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

Mark S Popov,Nikolay V Ul’Yanovskii,Dmitry S Kosyakov

doi:10.3390/molecules26195743

Abstract

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-d5 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.

Highlights

The use of highly toxic rocket fuel based on 1,1-dimethylhydrazine in many types of Russian, Indian, EU, and Chinese launch vehicles inevitably gives rise to a risk of environmental pollution
Given the high polarity of many nitrogen-containing compounds, their separation is impossible in reverse-phase HPLC mode, hydrophilic interaction liquid chromatography [9], stationary phases based on porous graphitized carbon [10], and analyte derivatization methods [11,12,13] were used to achieve acceptable chromatographic retention
Accelerated water sample preparation (AWASP) technique with complete water removal ensures the achievement of high efficiency of extraction of rocket fuel 1,1-dimethylh ydrazine polar nitrogen-containing transformation products from aqueous matrices

Summary

Introduction

The use of highly toxic rocket fuel based on 1,1-dimethylhydrazine (unsymmetrical dimethylhydrazine, UDMH) in many types of Russian, Indian, EU, and Chinese launch vehicles inevitably gives rise to a risk of environmental pollution. It can be associated with an ingress of rocket fuel into soils and water bodies in fall sites of spent rocket stages, emergency situations, as well as the disposal of UDMH containing wastewater generated at launch sites during storage, transportation of fuel, and refueling the carrier rockets [1,2]. In combination with mass spectrometric detection, it has found application for the search, identification, and determination of dozens of UDMH transformation products in soils [5,14,15,16,17,18,19]

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