Page 323 - Inorganic Mass Spectrometry - Fundamentals and Applications
P. 323

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            measurements  the  ability  to  resolve  small  isotopic  variations limited, in  part,  by
            the  need to correct for mass  discrimination  and  mass  fractionation  during  the  course
                                                                 of
            of the  analysis,  normally by alternating the sample  with  a  standard known  com-
            position.  Natural  isotopic  fractionations  among  heavy  elements  are  typically  too
            small to measure  with  such  techniques.  However,  Mar6chal et al.  (1997),  using
            MC-ICP-MS,  report  success  with  the  measurement natural frac~ionations in  Cu
                                                     of
            isotopic  compositions  using  Zn  to correct for inst~ment~ mass  bias,  and  vice
            versa.  Similarly, it appears  possible  to  measure  natural  Ga  isotopic  variations  in
            meteorites  by  monitoring  instrumental  mass  bias  using  admixed  Ge  (Hirata  1997).
            Recently, the natural  isotopic  variations  in T1 produced by mass-dependent frac-
            tionation  have  been  measured  by  admixing  Pb  of  known  isotopic  composition
             (Re~~per and  Halliday,  1999).
                 Many  of the  problems  associated  with  ICP-MS  are  not  relevant  to  MC-ICP-
            MS.  Most  solution  work performed  on  reasonably  pure  solutes separated  trace
                                is
                                                               of
             elements, so artifacts  associated  with  the  level of total  dissolved  solids  (Williams
             and  Gray,  1988)  are  negligible.  Plasma  instability  problems  (Begley  and  Sharp,
             1994)  are  not  so much of a  concern  with  MC-ICP-MS  because of the use of static
             multiple  collection. The effects of plasma  instability  therefore  largely  cancel out.
             The  most  recent inst~ments (notably  the  Micromass  instrument)  are  extremely
             stable,  especially  when  used  in  conjunction  with  the  MCN-6000,  Polyatomic  ion
             interferences  (Date et al.,  1987;  Gray  and  Williams, 1987; Marshall  and  Franks,
             1990) are only of concern  below  about  mass 80 and  most  applications of MC-ICP-
             MS are  used for studying  higher  masses. The contributions of hydrides  and  oxides
             are  negligible  because  a  dry plasma is used, either in laser ablation  mode  or  with
             a  desolvating  nebulizer.  Use of  adjustable  high  resolution,  as  on all the latest in-
             struments, makes it possible  to see which  interferences  may  be  present.  Use of the
             hexapole  collision cell, as  on  the  Micromass  instrument,  provides  a  means  to  elim-
             inate  many of them  altogether.
                 Problems  with internal standar~zation and  calibration of signal intensities
             for concentration  measurements  with  ICP-MS  (Walsh,  1992)  are  irrelevant  to  MC-
             ICP-MS  because  most  applications  are  concerned  with  isotopic  compositions  and
                                                          Yi
             isotope  dilution  measurements  (Lee  and  Halliday,  1995b; et al.,  1995).  Internal
             standar~zation is only of  significance  in  the  application  of  laser  ablation  tech-
             niques to the measurement of paren~daughter ratios by  MC-ICP-MS.  Work  has
             started in this area  (Halliday et al.,  1998a),  and  though the results of the first  ex-
             periments  are  encouraging,  they  mandate  a great  deal of further effort.







             The potential  range of application of  MC-ICP-MS is enormous.  Reviews of some
             of the geochemical  applications  can be found in Halliday et al.  (1998b).  Here we
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