Evidence of anaerobic coupling reactions between reduced intermediates of 4-nitroanisole

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

Nitroaromatic compounds are widely used in agricultural pesticides, pharmaceuticals, military explosives, and other applications. They enter the environment via manufacturing and municipal wastewater discharges and releases from agricultural and military operations. Because of their ubiquity and toxicity, they are considered an important class of environmental contaminants. Nitroaromatics are known to undergo reductive transformation to aromatic amines, and under aerobic conditions they are susceptible to coupling reactions which may lead to their irreversible incorporation into soil organic matter. However, there is also evidence of coupling reactions in the absence of oxygen between reduced intermediates of the insensitive munitions compound 2,4-dinitroanisole, leading to the formation of azo dimers. The formation of such products is a concern since they may be more toxic than the original nitroaromatic compounds. The objective of this research is to provide evidence of the anaerobic formation of azo coupling products. 4-Nitroanisole was used as a model compound and was spiked into incubations containing anaerobic granular sludge with H2 as the electron donor. Using liquid chromatography, UV–Vis spectroscopy, and mass spectrometry, the formation of the azo dimer 4,4′-dimethoxyazobenzene was confirmed. However, due to the instability of the azo bond under the reducing conditions of our incubations, the azo dimer did not accumulate. Consequently, 4-aminoanisole was the major product formed in our experiment. Other minor suspected coupling products were also detected in our incubations. The results provide clear evidence for the temporal formation of at least one azo dimer in the anaerobic reduction of a model nitroaromatic compound.

Original languageEnglish (US)
Pages (from-to)372-380
Number of pages9
JournalChemosphere
Volume195
DOIs
StatePublished - Mar 1 2018

Fingerprint

Poisons
Waste Water
Sewage
Pesticides
Liquid Chromatography
Dimers
Amines
Mass Spectrometry
Spectrum Analysis
Soil
Electrons
Oxygen
incubation
Research
Pharmaceutical Preparations
Military operations
Liquid chromatography
oxic conditions
Biological materials
Drug products

Keywords

  • 2,4-Dinitroanisole (DNAN)
  • Anaerobic biotransformation
  • Azobenzenes
  • Insensitive munitions compounds
  • Nitroaromatics

ASJC Scopus subject areas

  • Environmental Chemistry
  • Chemistry(all)

Cite this

Evidence of anaerobic coupling reactions between reduced intermediates of 4-nitroanisole. / Kadoya, Warren M.; Sierra Alvarez, Maria Reye; Wong, Stanley; Abrell, Leif M; Mash, Eugene A; Field, James A.

In: Chemosphere, Vol. 195, 01.03.2018, p. 372-380.

Research output: Contribution to journalArticle

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