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

JOURNAL OF HAZARDOUS MATERIALS

卷:413

Article

Menezes, Osmar^1,2  Kadoya, Warren M.¹  Gavazza, Savia²  Sierra-Alvarez, Reyes¹  Mash, Eugene A.³  Abrell, Leif^3,4  Field, Jim A.¹ 

[1] Univ Arizona, Dept Chem & Environm Engn, Tucson, AZ 85721 USA

[2] Univ Fed Pernambuco, Dept Engn Civil & Ambiental, Lab Saneamento Ambiental, BR-50740530 Recife, PE, Brazil

[3] Univ Arizona, Dept Chem & Biochem, Tucson, AZ 85721 USA

[4] Univ Arizona, Dept Environm Sci, Tucson, AZ 85721 USA

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

DOI  :  10.1016/j.jhazmat.2021.125459

来源: Elsevier

【 摘 要 】

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.

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