J. Appl Meteor, 7, 444-448.