The first method for quantitative trace analysis of peroxide-based explosives is described. A reversed-phase high-performance liquid chromatography method with post-column UV irradiation and fluorescence detection for the analysis of triacetone triperoxide (TATP) and hexamethylene triperoxide diamine (HMTD) has been developed. After separation, the analytes are degraded photochemically to hydrogen peroxide, which is subsequently determined on the basis of the peroxidase-catalyzed oxidation of p-hydroxyphenylacetic acid to the fluorescent dimer. This two-step reaction scheme in combination with the respective blanks (photochemical reactor switched off) provides for high selectivity. The limits of detection were 2 x 10(-6) mol/L for both TATP and HMTD, respectively. The method has been applied to the analysis of real samples.

In the last few years, the need to determine peroxide-based explosives in solid samples and air samples has resulted in the development of a series of new analytical methods for triacetonetriperoxide (TATP, acetone peroxide) and hexamethylenetriperoxidediamine (HMTD). In this review, after a short introduction describing the state of the art in the field, these new analytical methods are critically discussed. Particular emphasis is placed on spectroscopic and mass spectrometric methods as well as on chromatographic techniques with selective detection schemes. The potential of these methods to analyse unknown solid samples that might contain one or more of the explosives and to analyse peroxide-based explosives in air is evaluated.

A rapid and simple field test for the detection of triacetone-triperoxide (TATP) and hexamethylenetriperoxidediamine (HMTD), two explosives which find significant illegal use, has been developed. Unknown samples are first treated with a catalase solution to remove hydrogen peroxide traces, in order to provide selectivity towards peroxide-based bleaching agents which are contained in commercial laundry detergents. Subsequently, the peroxide-based explosives are decomposed via UV irradiation, thus yielding hydrogen peroxide, which is determined by the horseradish peroxidase (POD) catalysed formation of the green radical cation of 2,2'-azino-bis(3-ethylbenzothiazoline)-6-sulfonate (ABTS). The limits of detection for this method are 8 x 10(-6) mol dm(-3) for TATP and 8 x 10(-7) mol dm(-3) for HMTD, respectively. As an option, p-hydroxyphenylacetic acid (pHPAA) may be used as peroxidase substrate, resulting in lower limits of detection (8 x 10(-7) mol dm(-3) for TATP and HMTD). The complete method uses a mobile setup to be applied under field conditions.

A nondestructive analytical method for peroxide-based explosives determination in solid samples is described. Reversed-phase high-performance liquid chromatography in combination with on-line Fourier transform infrared (FT-IR) detection is used for the analysis of triacetonetriperoxide (TATP) and hexamethylenetriperoxide diamine (HMTD). In contrast to other liquid chromatographic methods with optical detection, no derivatization or decomposition of the peroxides is required. The peroxides are identified and quantified via their characteristic absorption spectra in the mid-infrared range of the electromagnetic spectrum. The detection limit of 0.5 mmol L-1 for HMTD and 1 mmol L-1 for TATP allows the identification of the explosives in complex matrixes.