Carbon and Nitrogen Isotope Fractionations During Biotic and Abiotic Transformations of 2,4-Dinitroanisole (DNAN)

2,4-Dinitroanisole (DNAN) is a main constituent in various new insensitive munition formulations. Although DNAN is susceptible to biotic and abiotic transformations, in many environmental instances, transformation mechanisms are difficult to resolve, distinguish, or apportion on the basis solely of analysis of concentrations. We used compound-specific isotope analysis (CSIA) to investigate the characteristic isotope fractionations of the biotic (by three microbial consortia and three pure cultures) and abiotic (by 9,10-anthrahydroquinone-2-sulfonic acid [AHQS]) transformations of DNAN. The correlations of isotope enrichment factors (Λ^N/C) for biotic transformations had a range of values from 4.93 ± 0.53 to 12.19 ± 1.23, which is entirely distinct from Λ^N/C values reported previously for alkaline hydrolysis, enzymatic hydrolysis, reduction by Fe²⁺-bearing minerals and iron-oxide-bound Fe²⁺, and UV-driven phototransformations. The Λ^N/C value associated with the abiotic reduction by AHQS was 38.76 ± 2.23, within the range of previously reported values for DNAN reduction by Fe²⁺-bearing minerals and iron-oxide-bound Fe²⁺, albeit the mean Λ^N/C was lower. These results enhance the database of isotope effects accompanying DNAN transformations under environmentally relevant conditions, allowing better evaluation of the extents of biotic and abiotic transformations of DNAN that occur in soils, groundwaters, surface waters, and the marine environment.