Analysis of triacetone triperoxide by gas chromatography/mass spectrometry and gas chromatography/tandem mass spectrometry by electron and chemical ionization

Abstract

The explosive triacetone triperoxide (TATP) has been analyzed by gas chromatography/mass spectrometry (GC/MS) and sub-nanogram detection limits are reported by ammonia positive ion chemical ionization (PICI), electron ionization (EI) and methane negative ion chemical ionization (NICI). Analysis by methane PICI and ammonia NICI gave detection limits in the low nanogram range. Analyses were carried out on (linear) quadrupole and ion trap instruments. Analysis of TATP by PICI using ammonia reagent gas is the preferred analytical method, producing low limits of detection as well as an abundant (greater than 60% of base peak) diagnostic adduct ion at m/z 240 corresponding to [TATP + NH4]+. Isolation of the [TATP + NH4]+ ion with subsequent collision-induced dissociation (CID) produces extremely low abundance product ions at m/z values greater than 60, and the m/z 223 ion corresponding to [TATP + H]+ was not observed. Density functional theory (DFT) calculations at the B88LYP/DVZP level indicate that dissociation of the complex to form NH4+ and TATP occurs at energies lower than peroxide bond dissociation, while protonation of TATP leads to cleavage of the ring structure. These results provide a method for pico-gram detection levels of TATP using commercial instrumentation commonly available in forensic laboratories. As a point of comparison, a detection limit of 15 ng was obtained by flame ionization detection.

Determination of gas phase triacetone triperoxide with aspiration ion mobility spectrometry and gas chromatography–mass spectrometry

“…At high TATP concentrations, a smaller peak next to the peak of intact TATP was found in the chromatograms. The smaller peak was found also in the chromatograms of the highest concentrations of TATP standard and it was suggested to originate from a degradation product of TATP, supported by the fact that TATP degrades strongly under electron impact ionization [11]. Proposed degradation is in accordance with our mass spectrometric results (Fig.…”

“…GC-MS conditions from the earlier studies [10,11] were used as starting parameters. GC was equipped with non-polar (5%-phenyl)-methylpolysiloxane HP-5 column (30 m × 250 m × 0.25 m).…”

“…Stambouli et al identified TATP from post-explosion debris sample using solid phase micro-extraction and GC-MS [10]. GC-MS has been used also for the quantification of TATP [2,11,12]. Quantitative analysis of TATP by liquid chromatography (LC) with infrared detector [13] and LC combined with MS have been reported [14,15].…”

Ion spectrometric detection technologies for ultra‐traces of explosives: A review

“…þ produces low abundance of product ions (Sigman et al, 2006). The dissociation pathway and spectrum of TATP are depicted in Figures 14 and 15.…”

“…Sigman et al have detected TATP at sub-nanogram levels using electron ionization and chemical ionization both in positive and in negative modes with both methane and ammonia as reagent gases. Positive mode ionization with ammonia reagent gas gives low limits of detection and easily recognizable adduct ion [TATPþNH 4 ] þ (Sigman et al, 2006). The early studies of nitrogen containing explosives have been reviewed (Yinon, 1982).…”