Biodegradation of insensitive munition formulations IMX101 and IMX104 in surface soils.

The biodegradation potential of insensitive munition melt cast formulations IMX101 and IMX104 was investigated in two unamended training range soils under aerobic and anaerobic growth conditions. Changes in community profiles in soil microcosms were monitored via high-throughput 16S rRNA sequencing over the course of the experiments to infer key microbial phylotypes that may be linked to IMX degradation. Complete anaerobic biotransformation occurred for IMX101 and IMX104 constituents 2,4-dinitroanisole (DNAN) and 3-nitro-1,2,4-triazol-5-one during the 30-day incubation period with Camp Shelby (CS) soil. By comparison, soil from Umatilla chemical depot demonstrated incomplete DNAN degradation with reduced transformation rates for both IMX101 and IMX104. Aerobic soil microcosms for both soils demonstrated reduced transformation rates compared to anaerobic degradation for all IMX constituents with DNAN the most susceptible to biotransformation by CS soil. Overall, IMX constituents hexahydro-1,3,5-trinitro-1,3,5-triazine and 1-nitroguanidine did not undergo significant transformation. In CS soil, organisms that have been associated with explosives degradation, namely members of the Burkholderiaceae, Bacillaceae, and Paenibacillaceae phylotypes increased significantly in anaerobic treatments whereas Sphingomonadaceae increased significantly in aerobic treatments. Collectively, these data may be used to populate fate and transport models to provide more accurate estimates for assessing environmental costs associated with release of IMX101 and IMX104.

Transport of insensitive munitions constituents, NTO, DNAN, RDX, and HMX in runoff and sediment under simulated rainfall.

Insensitive munition constituents derived from residues of low order detonations and deposited on military training grounds present environmental risks. A series of rainfall simulation experiments on small soil plots examined the effect of precipitation, soil properties, and particle size on transport of IMX-104 munition components: NTO (3-nitro-1,2,4-triazol-5-one), DNAN (2,4-dinitroanisole), RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), and HMX (octahydro-1,3,5,7- tertranitro-1,3,5,7-tetrazocine). The primary pathways for rainfall driven transport were subsurface infiltration, off-site transport in solution, and transport in solid form including re-adsorption onto soil particles. The transport was solubility dependent with NTO moving mostly in solution, which was dominated by either runoff or infiltration depending on soil. DNAN, RDX, and HMX, were transported primarily in particulate form. The fine energetic fraction (<2 mm) showed the highest mobility, while the coarsest fraction (>4.75 mm) remained in-situ after rainfall. A simple linear model relating energetics transport with sediment yield and energetics particle size and was proposed. These findings provide the first comprehensive mass balance of munition constituents as affected by overland flow under rainfall. They improve our understanding of environmental fate of munitions, can further be used for predictive modelling, developing mitigation strategies, and regulatory compliance.

A laboratory rill study of IMX-104 transport in overland flow.

The deposition of explosive contaminants in particulate form onto the soil surface during low-order detonations can lead to ground and surface water contamination. The vertical fate and transport of insensitive munitions formulation IMX-104 through soil has been thoroughly studied, however the lateral transport of explosive particles on the surface is less known. The objective of this research was to understand the impact of overland flow on the transport of IMX-104 constituent compounds 3-nitro-1,2,4-triazol-5-one (NTO), 2,4-dinitroanisole (DNAN), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX). The effect of overland flow was examined in a rill flume using several flow rates (165-, 265-, and 300-mL min-1) and IMX-104 particle sizes (4.75-9.51 mm, 2.83-4.75 mm, 2-2.83 mm, and <2 mm). We found that the smaller particles were transported more in solution and with the sediment compared to the larger particles, which had a higher percent mass remaining on the surface. As flow rate increased, there was an increase in the percent mass found in solution and sediment and a decrease in the percent mass remaining on the surface. NTO fate was dominated by transport in solution, while DNAN, RDX and HMX were predominantly transported with the sediment. This research provides evidence of the role of overland flow in the fate of energetic compounds.

Outdoor dissolution and photodegradation of insensitive munitions formulations IMX-101 and IMX-104: Photolytic transformation pathway and mechanism study.

New munition compounds have been developed to replace traditional explosives to prevent unintended detonations. However, insensitive munitions (IM) can leave large proportion of unexploded charge in the field, where it is subjected to photodegradation and dissolution in precipitation. The photolytic reactions occurring on the surfaces of IMX-101 and IMX-104 formulations and the subsequent fate of photolytic products in the environment were thoroughly investigated. The constituents of IMX-101 and IMX-104 formulations dissolve sequentially under rainfall in the order of aqueous solubility: 3-nitro-1,2,4-triazol-5-one (NTO) > nitroguanidine (NQ) > 2,4-dinitroanisole (DNAN) > 1,3,5-hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). A linear relationship between DNAN dissolution and rainwater volume was observed (r2: 0.86-0.99). It was estimated that it would take 16-228 years to completely dissolve these formulation particles under natural environmental conditions in Oracle, AZ. We used LC/MS/MS and GC/MS to examine the dissolution samples from IMX-101 and 104 particles exposed to rainfall and sunlight and found six DNAN photo-transformation products including 2-methoxy-5-nitrophenol, 4-methoxy-3-nitrophenol, 4-methoxy-3-nitroaniline, 2-methoxy-5-nitroaniline, 2,4-dinitrophenol, and methoxy-dinitrophenol, which are in good agreement with computational modeling results of bond strengths. The main DNAN photodegradation pathways are therefore proposed. Predicted eco-toxicity values suggested that the parent compound DNAN, methoxy-nitrophenols, methoxy-nitroanilines and the other two products (2,4-dinitrophenol and methoxy-dinitrophenol) would be harmful to fish and daphnid. Our study provides improved insight about the rain dissolution and photochemical behavior of IM formulations under natural conditions, which helps to form target-oriented strategies to mitigate explosive contamination in military training sites.