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Anal. Chem. 1987, 59, 984-989
ACKNOWLEDGMENT The authors wish to thank Larry Hilscher for providing us with the UTP samples and Leisha Hester for the synthesis scheme used.
LITERATURE CITED Midelfort, D. F.; Rose, I. A. J . Biol. Chem. 1976, 2 5 7 , 5681. Schulten, H. R.; Beckey, H. D. Org. Mass Spectrom. 1873, 7, 861. Maruyama, I. N.; Tanaka, N.; Kondo, S.; Umezawa, H. Biochem. Biophys. Res. Commun. 1981, 9 8 , 970. Esmans, E. L.; Freyne, E. J.; Vanbroeckhoven, H. H.; Alderweireldt. F. C. Biomed. Mass Spectrom. 1980, 7,377. Blakely, C. R.; Carmody, J. J.; Vestal, M. L. J . Am. Chem. SOC. 1980, 702, 5931, Tsuchiya, M.; Kuwabara, H. Anal. Chem. 1984, 56, 14. Ens. W.: Standing, K. G.; Westmore. J. B.; Ogikle, K. K.; Nermer, M. J. Anal. Chem. 1982, 5 4 , 960. Aberth, W.; Straub. K. M.; Burlingame, A. L. Anal. Chem. 1982, 5 4 , 2029. McNeal, C. J.; Ogilvie, K. G.; Theriault. N. Y.; Nermer, M. J. J . Am. Chem. SOC. 1982, 104, 976. Della Negra, S.;Ginot, Y. M.; Lebeyec. Y.; Spiro, M.; Vigny, P. Nucl. Instrum. Methods 1982, 798, 159. McFarlane, R. D. Acc. Chem. Res. 1982, 75,266. Hardin, E. D.; Fan, T. P.; Blakely, C. R.; Vestel, M. L. Anal. Chem. 1984, 5 6 , 2. Barber, M.; Bordoli, R. S.; Sedgwick, R. D.; Tyler, A. N. J. Chem. SOC.,Chem. Commun. 1981, 325. Vu, V. T.; Fenselau, C. C.; Colvin, 0. M. J. Am. Cbem. SOC. 1981, 703, 7362. Sindona, G . ; Uccella, N.; Weclawek, K. J. J. Chem. Res., Synop. 1982, 184. Fenselau, C.; Vu, V. T.: Cotter, R. J.: Hansen, G.; Heller. D.; Chen, T.; Colvin. 0. M. Spectrosc. Int. J. 1982, 7 , 132. Mitchum. R. K.; Evans, F. E.; Freeman, J. P.; Roach, D. Int. J. Mass Spectrom. Ion Phys . 1983, 4 6 , 383. Eagles, J.; Javanaud, C.; Self, R. Biomed. Mass Spectrom. 1984, 7 1 . 41.
(19) Crow, F. W.; Tomer, K. B.; Gross, M. L. 37st Annual Conference on Mass Spectrometry and Allied Topics, Boston, MA, 1983, 726. (20) Crow, F. W.; Tomer, K. B.; Gross, M. L.; McCloskey, J. A,; Bergstrom, D. E. Anal. Biochem. 1984, 739, 243. (21) Kingston, E. E.; Beynon, J. H.; Newton, R. P. Biomed. Mass Spectrom. 1984. 1 1 . 367. (22) Slowikowski, D. L.; Schram, K. H. Nucleosides Nucleotides 1985, 4 , 347. (23) Slowikowski, D. L.; Schram, K. H. Nucleosides Nucleotides 1985, 4 , 309. (24) Hllscher, L. W.; Hanson, C. D.; Russell, D. H.; Raushel, F, M. Biochemistry 1985, 2 4 , 5888. (25) Barber, M.; Bordoli, R. S.; Sedgwick, R. D.; Tyler, A. N. Biomed. Mass Spectrom. 1982, 9 , 208. (26) Tondeur, Y. Org. Mass Spectrom. 1985, PO, 157. (27) Heerma, W.; Kamerling, J. P.; Slotboom, A. J.; van Scharrenburg, G. J. M.; Green, B. N.; Lewis, I . A. S. Biomed. Mass Spectrom. 1985, 10, 13. (28) Tomer, K. B.; Crow, F. W.; Gross, M. L. Anal. Chem. 1984, 56, 880. (29) Amster, J. I.; McLafferty, F. W. Anal. Chem. 1985, 5 7 , 1208. (30) Caprioli, R. M. ACS Symp. Ser. 1985, No. 297, 209. (31) Mallis, L. M.; Russell, D. H. Anal. Chem. 1988, 5 8 , 1076. (32) Risely, J. M.; Van Etten, R. L. J. Labelled Compd. Radiopharm. 1978, 75,533. (33) Gross, M. L.; Chess, E. K.; Lyon, P. A.; Crow, F. W.; Evans, S.; Tudge, H. I n t . J. Mass. Spectrom. Ion Phys. 1982, 42, 243. (34) Russell, D. H.; Smith, D. H.; Warmack. R. J.; Bertram, L. K. Int. J . Mass Spectrom. Ion Phys . 1980, 35, 38 1, (35) Mallis, L. M.; Russell, D. H., unpublished results
