Chemical oxidation of unsymmetrical dimethylhydrazine transformation products in water

Keywords: unsymmetrical dimethylhydrazine transformation products, 1-formyl-2, 2-dimethylhydrazine, dimethylaminoacetonitrile, N-nitrosodimethylamine, 1-methyl-1Н-1, 2, 4-triazole, chemical oxidation

Abstract

Oxidation of unsymmetrical dimethylhydrazine (UDMH) during a water treatment has several disadvantages including formation of stable toxic byproducts. Effectiveness of treatment methods in relation to UDMH transformation products is currently poorly studied. This work considers the effectiveness of chemical oxidants in respect to main metabolites of UDMH – 1-formyl-2,2-dimethylhydrazine, dimethylaminoacetontrile, N-nitrosodimethylamine and 1-methyl-1H-1,2,4-triazole. Experiments on chemical oxidation by Fenton's reagent, potassium permanganate and sodium nitrite were conducted. Quantitative determination was performed by HPLC. Oxidation products were identified by gas chromatography-mass spectrometry in combination with solid-phase microextraction. 1-Formyl-2,2-dimethylhydrazine was completely oxidized by Fenton's reagent with formation of formaldehyde N-formyl-N-methyl-hydrazone, 1,4-dihydro-1,4-dimethyl-5H-tetrazol-5-one by the action of potassium permanganate and N-methyl-N-nitro-methanamine in the presence of sodium nitrite. Oxidation of 1-formyl-2,2-dimethylhydrazine also resulted in formation of N-nitrosodimethylamine. Oxidation of dimethylaminoacetontrile proceeded with formation of hydroxyacetonitrile, dimethylformamide and 1,2,5-trimethylpyrrole. After 30 days, dimethylaminoacetontrile was not detected in the presence of Fenton’s reagent and potassium permanganate, but it’s concentration in samples with sodium nitrite was 77.3 mg/L. In the presence of Fenton’s reagent, potassium permanganate and sodium nitrite after 30 days, N-nitrosodimethylamine concentration decreased by 85, 80 and 50%, respectively. In control sample, N-nitrosodimethylamine concentration decreased by 50%, indicating that sodium nitrite has no effect of on N-nitrosodimethylamine concentration. Only Fenton's reagent allowed to reduce the concentration of 1-methyl-1H-1,2,4-triazole to 50% in 30 days. In the presence of other oxidants, 1-methyl-1H-1,2,4-triazole concentration decreased by 15-20%. As a result of the experiment, Fenton's reagent proved to be the most effective oxidant.

Author Biographies

Madi Abilev, al-Farabi Kazakh National University, Almaty
Ph.D. student
Bulat Kenessov, al-Farabi Kazakh National University, Almaty
Professor
Svetlana Batyrbekova, al-Farabi Kazakh National University, Almaty
Center of Physical Chemical Methods of Research and Analysis, Chief Scientist
Tim Grotenhuis, Wageningen University, Wageningen
Associate Professor

References

1 Rodin IA (2009) Identification and determination of transformation products of unsymmetrical dimethylhydrazine by liquid chromatography-mass spectrometry [Identifikatsiya i opredeleniye produktov transformatsii nesimmetrichnogo dimetilgidrazina metodom zhidkostnoy khromato-mass-spektrometrii]. Dissertation for the Degree of Candidate of Chemical Science. Moscow, Russia. (In Russian)

2 Kenessov BN, Koziel JA, Grotenhuis T, Carlsen L (2010) Anal Chim Acta 674:32-39. http://dx.doi.org/10.1016/j.aca.2010.05.040

3 Kenessov B, Alimzhanova M, Sailaukhanuly Y, Baimatova N, Abilev M, Batyrbekova S, Carlsen L, Tulegenov A, Nauryzbayev M (2012) Sci Total Environ 427:78-85. http://dx.doi.org/10.1016/j.scitotenv.2012.04.017

