J. Mass Spectrom. Soc. Jpn., 64(6) (2016)
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1 J. Mass Spectrom. Soc. Jpn. Vol. 64, No. 6, 2016 REVIEW New Ion Collector for Elemental and Isotope Imaging 1, * ,3 Takafumi Hirata, Michitaka Tanaka, Hideyuki O-bayashi, Kentaro Hattori, and Shuhei Sakata 1 Geochemical Research Center, The University of Tokyo 2 Laboratory for Planetary Sciences, Kyoto University 3 Department of Chemistry, Faculty of Science, Gakushuin University Several important developments in the mass spectrometry techniques have been made in the last decade, including higher ionization efficiency, higher transmission efficiency, and faster mass scan capability, as well as a wide dynamic range for the ion collection. Especially, dynamic range and stability of the ion detection system is a still key issue for both elemental and isotopic analyses of geochemical and biochemical samples. Extremely high sensitivity can be achieved by the electron multiplier technique, but there still remains a problem associated with long- to medium-term gain stability. Time changes in gain of the EM was the major reason why multiple collection using the EMs was not developed. In strike contrast, it is widely recognized that Daly ion collector can provide higher gain stability and a wider dynamic range for the ion detection. In this study, long-term and medium-term stability, together with the dynamic range of the Daly ion collector were rigorously tested. The result showed that both linearity and stability was significantly better than the EMs. The resulting analytical capabilities and basic performance revealed that the Daly detectors can provide much more precise and accurate elemental and isotope ratio data for traceelements in both the geochemical and biological samples. Details of the system configuration and analysis capability for the isotope ratio measurements will be described in this paper. DOI: /massspec Received June 17, 2016; Accepted September 21, * Correspondence to: Takafumi Hirata, Geochemical Research Center, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo , JAPAN, hrt1@eqchem.s.u-tokyo.ac.jp U 206 Pb, 87 Rb 87 Sr, 26 Al 26 Mg
2 T. Hirata et al C 14 C 5, N 14 C 14 C 14 N, C, O, F ICP a b c d e inductively coupled plasma; ICP 8,000 C ICP ICP ICP multiple collector; MC MC-ICPMS U Pb 206 Pb/ 238 U Pb/ 238 U Pb/ 238 U ICP ppm 8 226
3 1. ICP Faraday Collector; FC FC FC FC Faraday bucket 2. a b 10 2 a FC 2 a FC 227
4 T. Hirata et al. Negative feedback amplifier circuit FC FC 7 FC FC cps count per second; s 1 FC FC 5 10 FC Johnson Nyquist Noise ,000 cps FC FC V 0, V 2 V V 0 (1 e t/rc ) 1 t 3. FC a b R CC 10 pf R C C/ 1 G G 0.1 τ FC R, C 3 11 ICP 1 5 V 3 a 228
5 4. a EM b FC 65 Cu/ 63 Cu 3 b FC 3 b FC FC FC 1,000 cps S/N EM FC 1,000 cps 1 electron multiplier; EM EM 13 4 a EM 1 τ 5 30 ns N true 229
6 T. Hirata et al. 5. N obsd N true 2 5 b-1 5 b-2 10 ns 10 5 cps cps 10 8 cps 5 b-2 N true 6 ICP 115 In/ 113 In In 115 In/ 113 In 115 In/ 113 In τ τ τ τ EM EM 100,000 cps FC 9 14 EM first dynode a b Debye Length EM 7 230