RECEIVED for review July 24, 1986. Accepted December 1, 1986. This work was supported by grants from the National Science Foundation (CHE-8418457) and the National Institute of Health-General Medical Sciences (DHR, GM33780-01; FMR, GM33894). Partial support for L.M.M. and funds used for the purchase of equipment for these studies were obtained from the TAMU Center for Energy and Mineral Resources.
Osmium Isotopic Ratio Measurements by Inductively Coupled Plasma Source Mass Spectrometry G . Price Russ III* and Jeanne M. Bazan
Lawrence Livermore National Laboratory, Livermore, California 94550 Alan R. Date
British Geological Survey, London, England
The Isotopic composition of nanogram quantltles of osmlum was measured by uslrrg an lnducthrely coupled plasma w r c e mass spectrometer. Sensitlvlty was enhanced a factor of 4 0 0 by the use of an osmlum tetraoxide vapor generator rather than nebuliratlon of solution. For 88mpies 1 5 ng, the ratlos rgoOs/1920s,i8gOS/1g20S, and i8gOs/1g20swere determined to better than * O S % (la,,,) precision. For the mlnor isotopes, the ratios i 8 7 0 S / 1 g 2 0 ~and 18'Os/1g20s were determined to fl%, and i 8 4 0 ~ / 1 (4gX*lo4) ~ was determlned to ==lo %. Isotope ratlos for common osmlum are reported.
The ability to measure the isotopic composition of nanogram or smaller quantities of osmium is necessary for the development of the 1s7Re1s70s dating technique for geological samples and would provide a sensitive method of measuring osmium concentrations in rocks or other materials by isotope dilution. Such measurements have been hampered by the difficulties in isolating osmium from samples and finding
suitable mass spectrometric techniques. It has been shown that osmium isotopic measurements can be made with an ion microprobe (1, 2). However osmium isotopic assay by ion microprobes requires extensive sample preparation. The collected spectra are subject to polyatomic ion interferences, and the equipment is expensive and not widely available. Measurements have also been made with the laser microprobe mass analyzer (LAMMA) ( 3 ) ,but in addition to having the same problems as the ion probe, interpretation of LAMMA spectra was complicated by severe nonlinearities in the detector system. Recently there have been reports of osmium isotopic ratio measurements by resonance ionization mass spectrometry (4)and accelerator mass spectrometry (5). As part of a project to measure the 18'Re half-life (4.35 X 1O'O years) (6),we investigated inductively coupled plasma source mass spectrometry (ICP-MS) (7) as a tool for making such measurements. In ICP-MS, samples are usually liquids, which are introduced into the plasma by means of a nebulizer and spray chamber. Even though this process is only ~ 1 efficient, % the
0003-2700/87/0359-0984$01.50/00 1987 American Chemical Society
ANALYTICAL CHEMISTRY, VOL. 59, NO. 7, APRIL 1, 1987 985 Vacuum chamber
-Ion
detector
Torch hwsing-
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Ion lens-
Plasma torch,
Coolant and plasma gas inlett
r R F load coil
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gar line
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5000
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Flgure 1. Schematic layout of the ICP-MS with the OsO, vapor
generator attached. detection limits for many elements including the noble metals are at the
