Mass spectral fragmentation pathways in 2,4,6‐trinitrotoluene derived from a MS/MS unimolecular and collisionally activated dissociation study

The fragmentation pathways of 2,4,6‐trinitrotoluene have been examined using 15N and 2H isotopic labelling in conjunction with tandem mass spectrometry. Both the unimolecular and collisionally activated decomposition modes were investigated. Fragmentation pathways were established in both modes and isotopic shifts were used to determine the groups lost. The major pathways include the loss of OH or H2O, followed by the subsequent loss of NO or NO2. There is virtually no ring disintegration until the majority of the attached groups are lost.