Page 239 - Inorganic Mass Spectrometry - Fundamentals and Applications
P. 239

Isotope ~il~tion Mass ~pe~tromet~                             225


                                             is
         the  process  detection limit. A process ~Za~k one that tests the whole  chemical
         procedure,  including the instrument  and all reagents. A known  amount of calibrated
         spike is added  to  the  solvent  (usually  acid)  and the mixture  subjected to all steps
         a real sample  would  undergo. The amount of the target element is measured  in  the
         same  way  a  normal isotope dilution  analysis is carried out.  If  the  blank is unac-
                             of
         ceptably  high,  the  source conta~nation must be identified  and  eliminated. This
                                                           is
         can  be  a  tedious, time-consu~ng operation.  Once  the  blank  level established,  sam-
         ples  must  be  corrected for its contribution  unless it is deemed  insignificant.
              Isotope  dilution  involves  isotopes the  same  element,  thus  eliminating  differ-
                                        of
         ences in  chemical  behavior  that  can  plague  techniques  that  use  different  elements
         for the  spike  than the one being  analyzed.  This,  along  with the fact  that  quantita-
         tive  recovery is not  necessary once spike  and  sample  have  been  equilibrated,  makes
                                                                        el-
         isotope dilution less subject  to  error  arising  in  chemical  processing  than  many
         emental  assay  techniques,  a  fact of great  importance at low  concentration  levels.


           .3  I

                                                      [l].
         Isotope  dilution  was  first  developed  by  Inghram  in  1954 Since that time its ap-
                                                       in
          plication  has  become  very  widespread,  and  has  been  used numerous  disciplines.
          The following  derivation is based  on that of Hintenberger  [5]. The following  no-
          tation is used:
              C = concentration
               W = weight
              A = atomic  weight
              a = atomic  abundance
              R = ratio
              N = number of atoms
          The subscripts  are  defined  as  follows:
               S = unspiked  sample
               t = tracer  (spike)
               m = mixture of spike  and  sample
               i = major isotope in the sample
               k = major isotope in the spike
          The ratios (Rx )are  defined  as  follows:

               R, = ax /axk
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