Page 245 - Advances in Forensic Applications of Mass Spectrometry - Jehuda Yinon
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                             is analyzed by acquiring a precursor ion with no collision energy added. In
                             a chemical-class specific analysis, an ion at m/z 71 or 85 is chosen for mon-
                             itoring alkanes and is subsequently reconstructed for data review and assess-
                             ment as in GC/MS. This ion is acquired in a very similar fashion to that in
                             selected ion monitoring (SIM) in GC/MS. As evidence of branched alkanes
                             is required for distillate or gasoline identification, this class represents the
                             limiting factor in sensitivity for MS/MS. Beyond zero energy addition, other
                             instrumental parameters can be modified to enhance alkane class sensitivity.
                             Some researchers have worked on obtaining a response for the molecular ion
                             to use as a precursor ion in order to obtain an associated daughter ion in
                                                                                          16
                             MS/MS. These parameters have been recently reported by researchers who
                             have also recognized that the alkane class is a limitation to the sensitivity of
                             a target-class specific GC/MS/MS analysis.
                                Using this approach,  the analysis of  a stair  tread had some of  these
                             criteria, but there were insufficiently clear characteristics to define a positive
                             result to present in court (see Figure 5.22). In review of the TIC in the initial
                             analysis,  this sample  would have been  reported as negative  by GC/MS,
                             whereas the TIC from the GC/MS/MS analysis shows that the sample has
                             many additional compounds not seen in the GC/MS analysis.
                                A part of the examination of the stair tread sample, Figure 5.23 illustrates
                             the improved comparability of this sample to a gasoline reference for these

                             MCounts                                          file5690.ms RIC all
                               1.25                    GC/MS of Sample
                                                       Result Would be Negative!
                               1.00
                               0.75
                                    TIC is dominated by strong pyrolysates
                               0.50  Some Ignitable Liquid components were detected
                               0.25

                               0.00
                             kCounts                                           f5704ms2.ms RIC all
                                                         GC/MS/M S of Sample
                                30
                                                                  TIC shows the focus on Ignitable Liquid Components,
                                                                        pyrolysates effectively removed
                                20

                                10

                                 0
                                              2.5         5.0         7.5         10.0     minutes
                             Figure 5.22  Top profile: Sample of a stair tread by GC/MS; bottom profile:
                             same sample by GC/MS/MS illustrating increased detection of ignitable liquid
                             components and reduced effect by pyrolysates.

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