Page 280 - Advances in Forensic Applications of Mass Spectrometry - Jehuda Yinon
P. 280

1522_book.fm  Page 253  Thursday, November 13, 2003  9:58 AM









                                                                    3.49
                                    100
                                                                                  m/z 281 -> 46
                                     %                          MNX
                                      0
                                                                  3.19
                                   Standards  %               DNX                 m/z 265 -> 46
                                     100
                                      0
                                                                2.97
                                     100
                                                                                  m/z 249 -> 113
                                     %                       TNX
                                      0
                                                                    3.49
                                     100
                                                                                  m/z 281 -> 46
                                     %
                                      0
                                                                  3.19
                                     100
                                   Sample  %                                      m/z 265 -> 46
                                      0
                                                                3.06
                                    100
                                                                                  m/z 249 -> 113
                                     %
                                      0
                                          0.50  1.00  1.50  2.00  2.50  3.00  3.50  4.00  4.50  5.00  5.50
                                                           Retention time (min)
                             Figure 6.14  Mass chromatograms of LC/MS/MS in the selected reaction mon-
                             itoring mode of the [M + 75]  adduct ions of MNX, DNX and TNX in a standard
                                                    –
                             and in a groundwater sample. (Reprinted with permission from Beller, H.R. and
                             Tiemeier, K., Use of liquid chromatography/tandem mass spectrometry to detect
                             distinctive indicators of in situ RDX transformation in contaminated groundwa-
                             ter, Environ. Sci. Technol., 36, 2060, 2002. © American Chemical Society.)

                             Detection limits were between 0.032 and 0.047 mg/l. Figure 6.14 shows the
                             mass  chromatograms of  LC/MS/MS in the selected  reaction monitoring
                                                –
                             mode of the [M + 75] adduct ions of MNX, DNX, and TNX, in a standard
                             and in a groundwater sample.
                                Another study of RDX and its degradation products in water was carried
                             out using a Micromass Quattro LC (Z-spray) triple quadrupole mass spec-
                                                                                  39
                             trometer,  operated in the electrospray,  negative-ion mode.   The isocratic
                             mobile phase was methanol–water (50:50) at a flow rate of 0.2 ml/min, the
                             HPLC column was a Waters Nova-Pak C column (150 ¥ 2.1 mm, 4 mm
                                                                  18
                             particle size). Argon was used as MS/MS collision gas. LC/MS mass spectra
                             of standards of RDX, MNX, DNX, and TNX (Scheme 6), showed major [M
                                 –
                                              –
                                                                          –
                             + 75] and [M + 45] adduct ions and small [M – H] ions in all 4 compounds.
                                                  –
                             MS/MS of the [M + 75] ions of all 4 compounds yielded daughter ions at
                                        –
                             m/z  46,  NO .  Detection limits of  RDX and its degradation products in
                                        2
                             groundwater were 0.1 mg/l.
                                A series of explosives, including RDX and HMX, were analyzed by ESI-
                                                                                     40
                             ion mobility spectrometry–mass spectrometry (ESI-IMS-MS).   The IMS
                             © 2004 by CRC Press LLC
   275   276   277   278   279   280   281   282   283   284   285