Gas Chromatography–Mass Spectrometry Quantification of 1,1-Dimethylhydrazine Transformation Products in Aqueous Solutions: Accelerated Water Sample Preparation

The use of highly toxic rocket fuel based on 1,1-dimethylhydrazine (UDMH) in many types of carrier rockets poses a threat to environment and human health associated with an ingress of UDMH into wastewater and natural reservoirs and its transformation with the formation of numerous toxic nitrogen-containing products. Their GC-MS quantification in aqueous samples requires matrix change and is challenging due to high polarity of analytes. To overcome this problem, accelerated water sample preparation (AWASP) based on the complete removal of water with anhydrous sodium sulfate and transferring analytes into dichloromethane was used. Twenty-nine UDMH transformation products including both the acyclic and heterocyclic compounds of various classes were chosen as target analytes. AWASP ensured attaining near quantitative extraction of 23 compounds with sample preparation procedure duration of no more than 5 min. Combination of AWASP with gas chromatography–mass spectrometry and using pyridine-d(5) as an internal standard allowed for developing the rapid, simple, and low-cost method for simultaneous quantification of UDMH transformation products with detection limits of 1–5 μg L(−1) and linear concentration range covering 4 orders of magnitude. The method has been validated and successfully tested in the analysis of aqueous solutions of rocket fuel subjected to oxidation with atmospheric oxygen, as well as pyrolytic gasification in supercritical water modelling wastewater from carrier rockets launch sites.