1571632008 ChikyukagakuGeochemistry1571632008 ICP-MS Fundamental of collision/reaction cell ICP-MS Katsuhiko KAWABATA IAS Inc. 4th Floor, No.5 Ikeda building, 1-4-4 Higashi, Kunitachi, Tokyo 186-0002, Japan Inductively coupled plasma mass spectrometry (ICP-MS) has been an indispensable tool for analysis of metals at ultra trace level. Looking back upon the history of ICP-MS, how to increase the sensitivity with lower background and how to eliminate interferences have been major research themes. Various techniques have been developed to eliminate interferences, and the most popular technique for a time being is collision cell and reaction cell technologies. These two techniques are similar, but they are in fact completely different in terms of the way of interference elimination. In addition, there is another important differentiation in terms of elimination of by-product ions generated in the cell. In this paper, a principle of collision and reaction cell technologies will be described. ICP-MS ICP-MS 1980 Houk et al., 1980 3 Koppenaal, 1994; Park et al., 1987; Sakata and Kawabata., 1994; Nonose et al., 1994; Tanner and Baranov., 1999; Feldmann et al., 1999 2 ICP-MS 1860002 144 54 Morita et al., 1989 QMS ICP- QMS Kinetic Energy Discrimination: KED Dynamic Bandpass Tuning: DBT2
ICP-QMS ICP-MS ICP-QMS Fig. 1 1mm 500 Pa 0.5 mm 0.9 mm 0.1 Pa ICP-QMS ICP-QMS 2mm4mm 10 4 Pa U Vcost B U VcostB - U -Vcost B Fig. 1 Schematic diagram of collision/reaction cell ICP-MS.
ICP-MS Fig. 2 Stable diagram of quadrupole mass filter (Left) and enlarged at 0 region (right). U V Fig. 2 Dawson and Whetten, 1976 a q UV rme n a2 nn1 eu m 2 r 2 qnn1 ev m 2 r 2 a q Fig. 2 a q 0 Fig. 2 a q r U V a q 0.230.7 1a.m.u a q 10 2 10 3 Pa 10.1 Pa Collision-Induced Dissociation: CID
40 Ar 16 O m1aro m2 ArO Eini ArO E E Eini m1 m1m2 20 ev 1 800.95 ev56 1.33 ev 282.5 ev ArC ArOArNaArMgArCa 1eV 1 ClON2CO 48eV Charge Transfer A B AB H H H 40 Ca 40 Ar NH3 40 Ar Ar NH3 Ar NH3 Ca ArCaNH3 15.86.110.2 ev Ar NH3 Ca NH3 10 ev 10 ev NH3 10.2 ev H-atom Transfer A H2 AH HH 40 Ar 40 Ca Ar 40 Ar 1 H 40 Ca 1 H Proton Transfer H AH H2 AH3 H 40 Ar 1 H H3 40 Ar Oxidization, Halogenation 3.13.4 A BO AO BH 75 As 40 Ar 35 Cl ArCl 75 75 As 75 As 16 O 91 As Einim1
ICP-MS m2 E E Eini 2 m12 m2 m1m 2 2 100 ev m140m24 84 ev m220 56 ev 100 ev m174056 548488 ev Kinetic Energy Discrimination: KEDKED 80 Se 40 Ar 40 Ar 40 Ar 40 Ar 2100 ev 40 Ar 40 Ar 3eV36 80 Se 18 18 ev 4eV 40 Ar 40 Ar 80 Se KED DBT KED KED 0 35eV DBT
a0q= 0.256 Fig. 3 a 0U0V V qr m 100 V r X q q 0.9 12 ArO 17 NH3 NH3 56 q 0.5 250 V Fig. 4 q 0.930 30 17 NH3 NH3 a 0 NH3 DBT DBT KED Axial Field Technology: AFTBandura et al., Fig. 3 Stable diagram of quadrupole mass filter (a 0, q0.2). Fig. 4 Stable diagram of quadrupole mass filter (a 0, q0.5).
ICP-MS 2002AFT T 4 ICP-QMS (2002) Inductively coupled plasma mass spectrometer with axial field in a quadrupole reaction cell. Journal of the American Society for Mass Spectrometry 13, 11761185. Dawson, P. H. and Whetten, N. R. (1976) Quadrupole mass spectrometry.chapter1, 9, Elsevier. Feldmann, I., Jakubowski, N. and Stuewer, D. (1999) Application of a hexapole collision and reaction cell in ICP-MS Part I: Instrumental aspects and operational optimization. Fresenius Journal of Analytical Chemistry 365, 415421. Houk, R. S.,Fassel, V. A. Flesch, G. D. Svec, H. J., Gray, A. L. and Taylor, C. E. (1980) Inductively coupled argon plasma as an ion source for mass spectrometric determination of trace elements. Analytical Chemistry 52,22832289. Koppenaal, D. W, Barinaga, C. J. and Smith, M. R. (1994) Performance of an inductively coupled plasma source ion trap mass spectrometer. Journal of Analytical Atomic Spectrometry 9, 10531058. Morita, M., Ito, H., Uehiro, T. and Otsuka. K. (1989) High resolution mass spectrometry with inductively coupled plasmaionization source. Analytical Sciences 5, 609610. Nonose, N. S., Matsuda, N., Fudagawa, N. and Kubota, M. (1994) Some characteristics of polyatomic ion spectra in inductively coupled plasma mass spectrometry. Spectrochimica Acta 49B, 955974. Park, C. J., VanLoon, J. C., Arrowsmith, P. and French, J. B. (1987) Sample analysis using plasma source mass spectrometry with electrochemical sample introduction. Analytical Chemistry 59, 21912196. Sakata, K. and Kawabata, K. (1994) Reduction of fundamental polyatomic ions in inductively coupled plasma mass spectrometry. Spectrochimica Acta 49B, 10271038. Tanner, S. D. and Baranov, V. I. (1999) Theory, design, and operation of a dynamic reaction cell for ICP-MS. Atomic Spectroscopy 20,4552. Bandura, D. R., Baranov, V. I. and Tanner. S. D