Alberto, R.

Fujita, T.

Hiraga, H.

Kim, J. I.

Mutalib, A.

Sekine, T.

Yoshihara, K.

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Radiochimica Acta 63, 4 5 - 4 7 (1993) © R. Oldenbourg Verlag, München 1993 - 0033-8230/93 $ 3.00 + 0.00 Determination of Technetium by Laser Induced Photoacoustic Spectroscopy Coupled with a Wave-Length Shifter Method By T. Fujita, T, Sekine, H. Hiraga, K. Yoshihara, A. Mutalib, R. Alberto*, and J. I. Kim** Department of Chemistry, Faculty of Science, Tohoku University, Sendai 980, Japan * Labor für Radiopharmazie, Paul Scherrer Institut, CH 5232 Villigen, Switzerland ** Institut für Radiochemie, Technische Universität München, D-8046 Garching, Germany (Received May 12, 1993) Laser induced photoacoustic spectroscopy / Technetium / PZT detection / Hexakis( thiocyanato ) technetate Abstract Laser induced photoacoustic spectroscopy (LPAS) was applied to the determination of " T c in a Solution, coupled with quantita-tive complexation of Tc by thiocyanate ion (NCS~) to form [TC(IV)(NCS)6]^", which had an intense absorption peak at 500 nm. Sensitivity of the quantitative detection could be im-proved down to a concentration of 10"® mol dm"^ which was one Order of magnitude better than that for thiourea complex. Introduction The long-lived radioactive nuclide, ®'Tc, is one of the most important fission products with high fission yields (6.06%). Its long half life (2.13 x 10^ y) and characteristic pure ß~ emission make its determi-nation difficult. The authors have tried to develop a specific determination by ®®Tc(y,y')®®'"Tc nuclear excitation [1 — 3], as well as by laser induced photoacoustic spectroscopy (LPAS) coupled with quantitative a complexation of technetium with thio-urea (tu) to form Tc(tu)i+ [4]. In the case of the LPAS method using Tc(tu)6 , which has an intense absorp-tion peak at 488 nm with a molar extinction coefficient of 6400 dm^ m o l " ' c m " ' [4], a detection limit of ^®Tc could be obtained down to the order of 10"® mol dm"^ . In this paper, the hexakis(thiocyanato)techne-tate(IV) ion ([Tc(NCS)6]^") has been chosen to im-prove the determination limit, because its absorption peak has a molar extinction coefficient larger than that for Tc(tu)6 ^. This work has been undertaken to provide a basis for development of a new chemical speciation using LPAS. Experimental The LPAS system consists of a nitrogen gas laser (Laserpho tonics Co., UV24), a dye laser (Laserphoto-nics Co., DL14), and a gated boxcar averager system (Stanford Research Systems, SR250). The detection part which includes piezo-electric tranducers (PZT) (Tohoku Kinzoku Co.) was home-made, and Oper-ation details was given in a previous report [4]. A 2 ml sample Solution in a quartz cell (1 cm path length) was submitted to LPAS measurements by exci-tation with monochromatic laser pulse. The wave length of the excitation beam was adjusted to 500 nm using Coumarin-481 dye material. [Tc(NCS)6]^ " was prepared by the method accord-ing to Crouthamel [6]. A Solution of 1 M NH4SCN was added into a 4 M H2SO4 Solution containing pertechnetate. Within 5 min, during stirring, the color of the Solution changed to red-violet. Then a 1.5 times larger volume of acetone was added to stabilize the complex. An aliquot of this stock Solution was diluted with distilied water to give an appropriate concen-tration of technetium for the LPAS measurements. An optical absorption spectrum was measured with a spectrophotometer (Hitachi 50 — 100). The radioac-tivity of Tc was determined with a liquid scintillation counter (Aloka LSC-700). Results and discussion The molar extinction coefficient of [Tc(NCS)6]^~ at 500 nm was obtained as 46900 dm^ mol"^ c m " ' by optical absorption spectrophotometry, which was in good agreement with the reported value [6] in the presence of acetone. Fig. 1 shows change of ab-sorbance at 500 nm after mixing a pertechnetate Solu-tion with 1 M NH4SCN in the presence of acetone. It confirmed quantitative formation of [Tc(NCS)6]^" and its stability was guaranteed for standing of up to one day. In the absence of acetone, the absorption spectrum gradually changed to give another tech-netium species which has an absorption maximum at 410 nm, as shown in Fig. 2. This species could be attributed to [Tc(III)(NCS)6]^" produced by further reductionof [Tc(IV)(NCS)6p" [7, 8]. When the acetone containing Solution was submit-ted to the LPAS measurement, gas evolution could be observed and the true photoacoustic signals were drastically disturbed by this cavitation. Degasfication 46 T. Fujita, T. Sekine, H. Hiraga, K. Yoshihara, A. Mutalib, R. Alberto, and J. I. Kim 0.4 I € 0 rrc]=5.6 X 10"®mol dm'^ 0 200 400 600 800 1000 1200 1400 Time / min Fig. 1. The formation of [Tc(NCS)6]^~ after mixing pertechnetate and 1 M NH4SCN Solution in the presence of acetone. 