Page 246 - Advances in Forensic Applications of Mass Spectrometry - Jehuda Yinon
P. 246

1522_book.fm  Page 219  Thursday, November 13, 2003  9:58 AM









                             kCount                                                GC/MS Spectra
                               2.0 Stair Tread - GC/MS                      Scan 1161 from d:\data0199\file4886.msSpect 1
                               1.5                                         1317.234 min. Scan: 1161 Chan: 1 Ion: 46 us RIC: 7979382
                                                                            100%
                               1.0  Would be Negative
                                                                             75%
                               0.5
                                                                                             *
                               0.0
                             MCount                                          50%  Co-elutants
                                 Gasoline - GC/MS
                               0.7                   *        Poor comparability          146
                                                                             25%    91
                                                                                       115
                               0.5                                             41 51
                                                                                     105    160
                                                                                  69 77
                                                                                        1 1
                               0.2                                              50  75  100  125  150  175 m/z
                               0.0                                                  GC/MS/MS
                             kCount                                               Daughter Ion Spectra
                                   Stair Tread - GC/MS/MS
                                3   Confirmed Positive                       Scan 350 from d:\data0999\f5704ms
                                                                             2.msSpect 1BP 131 (2642=100%)
                                2                                           100% Scan: 350 Chan: 1 Ion: NA RIC: 111587.243 min.
                                                                                       19
                                                                               Clean & Isomer
                                1                                            75%  Specific
                                0                                                          **
                             kCount                                          50%
                               70  Gasoline - GC/MS/MS  **
                               60                               Excellent comparison  105
                               50
                               40                                            25%
                               30                                                   91    145
                               20
                               10                                               50  75  100  125  150  175 m/z
                                0                                               New Spectra = Additional
                                 4     5     6    7     8    9     10  11  minutes
                                                                                Identification Assurance
                             Figure 5.23  Stair tread sample: study of indanes.
                             indane profiles.  In addition,  the spectra  retrieved from the selected  com-
                             pounds illustrate that MS/MS spectra are cleaner and are most often signif-
                             icantly different,  thus improving selectivity and  confidence in the
                             identification. Upon further review, it was found that the compounds more
                             easily detected in the GC/MS/MS analysis were ignitable liquid components.
                             Thus, the analysis by GC/MS/MS determined that this sample was actually
                             positive for the presence of gasoline.
                                In answer to the fear that this technology, when applied to trace evidence,
                             may exceed an appropriate level of sensitivity, the sensitivity to alkanes is in
                             effect a self-limiting parameter and alkanes are characteristic for the deter-
                             mination of ignitable liquids. In GC/MS, alkanes are the primary character-
                             istic components for the identification of distillates, but some distillates have
                             little else to rely on but straight-chain and branched alkanes for identification.
                             This may be critical in some samples with a large quantity of pyrolysates —
                             many of which are alkenes — which significantly alter the alkane profile, thus
                             making identification difficult.  GC/MS/MS can significantly improve this
                             situation due to its high sensitivity for aromatic components. Trace aromatic
                             components that may be present are enhanced in GC/MS/MS, allowing addi-
                             tional identification criteria which are not readily apparent in the GC/MS
                             analysis. This is shown in Figure 5.24. GC/MS/MS thus provides more infor-
                             mation, reducing the sole reliance on alkanes.
                                In the class-specific approach, this analysis is not what could be called
                             too sensitive. It is not able to detect positive results in ambient air condi-
                             tions or environmental general deposition,  as determined in a specific
                                     15
                             research. GC/MS/MS can, however, be important in extending the useful
                             © 2004 by CRC Press LLC
   241   242   243   244   245   246   247   248   249   250   251