1 3 DOI 10.1007/s10337-017-3286-2 Chromatographia ORIGINAL Quantification of Transformation Products of Unsymmetrical Dimethylhydrazine in Water Using SPME and GC-MS Nadezhda V. Bakaikina 1 · Bulat Kenessov 1 · Nikolay V. Ul’yanovskii 2 · Dmitry S. Kosyakov 2 · Sergey A. Pokryshkin 2 · Miras Derbissalin 1 · Zhailaubay K. Zhubatov 3 Received: 11 December 2016 / Revised: 27 February 2017 / Accepted: 2 March 2017 © Springer-Verlag Berlin Heidelberg 2017 however, the list of analytes detected by this method can be further expanded. Accuracies determined by GC-MS were in the range of 75–125% for six analytes. Compared to other available methods based on non-SPME sample preparation approaches (e.g., liquid–liquid and solid-phase extraction), the developed method is simpler, automated and provides lower detection limits. It covers more UDMH transformation products than available SPME-based methods. The list of analytes could be further expanded if new standards become available. The developed method is recommended for assess- ing water quality in the territories affected by space activities and other related studies. Keywords SPME · GC-MS · Quantification · Transformation products · Dimethylhydrazine · Water Introduction Despite very high toxicity of a rocket fuel based on unsym- metrical dimethylhydrazine (UDMH), it is still used in heavy rockets in Russia, Kazakhstan and China [1]. Unburned UDMH remaining in tanks is spilled into the environment [2] with formation of >50 known transforma- tion products including nitrosoamines, tetrazenes, triazoles, pyrazoles, tetrazoles, imidazoles, pyrazines, aldehydes and other classes of compounds. Most of these transforma- tion products are polar, have high water solubility and can accumulate in surface and ground waters used for drinking and household purposes. Despite most spilled fuel accu- mulates in soil [3], the greatest health risks are associated with water pollution. Ul’yanovskii et al. [4] showed that concentrations of 1-methyl-1H-1,2,4-triazole (MTA) and N,N-dimethylformamide (DMF) in water samples from fall regions of rockets can reach 600 μg L -1 . Abstract Quantification of trace concentrations of trans- formation products of rocket fuel unsymmetrical dimethyl- hydrazine (UDMH) in water requires complex analytical instrumentation and tedious sample preparation. The goal of this research was to develop a simple and automated method for sensitive quantification of UDMH transformation prod- ucts in water using headspace (HS) solid-phase microex- traction (SPME) in combination with GC-MS and GC-MS/ MS. HS SPME is based on extraction of analytes from a gas phase above samples by a micro polymer coating followed by a thermal desorption of analytes in a GC inlet. Extrac- tion by 85 μm Carboxen/polydimethylsiloxane fiber at 50 °C during 60 min provides the best combination of sensitivity and precision. Tandem mass spectrometric detection with positive chemical ionization improves method accuracy and selectivity. Detection limits of twelve analytes by GC-MS/ MS with chemical ionization are about 10 ng L -1 . GC-MS provides similar detection limits for five studied analytes; Electronic supplementary material The online version of this article (doi:10.1007/s10337-017-3286-2) contains supplementary material, which is available to authorized users. * Bulat Kenessov bkenesov@gmail.com 1 Faculty of Chemistry and Chemical Technology, Center of Physical Chemical Methods of Research and Analysis, Al- Farabi Kazakh National University, 96A Tole Bi Street, Lab. 101, 050012 Almaty, Kazakhstan 2 Core Facility Center ‘Arktika’, Northern (Arctic) Federal University, 17 Severnaya Dvina Embankment, 163002 Arkhangelsk, Russia 3 Scientific Research Center “Garysh-Ecologiya”, Aerospace Committee of the Ministry of Investments and Development of the Republic of Kazakhstan, 108 Nauryzbay Batyr Street, 050000 Almaty, Kazakhstan