10"'' 10-° 10-' The concentration of Tc / M Fig. 4. The normalized FFT peak intensity as a function of the concentration of "Tc. 0.4 I > 0.21 Tc(i\J l®Tc].8.6x lO'^moldm'^  / 8 min N^  / / Tc(iO 400 500 Wavelength / nm 600 Fig. 2. The changes in absorption spectra of |Tc(NCS)6]^ in the absence of acetone. 20 40 60 80 Time / min 100 120 Fig. 3. The time dependence of absorbance of [Tc(NCS)6]^ when diluted with distilled water. of the Solution by ultrasonic treatment was not effec-tive. Gas generation was not observed in the absence of acetone. Therefore, an aliquot of the stock Solution of [Tc(NCS)6]^ ~ stabilized by acetone was diluted with distilled water, and LPAS measurements were made immediately. The absorbance of the diluted Solution at 500 nm slowly decreased with increasing time, as shown in Fig. 3. This change was slow enough to allow a quick measurement with 3 min after the sample preparation by increasing the laser pulse repetition to 20 Hz and by repeating 3 data averagings. Fast Fourrier Transfer (FFT) analysis was used for the averaged data to evaluate peak intensity [4], The pressure wave, p, which is related to the inten-sity of photoacoustic signal, can be expressed by [9], p = const. ß V^EoilCp (1) where ß i s a thermal expansion coefficient, E is pulsed laser energy, Cp is specific heat at constant pressure, Va is acoustic velocity, and a is optical absorbance. a must be the value for a solute, eC (e: molar extinction coefficient, C: concentration) in a given medium. The net photoacoustic intensity of the solute can be obtained by subtracting the photoacoustic signal of the medium itself. Thus, the net acoustic pressure nor-malized to E can be directly related to the concen-tration of the solute, [TcCNCS)^]^". In order to per-form LPAS measurements for various concentrations of [Tc(NCS)6]^", different volumes of the stock Solu-tion containing acetone were diluted with distilled water to give a constant volume of 2 ml. This resulted in different compositions of water and acetone for each sample, which varies ß and Cp in Equation (1). Acetone mixing would cause an increased back-ground, because the increase of ß and decrease of Cp are expected by addition of acetone. However, this effect was sufficiently small in the case of the reference solutions which changed the concentration of acetone up to 8%. Almost constant photoacoustic signals were obtained, irrespective of change in the acetone concen-tration. The FFT peak intensity normalized to the laser power is plotted against the concentration of in Fig. 4. A linear relationship could be obtained over the concentration ränge —10"' moldm"^ and the determination limit was improved by one order of magnitude better than the case using thiourea com-plex. Conclusion The determination limit was improved down to the order of 10"® mol dm"^ ®®Tc; 2 ml of this Solution is Determination of Technetium by Laser Induced Photoacoustic Spectroscopy Coupled with a Wave-Length Shifter Method 47 equivalent to about 440 mBq of This value is comparable to that obtained by activation analysis [1], Acknowledgement This work was supported by the Grant-in-Aid of Min-istry of Education, Culture and Science N o . 03558022. References 1. Sekine, T., Yoshihara, K., Nemeth, Zs., Lakosi, L., Veres, Ä.: J. Radioanal. Nucl. Chem. Articles 130, 269 (1989). 2. Sekine, T., Yoshihara, K., Lakosi, L., Nemeth, Zs., Veres, Ä.: Appl. Radiat. Isot. 42, 149 (1991). 3. Vagi, M., Sekine, T., Yoshihara, K.: J. Radioanal. Nucl. Chem. Lett. 155, 435 (1991). 4. Sekine, T., Hiraga, M., Fujita, T., Mutalib, A., Yoshihara, K.: J. Nucl. Sei. Technol., in press. 5. Hashimoto, K.: PhD Thesis, Tohoku University 1987. 6. Crouthamel, C. E.: Anal. Chem. 29, 1756 (1957). 7. Trop, H. S., Davison, A., Carey, G. H., DePamphilis, B. V., Jones, A. G., Davis, M. A.: J. Inorg. Nucl. Chem. 41, 271 (1979). 8. Trop, H. S., Davison, A., Jones, A. G., Davis, M. A., Szalda, D. J., Lippard, S. J.: Inorg. Chem. 19, 1105 (1980). 9. Patel, C. K. N., Tam, A. C.: Rev. Mod. Phys. 53, 517 (1981). 

Determination of Technetium by Laser Induced Photoacoustic Spectroscopy Coupled with a Wave-Length Shifter Method

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