7 7. EM 15 6 EM EM 0.1 EM attenuator lens EM Nu Instruments AttoM HR-ICPMS Pb, Th, U 206 Pb/ 238 U Pb 100 cps 238 U 10 7 cps 238 U 1/200 1/ cps 10 5 cps EM EM 300 amu EM 19 Thermo Fischer Scientific Element2 HR-ICPMS 6. 4 DC Daly collector; DC kv Daly knob 4 b EM DC 231
8 T. Hirata et al. 8. Nu Instruments Nu Plasma II 206 Pb 207 Pb2 Daly DC DC 4 Nu Instruments DC deflector DC 8 DC 9 NIST SRM EM DC cps EM DC 208 Pb EM / 206 Pb Daly 207 Pb Daly / 206 Pb Daly 10 9 ICP 206 Pb DC 207 Pb DC 10 cps, 208 Pb EM 20 cps 1 5 EM/DC 208 Pb/ 206 Pb ICP 100 DC/DC 207 Pb/ 206 Pb EM/DC EM/EM 1 DC EM DC EM 10 peak height analysis; PHA 232
9 discrimination setting a EM DC 208 Pb EM / 206 Pb Daly b DC 207 Pb Daly / 206 Pb Daly ICP 206 Pb, 207 Pb 10 cps, 208 Pb 20 cps 1 5 EM 10 a EM PHA EM 20 cps 10 DC 10 b kev Daly DC 11 DC cps ng/g 180 W cps 100 cps 10. PHA a EM, b DC EM DC discrimination 233
10 T. Hirata et al W 100 cps 1,000 cps 10 7 cps 10 7 cps FC DC FC 11 5 DC Debye ICP 2 DC 207 Pb/ 206 Pb Pb/ 206 Pb 2SD 206 Pb cps Pb 207 Pb 207 Pb/ 206 Pb Pb/ 206 Pb n 50 2SD 206 Pb 206 Pb 207 Pb DC 7. TIMS IRMS Noble Gas MS SIMS AMS DC cps FC 10 3 cps 234
11 cps DC FC DC FC cps cps 13 DC FC cps crossover range DC FC 2 DC FC 11 LA-ICPMS ICP Robert W. NesbittDetlef Günther Phil Freedman Nu Instruments A , T. Hirata, Isotopic Analysis: Fundamentals and Applications using ICP-MS, Frank Vanhaecke and Patrick Degryse eds., Wiley-VCH Verlag GmbH & Co. KGaA 2012, pp Chapter 4. 3 J. Hoefs, Stable Isotope Geochemistry, Springer-Verlag, 6th ed. 2009, ISBN , , J. Mass Spectrom. Soc. Jpn., 63, R. E. Russo, A. A. Bol shakov, X. Mao, C. P. McKay, D. L. Perry, and O. Sorkhabi, Spectrochim. Acta, 66B, X. Mao, A. A. Bol shakov, D. L. Perry, O. Sorkhabi, and R. E. Russo, Spectrochim. Acta, 66B, M. Dong, X. Mao, J. J. Gonzalez, J. Lu, and R. E. Russo, Anal. Chem., 85 5, K. L. Brown and G. W. Tautfest, Review of Scientific Instruments, 27, T. Hirata, Y. Hayano, and T. Ohno, J. Anal. Atom. Spectrom., 18 10, J. Kimura, Q. Chang, K. Itano, T. Iizuka, B. S. Vaglarov, and K. Tani, J. Anal. Atom. Spectrom., 30 2, J. Allen, Phys. Rev., 55 10, E. G. Burroughs, Review of Scientific Instruments, 40, S. Richter, A. Alonso, Y. Aregbe, R. Eykens, F. Kehoe, H. Kühn, N. Kivel, A. Verbruggen, R. Wellum, and P. D. P. Taylor, Int. J. Mass Spectrom., 281 3, S. Richter, S. A. Goldberg, P. B. Mason, A. J. Traina, and J. B. Schwieters, Int. J. Mass Spectrom., 206 1, , S. Sakata, K. Hattori, H. Iwano, T. D. Yokoyama, T. Danhara, and T. Hirata, Geostand. Geoanal. Res., 38, R. J. Beuhler and L. Friedman, Int. J. Mass Spectrom. Ion Phys., 23, N. R. Daly, Review of Scientific Instruments, 31, Thomas Walczyk J. Mass Spectrom. Soc. Jpn., 63, , Keywords: Daly ion collector, Elemental analysis, Isotope analysis, Imaging, Wide dynamic range 235
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