2. Academic Validation
  3. Covalent binding with model quinone compounds unveils the environmental fate of the insensitive munitions reduced product 2,4-diaminoanisole (DAAN) under anoxic conditions

Covalent binding with model quinone compounds unveils the environmental fate of the insensitive munitions reduced product 2,4-diaminoanisole (DAAN) under anoxic conditions

  • J Hazard Mater. 2021 Jul 5:413:125459. doi: 10.1016/j.jhazmat.2021.125459.
Osmar Menezes 1,  Warren M Kadoya 2,  Savia Gavazza 3,  Reyes Sierra-Alvarez 2,  Eugene A Mash 4,  Leif Abrell 5,  Jim A Field 6
Affiliations

Affiliations

  • 1 Department of Chemical and Environmental Engineering, The University of Arizona, Tucson, AZ 85721, USA; Laboratório de Saneamento Ambiental, Departamento de Engenharia Civil e Ambiental, Universidade Federal de Pernambuco, Recife, PE 50740-530, Brazil.
  • 2 Department of Chemical and Environmental Engineering, The University of Arizona, Tucson, AZ 85721, USA.
  • 3 Laboratório de Saneamento Ambiental, Departamento de Engenharia Civil e Ambiental, Universidade Federal de Pernambuco, Recife, PE 50740-530, Brazil.
  • 4 Department of Chemistry and Biochemistry, The University of Arizona, Tucson, AZ 85721, USA.
  • 5 Department of Chemistry and Biochemistry, The University of Arizona, Tucson, AZ 85721, USA; Department of Environmental Science, The University of Arizona, AZ 85721, USA.
  • 6 Department of Chemical and Environmental Engineering, The University of Arizona, Tucson, AZ 85721, USA. Electronic address: jimfield@email.arizona.edu.
PMID: 33930971 DOI: 10.1016/j.jhazmat.2021.125459
Abstract

2,4-Dinitroanisole (DNAN) is an insensitive munitions compound expected to replace 2,4,6-trinitrotoluene (TNT). The product of DNAN's reduction in the environment is 2,4-diaminoanisole (DAAN), a toxic and carcinogenic aromatic amine. DAAN is known to become irreversibly incorporated into soil natural organic matter (NOM) after DNAN's reduction. Herein, we investigate the reactions between DAAN and NOM under anoxic conditions, using 1,4-benzoquinone (BQ) and methoxybenzoquinone (MBQ) as model humic moieties of NOM. A new method stopped the fast reactions between DAAN and Quinones, capturing the fleeting intermediates. We observed that DAAN incorporation into NOM (represented by BQ and MBQ models) is quinone-dependent and occurs via Michael addition, imine (Schiff-base) formation, and azo bond formation. After dimers are formed, incorporation reactions continue, resulting in trimers and tetramers. After 20 days, 56.4% of dissolved organic carbon from a mixture of DAAN (1 mM) and MBQ (3 mM) had precipitated, indicating an extensive polymerization, with DAAN becoming incorporated into high-molecular-weight humic-like compounds. The present work suggests a new approach for DNAN environmental remediation, in which DNAN anaerobic transformation can be coupled to the formation of non-extractable bound DAAN residues in soil organic matter. This process does not require aerobic conditions nor a specific catalyst.

Keywords

2,4-Dinitroanisole (DNAN); Aromatic amine; Humic material; Insensitive high explosive; Quinone.

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