(Bio)transformation of 2,4-dinitroanisole (DNAN) in soils

Christopher I. Olivares, Leif Abrell, Raju Khatiwada, Jon Chorover, Reyes Sierra-Alvarez, Jim A. Field

Research output: Research - peer-reviewArticle

  • 7 Citations

Abstract

Recent studies have begun to assess the environmental fate and toxicity of 2,4-dinitroanisole (DNAN), an insensitive munition compound of interest to defense agencies. Aerobic and anaerobic DNAN biotransformation in soils was evaluated in this study. Under aerobic conditions, there was little evidence of transformation; most observed removal was attributed to adsorption and subsequent slow chemical reactions. Under anaerobic conditions, DNAN was reductively (bio)transformed and the rate of the transformation was positively correlated with soil organic carbon (OC) up to a threshold of 2.07% OC. H2 addition enhanced the nitroreduction rate compared to endogenous treatments lacking H2. Heat-killed treatments provided rates similar to the endogenous treatment, suggesting that abiotic factors play a role in DNAN reduction. Ten (bio)transformation products were detected by high-resolution mass spectrometry. The proposed transformation pathway involves reduction of DNAN to aromatic amines, with putative reactive nitroso-intermediates coupling with the amines to form azo dimers. Secondary reactions include N-alkyl substitution, O-demethylation (sometimes followed by dehydroxylation), and removal of an N-containing group. Globally, our results suggest that the main reaction DNAN undergoes in anaerobic soils is nitroreduction to 2-methoxy-5-nitroaniline (MENA) and 2,4-diaminoanisole (DAAN), followed by anaerobic coupling reactions yielding azo-dimers. The dimers were subsequently subject to further (bio)transformations.

LanguageEnglish (US)
Pages214-221
Number of pages8
JournalJournal of Hazardous Materials
Volume304
DOIs
StatePublished - Mar 5 2016

Fingerprint

biotransformation
soil
rate
Dimers
Soils
Biotransformation
2,4-dinitroanisole
Soil
organic carbon
amine
removal
Organic carbon
Amines
dehydroxylation
environmental fate
oxic conditions
chemical reaction
anoxic conditions
substitution
mass spectrometry

Keywords

  • 2,4-Dinitroanisole
  • Biodegradation
  • Insensitive munitions
  • Nitroaromatics
  • Soil

ASJC Scopus subject areas

  • Health, Toxicology and Mutagenesis
  • Pollution
  • Waste Management and Disposal
  • Environmental Chemistry
  • Environmental Engineering

Cite this

(Bio)transformation of 2,4-dinitroanisole (DNAN) in soils. / Olivares, Christopher I.; Abrell, Leif; Khatiwada, Raju; Chorover, Jon; Sierra-Alvarez, Reyes; Field, Jim A.

In: Journal of Hazardous Materials, Vol. 304, 05.03.2016, p. 214-221.

Research output: Research - peer-reviewArticle

@article{11c85c17854842ca9dc430d5f28cce4a,
title = "(Bio)transformation of 2,4-dinitroanisole (DNAN) in soils",
abstract = "Recent studies have begun to assess the environmental fate and toxicity of 2,4-dinitroanisole (DNAN), an insensitive munition compound of interest to defense agencies. Aerobic and anaerobic DNAN biotransformation in soils was evaluated in this study. Under aerobic conditions, there was little evidence of transformation; most observed removal was attributed to adsorption and subsequent slow chemical reactions. Under anaerobic conditions, DNAN was reductively (bio)transformed and the rate of the transformation was positively correlated with soil organic carbon (OC) up to a threshold of 2.07% OC. H2 addition enhanced the nitroreduction rate compared to endogenous treatments lacking H2. Heat-killed treatments provided rates similar to the endogenous treatment, suggesting that abiotic factors play a role in DNAN reduction. Ten (bio)transformation products were detected by high-resolution mass spectrometry. The proposed transformation pathway involves reduction of DNAN to aromatic amines, with putative reactive nitroso-intermediates coupling with the amines to form azo dimers. Secondary reactions include N-alkyl substitution, O-demethylation (sometimes followed by dehydroxylation), and removal of an N-containing group. Globally, our results suggest that the main reaction DNAN undergoes in anaerobic soils is nitroreduction to 2-methoxy-5-nitroaniline (MENA) and 2,4-diaminoanisole (DAAN), followed by anaerobic coupling reactions yielding azo-dimers. The dimers were subsequently subject to further (bio)transformations.",
keywords = "2,4-Dinitroanisole, Biodegradation, Insensitive munitions, Nitroaromatics, Soil",
author = "Olivares, {Christopher I.} and Leif Abrell and Raju Khatiwada and Jon Chorover and Reyes Sierra-Alvarez and Field, {Jim A.}",
year = "2016",
month = "3",
doi = "10.1016/j.jhazmat.2015.10.059",
volume = "304",
pages = "214--221",
journal = "Journal of Hazardous Materials",
issn = "0304-3894",
publisher = "Elsevier",

