Rapid quantification and screening of nitrogen-containing rocket fuel transformation products by vortex assisted liquid-liquid microextraction and gas chromatography – high-resolution Orbitrap mass spectrometry

Ul’yanovskii, N. V.; Kosyakov, D. S.; Popov, M. S.; Shavrina, I. S.; Ивахнов, А. Д.; Kenessov, Bulat; Lebedev, A. T.

doi:10.1016/j.microc.2021.106821

Cited by 8 publications

(3 citation statements)

References 44 publications

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“…The comparison of the developed method with those described in the literature for single analytes and based on GC [ 14 , 34 , 35 ] or HPLC [ 12 ] separations showed sensitivity similar to GC-MS or HPLC-MS and at least one order of magnitude gain in LOD for SDMU when compared with the GC-NPD method provided by the U.S. Environmental Protection Agency (EPA) [ 36 ]. It is worth noting that the SFC-MS/MS method, unlike those mentioned, is distinguished with exceptional rapidity (1.5 min), low consumption of organic solvent, and low cost of the mobile phase.…”

Section: Resultsmentioning

confidence: 99%

Rapid Simultaneous Quantification of 1-Formyl-2,2-Dimethylhydrazine and Dimethylurea Isomers in Environmental Samples by Supercritical Fluid Chromatography–Tandem Mass Spectrometry

et al. 2022

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When released to the environment, the rocket fuel unsymmetrical dimethylhydrazine (UDMH) undergoes oxidative transformations, resulting in the formation of an extremely large number of nitrogen-containing transformation products, including isomeric compounds which are difficult to discriminate by common chromatography techniques. In the present work, supercritical fluid chromatography–tandem mass spectrometry (SFC-MS/MS) was proposed for resolving the problem of fast separation and simultaneous quantification of 1-formyl-2,2-dimethylhydrazine (FADMH) as one of the major UDMH transformation products, and its isomers—1,1-dimethylurea (UDMU) and 1,2-dimethylurea (SDMU). 2-Ethylpyridine stationary phase provided baseline separation of analytes in 1.5 min without the distortion of the chromatographic peaks. Optimization of SFC separation and MS/MS detection conditions allowed for the development of rapid, sensitive, and “green” method for the simultaneous determination of FADMH, UDMU, and SDMU in environmental samples with LOQs of 1–10 µg L−1 and linear range covering three orders of magnitude. The method was validated and successfully tested on the real extracts of peaty and sandy soils polluted with rocket fuel and UDMH oxidation products. It was shown that both UDMU and SDMU are formed in noticeable amounts during UDMH oxidation. Despite relatively low toxicity, UDMU can be considered one of the major UDMH transformation products and a potential marker of soil pollution with toxic rocket fuel.

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Section: Resultsmentioning

confidence: 99%

Rapid Simultaneous Quantification of 1-Formyl-2,2-Dimethylhydrazine and Dimethylurea Isomers in Environmental Samples by Supercritical Fluid Chromatography–Tandem Mass Spectrometry

et al. 2022

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“…Gas chromatography is a more universal solution for separating the widest possible range of UDMH transformation products (with the exception of hydrazines and some thermolabile compounds). 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].…”

Section: Introductionmentioning

confidence: 99%

“…The use of GC-MS for the analysis of aqueous samples is limited by the need to change the matrix, since the introduction of even small amounts of water into the chromatographic column leads to distortion of the shape of the chromatographic peaks, loss of separation efficiency, and instability of the analyte retention times. To solve this problem, liquid-liquid extraction (LLE) from a saturated saline solution [14,16,19], as well as solid-phase microextraction (SPME) from the vapor phase [20,21] were used. Despite the possibility of significant preconcentration of analytes, these methods also have a number of disadvantages.…”

Section: Introductionmentioning

confidence: 99%

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

2021

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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.

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Analysis of nitrogen‐containing rocket fuel transformation products in loamy soil by thermal desorption gas chromatography‐tandem mass spectrometry

Popov,

Kosyakov,

Ul'yanovskii

2024

J of Separation Science

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Unsymmetrical dimethylhydrazine (UDMH) based rocket fuel, when released into the soil, undergoes oxidative transformations to form a variety of toxic nitrogen‐containing products (TPs). Loamy soils containing aluminosilicates (clay) are capable of strong binding and retention of UDMH TPs due to a combination of polar sorption and cation‐exchange properties, posing challenges for their extraction and quantification. To overcome this problem, the present study proposes direct thermal desorption (TD) of analytes from loam facilitated by the addition of modifiers competing with UDMH TPs for sorption centers and ensuring their conversion into molecular form. Among tested additives, the mixture of potassium chloride and hydroxide demonstrated the best performance and provided recoveries of the most UDMH TPs exceeding 70% under optimized TD conditions (200°C, 30 min). The online combination of TD with gas chromatography‐tandem mass spectrometry allowed for the development of a method for the determination of 15 UDMH TPs in loamy soils with limits of detection in the range of 0.2–15 µg/kg. The use of matrix‐matched calibration and deuterated internal standards ensured high accuracy (80%–100%) and precision (relative standard deviation < 18%) of the analysis. The developed method was validated and successfully tested in the analyses of real loamy soil samples polluted with rocket fuel.

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Rapid quantification and screening of nitrogen-containing rocket fuel transformation products by vortex assisted liquid-liquid microextraction and gas chromatography – high-resolution Orbitrap mass spectrometry

Cited by 8 publications

References 44 publications

Rapid Simultaneous Quantification of 1-Formyl-2,2-Dimethylhydrazine and Dimethylurea Isomers in Environmental Samples by Supercritical Fluid Chromatography–Tandem Mass Spectrometry

Rapid Simultaneous Quantification of 1-Formyl-2,2-Dimethylhydrazine and Dimethylurea Isomers in Environmental Samples by Supercritical Fluid Chromatography–Tandem Mass Spectrometry

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

Analysis of nitrogen‐containing rocket fuel transformation products in loamy soil by thermal desorption gas chromatography‐tandem mass spectrometry

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