International Journal of Mass Spectrometry 291 (2010) 133–139 Contents lists available at ScienceDirect International Journal of Mass Spectrometry journal homepage: www.elsevier.com/locate/ijms Identification and determination of trinitrotoluenes and their degradation products using liquid chromatography–electrospray ionization mass spectrometry Jitka Beˇ canová a,∗ , Zdenˇ ek Friedl b , Zdenˇ ek ˇ Simek a a Faculty of Science, Research Centre for Environmental Chemistry and Ecotoxicology, Masaryk University, 126/3 Kamenice, 625 00 Brno, Czech Republic b Institute of Chemistry and Technology of Environmental Protection, Faculty of Chemistry, Brno University of Technology, 118 Purkynova, 612 00 Brno, Czech Republic article info Article history: Received 5 November 2009 Received in revised form 22 December 2009 Accepted 22 January 2010 Available online 29 January 2010 Keywords: Explosives Trinitrotoluene (TNT) Degradation products HPLC–ESI-MS–MS abstract In the environs of ammunition plants and former military area, contaminations caused by explosives and their degradation products are of great environmental relevance. During the production of world- wide mostly used explosive compound – 2,4,6-trinitrotoluene its isomers were distributed into the environment. Therefore determination of 14 selected nitroaromatic compounds (trinitrotoluenes, amino dinitrotoluenes and diamino nitrotoluenes) by means of LC–MS–MS coupling utilizing electrospray ion- ization was developed. Therewith, these compounds were identified and quantified on the basis of specific precursor/product ion traces using the high selectivity and sensitivity of multiple reaction monitoring mode (MRM) of a triple quadrupole mass spectrometer. A new stationary phase designed especially for separation of EPA explosive mixture was used for separation of specific mixture of nitroaromatics compounds. Modification of HPLC properties enables base-line separation of all analytes and therefore improving of their MS identification and quantification. Limits of detection obtained using highly specific mass spectrometric detection MRM mode were in range 4–114 pg/L. MS–MS qualification and quantifi- cation of explosives and their biodegradation products is feasible also in case of samples with complex matrix and high amount of co-eluting compounds. © 2010 Elsevier B.V. All rights reserved. 1. Introduction The worldwide mostly used highly energetic compounds like 2,4,6-trinitrotoluene (2,4,6-TNT) and other polynitro organic com- pounds have been discharged into the environment since the WWI [1]. Contamination of soil and water by these compounds is caused by various military activities (manufacturing, testing, training, demilitarization, open burning/open detonation) and as a result of local military conflicts [2]. TNT and its consti- tutional isomers (2,4,5-trinitrotoluene and 2,3,4-trinitrotoluene) were distributed into the environment by wastewaters as a result of 2,4,6-TNT production (commonly known as the “red water”) [3]. Asymmetric trinitrotoluenes have almost similar properties as 2,4,6-TNT. Higher hygroscopicity and lower thermal stability were only determined [4]. Due to these properties are stud- ied compounds and other nitroaromatic compounds relatively widespread. 2,4,6-TNT is often biologically stepwise reduced to amino dini- trotoluenes (Am-DNTs), diamino nitrotoluenes (Dam-NTs) and ∗ Corresponding author. E-mail address: becanova@recetox.muni.cz (J. Beˇ canová). triaminotoluenes (Tam-Ts). However, only limited data about their toxicity and mutagenicity are available. TNTs and products of their degradation have been found to be cytotoxic presumably due to induced oxidative stress and demonstrated mutagenic capability. 2,4,6-TNT is classified as possible human carcinogen. The evidence for human carcinogenicity is inadequate, and the animal carcino- genicity data are limited [5]. 2,4,6-TNT and several of its reduced metabolites isolated from human and rat urine showed mutagenic activity without metabolic activation in Salmonella mutagenicity assay [6,7]. TNTs and products of their biotransformation may be strongly adsorbed by soils even covalently bonded to soil organic matter [1]. For that reasons their transport in the environment may be very slow. Therefore the precise identification and quantification of the TNTs and their degradation products in soils and ground waters at the level of low environmental concentration is essential. To be able to provide insight into the environmental fate of explosives and the risk associated with their presence, analytical tools capable to analyse such chemicals and their transformation products in vari- ous environmental media has to be available. Gas chromatography [8–11], capillary electrophoresis [12,13] and thin layer chromatog- raphy [14] have been used in special cases. High performance liquid chromatography (HPLC) has remained to be the best analytical tool 1387-3806/$ – see front matter © 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.ijms.2010.01.016