Department of Chemical and Environmental Engineering, ‡Department of Soil, Water & Environmental Science, and §Department of Chemistry & Biochemistry, University of Arizona , Tucson, Arizona 85721, United States.
Environ Sci Technol. 2017 Nov 21;51(22):13327-13334. doi: 10.1021/acs.est.7b03699. Epub 2017 Nov 6.
2,4-Dinitrosanisole (DNAN) is an insensitive munitions component replacing conventional explosives. While DNAN is known to biotransform in soils to aromatic amines and azo-dimers, it is seldom mineralized by indigenous soil bacteria. Incorporation of DNAN biotransformation products into soil as humus-bound material could serve as a plausible remediation strategy. The present work studied biotransformation of DNAN in soil and sludge microcosms supplemented with uniformly ring-labeled C-DNAN to quantify the distribution of label in soil, aqueous, and gaseous phases. Electron donor amendments, different redox conditions (anaerobic, aerobic, sequential anaerobic-aerobic), and the extracellular oxidoreductase enzyme horseradish peroxidase (HRP) were evaluated to maximize incorporation of DNAN biotransformation products into the nonextractable soil humus fraction, humin. Irreversible humin incorporation of C-DNAN occurred at higher rates in anaerobic conditions, with a moderate increase when pyruvate was added. Additionally, a single dose of HRP resulted in an instantaneous increased incorporation of C-DNAN into the humin fraction. C-DNAN incorporation to the humin fraction was strongly correlated (R = 0.93) by the soil organic carbon (OC) amount present (either intrinsic or amended). Globally, our results suggest that DNAN biotransformation products can be irreversibly bound to humin in soils as a remediation strategy, which can be enhanced by adding soil OC.
2,4-二硝基苯甲醚(DNAN)是一种钝感弹药成分,可替代传统炸药。虽然已知 DNAN 在土壤中生物转化为芳香胺和偶氮二聚体,但很少被土著土壤细菌矿化。将 DNAN 生物转化产物作为腐殖质结合物质掺入土壤中可能是一种合理的修复策略。本研究在添加均环标记的 C-DNAN 的土壤和污泥微宇宙中研究了 DNAN 的生物转化,以量化标记在土壤、水相和气相中的分布。评估了电子供体添加剂、不同的氧化还原条件(厌氧、需氧、顺序厌氧-需氧)和细胞外氧化还原酶辣根过氧化物酶(HRP),以最大程度地将 DNAN 生物转化产物掺入不可提取的土壤腐殖质部分——腐殖质中。在厌氧条件下,C-DNAN 不可逆地掺入腐殖质的速率较高,当添加丙酮酸时,速率适度增加。此外,单次 HRP 处理会导致 C-DNAN 立即增加到腐殖质部分的掺入。C-DNAN 对腐殖质部分的掺入与存在的土壤有机碳(OC)量(内在的或添加的)呈强相关性(R = 0.93)。总体而言,我们的结果表明,DNAN 生物转化产物可以作为一种修复策略不可逆地结合到土壤腐殖质中,通过添加土壤 OC 可以增强这一过程。