4 Carlsen L, Kenessov BN, Batyrbekova SYe (2009) Environ Toxicol Phar 27:415-423. http://dx.doi.org/10.1016/j.etap.2009.01.005

5 Lunn G, Sansone EB (1994) Chemosphere 29:1577-1590. http://dx.doi.org/10.1016/0045-6535(94)90287-9

6 Pestunova OP, Elizarova GL, Ismagilov ZR, Kerzhentsev MA, Parmon VN (2002) Catal Today 75:219-225. http://dx.doi.org/10.1016/S0920-5861(02)00072-X

7 Makhotkina OA, Kuznetsova EV, Preis SV (2006) Appl Catal B-Environ 68:85-91. http://dx.doi.org/10.1016/j.apcatb.2006.07.008

8 Mahmood TA, Reza G (2014) Ultrason Sonochem 23:257-265. http://dx.doi.org/10.1016/j.ultsonch.2014.09.007

9 Buryak AK, Serdyuk TM, Ulyanov AV (2011) Theor Found Chem Eng 45:550-555. http://dx.doi.org/10.1134/S0040579510051057

10 Shah AD, Mitch WA (2012) Environ Sci Technol 46:119-131. http://dx.doi.org/10.1021/es203312s

11 Kruchinin NA, Nekhoroshev NI (1997) Method of decontamination of soil from toxic organic substances [Sposob obezvrezhivaniya grunta i pochvy ot toksichnykh organicheskikh veshchestv]. Patent of Russian Federation [Patent Rossiyskoi Federatsii]. (In Russian)

12 Kruchinin NA, Nekhoroshev NI (2010) Method of detoxification of soil and water environments from organic pollutants [Sposob detoksikatsii pochvennykh i vodnykh sred ot organicheskikh zagryazniteley]. Patent of Russian Federation [Patent Rossiyskoi Federatsii]. (In Russian)

13 Lee C, Lee Y, Schmidt C, Yoon J, Von Gunten U (2008) Water Res 42:433-441. http://dx.doi.org/10.1016/j.watres.2007.07.035

14 Mitch WA, Gerecke AC, Sedlak DL (2003) Water Res 37:3733-3741. http://dx.doi.org/10.1016/S0043-1354(03)00289-6

15 Ismagilov ZR, Kerzhentsev MA, Ismagilov IZ, Sazonov VA, Parmon VN, Elizarova GL, Pestunova OP, Shandakov VA, Zuev YuL, Eryomin VN, Pestereva NV, Garin F, Veringa HJ (2002) Catal Today 75:277-285. http://dx.doi.org/10.1016/S0920-5861(02)00080-9

16 Sgroi M, Roccaro P, Oelker GL, Snyder SA (2014) Environ Sci Technol 48:10308-10315. http://dx.doi.org/10.1021/es5011658

17 Krasner SW, Mitch WA, McCurry DL, Hanigan D, Westerhoff P (2013) Water Res 47:4433-4450. http://dx.doi.org/10.1016/j.watres.2013.04.050

18 Li A, Chen Z, Yang L (2010) Adv Mat Res 113-116:1402-1406. http://dx.doi.org/10.4028/www.scientific.net/AMR.113-116.1402

19 Alimzhanova MB, Kenessov BN, Batyrbekova SYe, Carlsen L, Nauryzbaev MK (2009) Izvestiya Natsional'noi Akademii Nauk Respubliki Kazakhstan, Seriya Khimii i Tekhnologii 1:87-92. (In Russian)

20 Kenessov BN, Saylaukhanuly Ye, Musrepov BA, Kaldarov AK (2008) Chemical Bulletin of Kazakh National University 1:184-189.

Published
2015-03-31
How to Cite
Abilev, M., Kenessov, B., Batyrbekova, S., & Grotenhuis, T. (2015). Chemical oxidation of unsymmetrical dimethylhydrazine transformation products in water. Chemical Bulletin of Kazakh National University, (1), 20-29. https://doi.org/https://doi.org/10.15328/cb505
Section
Environmental Chemistry