title: Environmental fate of 2,4-dinitroanisole (DNAN) and its reduced products.
abstract: Several defense departments intend to replace 2,4,6-trinitrotoluene (TNT) in munitions formulations by the less sensitive 2,4-dinitroanisole (DNAN). To help understand environmental behavior and ecological risk associated with DNAN we investigated its key initial abiotic and biotic reaction routes and determined relevant physicochemical parameters (pKa, logKow, aqueous solubility (Sw), partition coefficient (Kd)) for the chemical and its products. Reduction of DNAN with either zero valent iron or bacteria regioselectively produced 2-amino-4-nitroanisole (2-ANAN) which, under strict anaerobic conditions, gave 2,4-diaminoanisole (DAAN). Hydrolysis under environmental conditions was insignificant whereas photolysis gave photodegradable intermediates 2-hydroxy-4-nitroanisole and 2,4-dinitrophenol. Physicochemical properties of DNAN and its amino products drastically depended on the type and position of substituent(s) on the aromatic ring. Sw followed the order (TNT<DNAN<2-ANAN<4-ANAN<DAAN) whereas logKow followed the order (DAAN<4-ANAN<2-ANAN<DNAN<TNT). In soil, successive replacement of -NO2 by -NH2 in DNAN enhanced irreversible sorption and reduced bioavailability under oxic conditions. Although DNAN is more soluble than TNT, its lower hydrophobicity and its tendency to form aminoderivatives that sorb irreversibly to soil contribute to make it less toxic than the traditional explosive TNT.
authors.affiliation: National Research Council Canada, 6100 Royalmount Ave, Montreal, Quebec H4P 2R2, Canada. Electronic address: jalal.hawari@cnrc-nrc.gc.ca.
authors.forename: J
authors.initials: J
authors.lastname: Hawari
authors.affiliation: National Research Council Canada, 6100 Royalmount Ave, Montreal, Quebec H4P 2R2, Canada.
authors.forename: F
authors.initials: F
authors.lastname: Monteil-Rivera
authors.affiliation: National Research Council Canada, 6100 Royalmount Ave, Montreal, Quebec H4P 2R2, Canada.
authors.forename: N N
authors.initials: NN
authors.lastname: Perreault
authors.affiliation: National Research Council Canada, 6100 Royalmount Ave, Montreal, Quebec H4P 2R2, Canada.
authors.forename: A
authors.initials: A
authors.lastname: Halasz
authors.affiliation: National Research Council Canada, 6100 Royalmount Ave, Montreal, Quebec H4P 2R2, Canada.
authors.forename: L
authors.initials: L
authors.lastname: Paquet
authors.affiliation: National Research Council Canada, 6100 Royalmount Ave, Montreal, Quebec H4P 2R2, Canada.
authors.forename: Z
authors.initials: Z
authors.lastname: Radovic-Hrapovic
authors.affiliation: National Research Council Canada, 6100 Royalmount Ave, Montreal, Quebec H4P 2R2, Canada.
authors.forename: S
authors.initials: S
authors.lastname: Deschamps
authors.affiliation: Defence Research Development Canada, Department of National Defence, Valcartier, QC, Canada.
authors.forename: S
authors.initials: S
authors.lastname: Thiboutot
authors.affiliation: Defence Research Development Canada, Department of National Defence, Valcartier, QC, Canada.
authors.forename: G
authors.initials: G
authors.lastname: Ampleman
mesh_terms: D019297:2,4-Dinitrophenol / Q000737:chemistry; D000840:Anisoles / Q000737:chemistry* / Q000633:toxicity; D002851:Chromatography, High Pressure Liquid; D002852:Chromatography, Ion Exchange; D053834:Explosive Agents / Q000737:chemistry* / Q000633:toxicity; D006868:Hydrolysis; D057927:Hydrophobic and Hydrophilic Interactions; D015394:Molecular Structure; D010655:Phenylenediamines / Q000737:chemistry; D012989:Soil Pollutants / Q000737:chemistry* / Q000633:toxicity; D012995:Solubility; D013053:Spectrophotometry
chemical_list: D000840:Anisoles; D053834:Explosive Agents; D010655:Phenylenediamines; D012989:Soil Pollutants; C539360:2,4-dinitroanisole; C007294:4-methoxy-3-phenylenediamine; C005306:4-nitroanisole; D019297:2,4-Dinitrophenol
keywords: 2,4-Diaminoanisole; 2,4-Dinitroanisole; Insensitive munition; Regioselectivity