}

TY - JOUR

T1 - (Bio)transformation of 2,4-dinitroanisole (DNAN) in soils

AU - Olivares,Christopher I.

AU - Abrell,Leif

AU - Khatiwada,Raju

AU - Chorover,Jon

AU - Sierra-Alvarez,Reyes

AU - Field,Jim A.

PY - 2016/3/5

Y1 - 2016/3/5

N2 - Recent studies have begun to assess the environmental fate and toxicity of 2,4-dinitroanisole (DNAN), an insensitive munition compound of interest to defense agencies. Aerobic and anaerobic DNAN biotransformation in soils was evaluated in this study. Under aerobic conditions, there was little evidence of transformation; most observed removal was attributed to adsorption and subsequent slow chemical reactions. Under anaerobic conditions, DNAN was reductively (bio)transformed and the rate of the transformation was positively correlated with soil organic carbon (OC) up to a threshold of 2.07% OC. H2 addition enhanced the nitroreduction rate compared to endogenous treatments lacking H2. Heat-killed treatments provided rates similar to the endogenous treatment, suggesting that abiotic factors play a role in DNAN reduction. Ten (bio)transformation products were detected by high-resolution mass spectrometry. The proposed transformation pathway involves reduction of DNAN to aromatic amines, with putative reactive nitroso-intermediates coupling with the amines to form azo dimers. Secondary reactions include N-alkyl substitution, O-demethylation (sometimes followed by dehydroxylation), and removal of an N-containing group. Globally, our results suggest that the main reaction DNAN undergoes in anaerobic soils is nitroreduction to 2-methoxy-5-nitroaniline (MENA) and 2,4-diaminoanisole (DAAN), followed by anaerobic coupling reactions yielding azo-dimers. The dimers were subsequently subject to further (bio)transformations.

AB - Recent studies have begun to assess the environmental fate and toxicity of 2,4-dinitroanisole (DNAN), an insensitive munition compound of interest to defense agencies. Aerobic and anaerobic DNAN biotransformation in soils was evaluated in this study. Under aerobic conditions, there was little evidence of transformation; most observed removal was attributed to adsorption and subsequent slow chemical reactions. Under anaerobic conditions, DNAN was reductively (bio)transformed and the rate of the transformation was positively correlated with soil organic carbon (OC) up to a threshold of 2.07% OC. H2 addition enhanced the nitroreduction rate compared to endogenous treatments lacking H2. Heat-killed treatments provided rates similar to the endogenous treatment, suggesting that abiotic factors play a role in DNAN reduction. Ten (bio)transformation products were detected by high-resolution mass spectrometry. The proposed transformation pathway involves reduction of DNAN to aromatic amines, with putative reactive nitroso-intermediates coupling with the amines to form azo dimers. Secondary reactions include N-alkyl substitution, O-demethylation (sometimes followed by dehydroxylation), and removal of an N-containing group. Globally, our results suggest that the main reaction DNAN undergoes in anaerobic soils is nitroreduction to 2-methoxy-5-nitroaniline (MENA) and 2,4-diaminoanisole (DAAN), followed by anaerobic coupling reactions yielding azo-dimers. The dimers were subsequently subject to further (bio)transformations.

KW - 2,4-Dinitroanisole

KW - Biodegradation

KW - Insensitive munitions

KW - Nitroaromatics

KW - Soil

UR - http://www.scopus.com/inward/record.url?scp=84946430357&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84946430357&partnerID=8YFLogxK

U2 - 10.1016/j.jhazmat.2015.10.059

DO - 10.1016/j.jhazmat.2015.10.059

M3 - Article

VL - 304

SP - 214

EP - 221

JO - Journal of Hazardous Materials

T2 - Journal of Hazardous Materials

JF - Journal of Hazardous Materials

SN - 0304-3894

ER -