Combined Biological and Chemical Mechanisms for Degradation of Insensitive Munitions in the Presence of Alternate Explosives
ER-2222
Objective
The Department of Defense (DoD) has developed several new explosives composites that have been updated with insensitive munitions (IM), including 2,4-dintroanisole (DNAN) and 3-nitro-1,2,4-triazole-5-one (NTO). These composites are segueing from research explosives to functional explosives for the military. Information is needed to assess the risk that IM compounds may represent once new ordnance is used routinely at military live-fire training ranges. This project will investigate a specific mechanism by which nitro-functional group-bearing explosives have been reported to degrade—mixed biological-abiotic degradation with ferric/ferrous iron as electron transfer intermediates. The broad objective is to understand how combined chemical and biological reactions influence degradation of the IM compounds DNAN and NTO. Specific objectives are to quantify the kinetics of NTO and DNAN degradation by biological versus chemical transformation mechanisms in the presence and absence of competing molecules that are found in the explosive composites; determine the intermediates that arise during chemical versus biological degradation; and characterize the mixed "biological-abiotic" degradation mechanisms in controlled systems as well as contaminated aquifer material.
Technical Approach
The following hypotheses will be tested in this project:
- Ferrous iron, as adsorbed ferrous iron or in the mineral phase magnetite, will directly reduce the nitro functional groups on DNAN and NTO.
- Biological degradation of NTO and DNAN will proceed via a reductive pathway rather than an oxidative pathway.
- Chemical transformation kinetics will be faster than biological transformation kinetics.
- Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), and 2,4,6-trinitrotoluene (TNT) will inhibit NTO and DNAN reduction.
- The primary reaction products of NTO and DNAN will be different based on chemical versus biological degradation pathways, with amine-group molecules (aniline) being the primary product during biological reduction and nitro-aryl-radicals being the primary product during chemical reduction.
- Mixed biotic-abiotic reactions will degrade NTO and DNAN at rates that are at least double that of either individual mechanism alone.
To address hypotheses 1-3, researchers will quantify the kinetics and assess potential mechanisms of NTO and DNAN degradation in controlled batch systems using strictly chemical or strictly biological degradation mechanisms. Hypothesis 5 will be addressed by identifying the dominant reaction products of NTO and DNAN when degraded by biological versus chemical pathways. NTO and DNAN will first be investigated as the sole electron acceptor/contaminant; there will be no competing electron acceptors in the form of explosives or other molecules that are environmentally relevant (e.g., nitrate). To address hypothesis 4, competing electron acceptors such as RDX and HMX will be included in the batch systems. Hypothesis 6 will be addressed by identifying the influence of combined biological-abiotic reactions on NTO and DNAN degradation in the presence and absence of competing electron acceptors.
Benefits
This project will improve understanding of the reactions and pathways by which IM compounds degrade, at what rate they degrade, and what products form that can be used to assess the extent to which they are attenuating under site conditions. The innovative aspects of the work relate to the use of combined biological and chemical reactions, with a specific emphasis on Fe(III) reduction and iron-mediated electron transfer to IM compounds, and competition from alternate explosives within the composites. (Anticipated Project Completion - 2015)
Points of Contact
Principal Investigator
Dr. Kevin Finneran
Clemson University
Phone: 864-656-4202
Document Types
- Fact Sheet - Brief project summary with links to related documents and points of contact.
- Final Report - Comprehensive report for every completed SERDP and ESTCP project that contains all technical results.
- Cost & Performance Report - Overview of ESTCP demonstration activities, results, and conclusions, standardized to facilitate implementation decisions.
- Technical Report - Additional interim reports, laboratory reports, demonstration reports, and technology survey reports.
- Guidance - Instructional information on technical topics such as protocols and user’s guides.
- Workshop Report - Summary of workshop discussion and findings.
- Multimedia - On demand videos, animations, and webcasts highlighting featured initiatives or technologies.
- Model/Software - Computer programs and applications available for download.
- Database - Digitally organized collection of data available to search and access.
