The Analysis of Black Powder Substitutes Containing Ascorbic Acid by Ion Chromatography/Mass Spectrometry

Bureau of Alcohol, Tobacco, Firearms and Explosives, Forensic Science Laboratory, Ammendale, MD 20705-1250, USA.
Journal of Forensic Sciences (Impact Factor: 1.16). 09/2009; 54(6):1315-22. DOI: 10.1111/j.1556-4029.2009.01144.x
Source: PubMed


Black powder substitutes containing ascorbic acid are a group of low explosives that utilize ascorbic acid as the fuel. The analysis of these powders is complicated by the degradation of ascorbic acid which occurs rapidly in solution and may also occur as the powder ages. Aqueous extracts of both intact powders and postblast residues were analyzed by an existing ion chromatography/mass spectrometry (IC/MS) method used at the Bureau of Alcohol, Tobacco, Firearms and Explosives. Results have shown that while ascorbic acid itself is not detected in this method, its diagnostic degradation products (threonic acid, monohydrated diketogulonic acid, and oxalic acid) can be identified. In addition, anions from the inorganic oxidizers (perchlorate and nitrate) and combustion products such as chloride, chlorate, and nitrite, can be identified within the same experiment. While this IC/MS method shows promise, future modifications are necessary because of limitations in identifying threonate in postblast residues, as well as coeluting compounds observed in postblast residues.

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    • "Significant research has been conducted advancing the accurate and sensitive detection of explosives, most frequently common military-grade nitrated organic explosives, including nitramines, nitroaromatics, and nitrate esters such as cyclotrimethylenetrinitramine (RDX), trinitrotoluene (TNT), and pentaerythritol tetranitrate (PETN). These explosives have been detected using a range of analytical techniques, including ion chromatography (IC) [1] [2], capillary electrophoresis (CE) [3] [4], high performance liquid chromatography (HPLC) [5], and most notably, ion mobility spectrometry (IMS) [6e13] and mass spectrometry (MS) [14e22]. The rapid analysis times and cost effectiveness of these field compatible instruments have led to widespread deployment of ion mobility spectrometry. "
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    ABSTRACT: Existing instrumental techniques must be adaptable to the analysis of novel explosives if science is to keep up with the practices of terrorists and criminals. The focus of this work has been the development of analytical techniques for the analysis of two types of novel explosives: ascorbic acid-based propellants, and improvised mixtures of concentrated hydrogen peroxide/fuel. In recent years, the use of these explosives in improvised explosive devices (IEDs) has increased. It is therefore important to develop methods which permit the identification of the nature of the original explosive from post-blast residues. Ascorbic acid-based propellants are low explosives which employ an ascorbic acid fuel source with a nitrate/perchlorate oxidizer. A method which utilized ion chromatography with indirect photometric detection was optimized for the analysis of intact propellants. Post-burn and post-blast residues if these propellants were analyzed. It was determined that the ascorbic acid fuel and nitrate oxidizer could be detected in intact propellants, as well as in the post-burn and post-blast residues. Degradation products of the nitrate and perchlorate oxidizers were also detected. With a quadrupole time-of-flight mass spectrometer (QToFMS), exact mass measurements are possible. When an HPLC instrument is coupled to a QToFMS, the combination of retention time with accurate mass measurements, mass spectral fragmentation information, and isotopic abundance patterns allows for the unequivocal identification of a target analyte. An optimized HPLC-ESI-QToFMS method was applied to the analysis of ascorbic acid-based propellants. Exact mass measurements were collected for the fuel and oxidizer anions, and their degradation products. Ascorbic acid was detected in the intact samples and half of the propellants subjected to open burning; the intact fuel molecule was not detected in any of the post-blast residue. Two methods were optimized for the analysis of trace levels of hydrogen peroxide: HPLC with fluorescence detection (HPLC-FD), and HPLC with electrochemical detection (HPLC-ED). Both techniques were extremely selective for hydrogen peroxide. Both methods were applied to the analysis of post-blast debris from improvised mixtures of concentrated hydrogen peroxide/fuel; hydrogen peroxide was detected on variety of substrates. Hydrogen peroxide was detected in the post-blast residues of the improvised explosives TATP and HMTD.
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