ABSTRACT
Homemade explosives become a significant challenge for forensic scientists and investigators. In addition to well-known materials such as acetone peroxide trimer, black powder, or lead azides, perpetrators often produce more exotic and less recognized Homemade Explosives (HMEs). Mixtures of hydrogen peroxide with liquid fuels are widely acknowledged as powerful explosives. Interestingly, similar explosive properties are found in mixtures of numerous solid materials with H2O2. Notably, powdered groceries, such as coffee, tea, grounded spices, and flour, are particularly interesting to pyrotechnics enthusiasts due to their easy production using accessible precursors, which do not attract the attention of security agencies. H2O2-based HMEs may become a dangerous component of improvised explosive devices for terrorists and ordinary offenders. For the four most powerful mixtures-HMEs based on coffee, tea, paprika, and turmeric-molecular markers useful for identification using the GC-MS technique have been proposed. Furthermore, the observed time-dependent changes in mixtures of H2O2 with these food products were studied and evaluated as a potential method for assessing the age of the evidence and reconstructing timelines of crimes. The paper also discusses the usefulness of FT-IR spectroscopy for identifying H2O2-based HMEs.
ABSTRACT
Polymeric porous adsorbents are reported for removal of explosives, namely picric acid, 1,3,5-trinitro-1,3,5-triazinane (RDX), and pentaerythritol tetranitrate (PETN) and their subsequent quantification using direct analysis with ambient plasma mass spectrometry. The adsorbents are obtained by functionalization of short-chain poly(2-oxazoline)s with methyl ester side chains using 4-(aminomethyl)pyridine with a degree of functionalization equal to 0, 5, 10, and 20%. The subsequent step consist of cross-linking using a high internal phase emulsion procedure by further side-chain amidation with diethylenetriamine as crosslinker. Picric acid, RDX, and PETN were chosen as the model compounds as they belong to three different groups of explosives, in particular nitroaromatics, nitroamines, and nitrate esters, respectively. The adsorption isotherms, kinetics, as well as the influence of pH and temperature on the adsorption process was investigated. The porous adsorbents showed the highest maximum adsorption capacity towards picric acid, reaching 334 mg g-1, while PETN (80 mg g-1) and RDX (17.4 mg g-1) were less efficiently adsorbed. Subsequent quantification of the adsorbed explosives is performed by a specially designed ambient mass spectrometry setup equipped with a thermal heater. The obtained limits of detection were found to be 20-times improved compared to direct analysis of analyte solutions. The effectiveness of the proposed analytical setup is confirmed by successful quantification of the explosives in river water samples. The research clearly shows that functional porous adsorbents coupled directly with ambient mass spectrometry can be used for rapid quantification of explosives, which can be, e.g., used for tracking illegal manufacturing sites of these compounds.
