Effects of oxidant and catalyst on the transformation products of rocket fuel 1,1-dimethylhydrazine in water and soil

Dmitry S Kosyakov; Nikolay V Ul'yanovskii; Ilya I Pikovskoi; Bulat Kenessov; Nadezhda V Bakaikina; Zhailaubay Zhubatov; Albert T Lebedev

doi:10.1016/j.chemosphere.2019.04.141

Effects of oxidant and catalyst on the transformation products of rocket fuel 1,1-dimethylhydrazine in water and soil

Chemosphere. 2019 Aug:228:335-344. doi: 10.1016/j.chemosphere.2019.04.141. Epub 2019 Apr 24.

Authors

Dmitry S Kosyakov¹, Nikolay V Ul'yanovskii², Ilya I Pikovskoi², Bulat Kenessov³, Nadezhda V Bakaikina³, Zhailaubay Zhubatov⁴, Albert T Lebedev⁵

Affiliations

¹ Core Facility Center "Arktika", M.V. Lomonosov Northern (Arctic) Federal University, Northern Dvina Emb. 17, Arkhangelsk, 163002, Russia. Electronic address: d.kosyakov@narfu.ru.
² Core Facility Center "Arktika", M.V. Lomonosov Northern (Arctic) Federal University, Northern Dvina Emb. 17, Arkhangelsk, 163002, Russia.
³ Center of Physical Chemical Methods of Research and Analysis, Al-Farabi Kazakh National University, 96A Tole Bi Street, 050012, Almaty, Kazakhstan.
⁴ Scientifc 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.
⁵ Core Facility Center "Arktika", M.V. Lomonosov Northern (Arctic) Federal University, Northern Dvina Emb. 17, Arkhangelsk, 163002, Russia; Department of Chemistry, M.V. Lomonosov Moscow State University, Leninskie Gory 1/3, Moscow, 119991, Russia.

PMID: 31039540
DOI: 10.1016/j.chemosphere.2019.04.141

Abstract

Existing methods for cleanup of wastewaters and soils polluted with the extremely toxic rocket fuel unsymmetrical dimethylhydrazine (UDMH) are mainly based on the treatment with various oxidative reagents. Until now, the assessment of their effectiveness was based on the residual content of UDMH and did not take into account the possibility of the formation of a large number of potentially dangerous nitrogen-containing transformation products (TPs). In this study, using the recently developed approach based on high-resolution Orbitrap mass spectrometry, the comprehensive characterization of UDMH TPs formed by the action of air oxygen and different oxidants (Fenton's reagent, KMnO₄, HOCl, H₂O₂ in the presence of Cu²⁺ and [Fe (EDTA)]^- catalysts) typically used to detoxify spill sites was performed. The range of the identified molecular formulas of TPs comprised 303 compounds of various classes. Among them, there is a number of major products not previously described in the literature. It was established that none of the investigated oxidative reagents ensures complete conversion of rocket fuel to safe compounds. The hydrogen peroxide based reagents, particularly H₂O₂ + Na [Fe (EDTA)] system currently used in Kazakhstan, give the greatest number of TPs, for many of which a toxicity was not characterized so far. The majority of the compounds found in model solutions was detected in extracts of soil from the crash site of the Proton carrier rocket, which was subjected to the on-site reagent treatment. During successive treatments, along with the decrease in the number of detectable UDMH TPs, their ratios change in favor of amines.

Keywords: 1,1-Dimethylhydrazine; High-resolution orbitrap mass spectrometry; Oxidative transformation; Rocket fuel; Soil cleanup.

MeSH terms

Dimethylhydrazines / analysis
Dimethylhydrazines / chemistry*
Mass Spectrometry / methods*
Oxidants / chemistry*
Soil / chemistry*
Water / chemistry*

Substances

Dimethylhydrazines
Oxidants
Soil
Water