Improved Understanding of the Fate and Effects of Insensitive Munitions Constituents
SERDP, Environmental Restoration Program Area
Released October 29, 2015
Closed January 7, 2016
FY 2017
The objective of this Statement of Need (SON) was to develop an improved understanding of the fate and effects of the components 2,4-dinitroanisole (DNAN) and nitrotriazolone (NTO) that are used in the insensitive munitions formulations. Specific objectives were as follows.
- Develop standardized computational and experimental evaluation methods for predicting the fate and transport of new insensitive munitions prior to development.
- Collect measurements of fate- and transport-determining properties of insensitive munitions including ionization constants (e.g., pKa); rate constants for hydrolysis, oxidation (including photooxidation), and biotic and abiotic reduction; water solubility; Henry’s law constant; and partitioning coefficients to octanol and native organic matter.
- Improve fate and transport models to predict exposure and risk of insensitive munitions in field scenarios.
- Determine long term toxicity of DNAN and NTO formulations in mammalian systems.
- Determine effects of insensitive munitions compounds on vegetation and fauna in terms of toxicity and uptake. Proposers may address one or more of the objectives listed above.
Proposals addressing compounds other than those listed in the objectives above were not considered.
Better understanding of the fate and effects of insensitive munitions can minimize the future costs for characterization, cleanup, and natural resource damages. The ASTM standard (E2552) provides a roadmap for such testing, and improving the cost-effectiveness and accuracy of these test methods should foster adoption of appropriate fate and effects assessments at each stage of the lifecycle of munitions constituents. In addition, development and use of improved fate and effects models and measurement techniques can help managers better predict and minimize the environmental impacts of range operations.
Munitions compounds may reach human receptors or be released into the environment at several points during manufacture, training, and combat. Those releases and exposures have resulted in significant costs to the DoD in the past, and continue to represent significant liabilities. The understanding of fate and effects of legacy munitions constituents is fairly robust, but additional research is necessary to fully understand the fate, transport, and effects of insensitive munitions constituents.
Although there are several existing models that can be used to predict fate-determining properties of chemicals, they are not satisfactory for munitions constituent chemicals. New efforts should build on prior art, starting with systematic assessment of the actual performance of existing tools, and any overlap and gaps in their coverage. Models responsive to this need may be of several types: (i) quantum chemical models for chemical properties from first principles (requires no experimental data for calibration); (ii) empirical/statistical correlation models (quantitative structure-activity relationships, QSARs); or (iii) expert systems that encode decision trees.
Existing fate and transport models use “fate-determining” property data that are either measured or predicted. Their output is generally contaminant concentration (potential exposure) distributed over time and space. The various models should be systematically compared in terms to application range, output capability, precision, accuracy, usability, and transparency for insensitive munitions. In addition, while fate and transport models generally provide contaminant concentrations over time/space, they could be extended to endpoints more directly relevant to risk assessment through coupling to risk models and incorporation of toxicology data.
Experimental data for fate-determining properties of insensitive munitions are still scarce, and often of uncertain reliability. More and better measured data are needed for the whole range of current and future munition constituents. In particular, studies of the processes that are relatively difficult to characterize are needed. Although most existing studies of the new insensitive munitions have focused on the simpler processes (e.g., partitioning and hydrolysis), potentially important processes that are more difficult to evaluate are critical to understand. The most important such processes include biodegradation and photodegradation.
Biodegradation data are needed for aerobic and anaerobic conditions in both soil and groundwater. Both pure and unpurified culture systems could yield data of interest, since there have been few studies of the biodegradation of specific insensitive munitions compounds, and some compounds do not have well characterized biodegradation potential. In particular, the identities and fates of degradation intermediates and byproducts need to be understood.
Fate and transport studies also need to be done with the actual formulations used, to evaluate the fate of munitions constituents in typical mixtures and the fates of the other materials used. Since mixtures with other munitions constituents are likely, these effects should be considered as well. In addition, impacts on other contaminants of concern should be evaluated. One notable example is the potential for acidity associated with NTO to enhance metals mobilization. Finally, improved tools for fate and transport studies would be helpful, such as reactive tracers to simulate insensitive munitions behavior in the environment.
Ranges depend on having vegetation (aquatic and terrestrial). Vegetation provides critical habitat, preserves soil and prevents runoff, and both retains and degrades contaminants. Vegetation can prevent downward migration of contaminants and eventual groundwater pollution both through uptake and by reducing water infiltration. It is therefore important to know if insensitive munitions compounds affect vegetation, and if so, how and at what concentrations. It is also important to understand if these compounds accumulate in the plants, or if they are transformed or degraded. Understanding the eventual fate of insensitive munitions compounds if consumed or degraded after plant death also may be important.
Ranges also depend on the animals present, both aquatic and terrestrial fauna, that serve vital environmental functions and also can be important receptors of concern. It is critical to understand if insensitive munitions compounds will affect the range fauna, and if so, how and at what concentrations. It is also critical to understand if fauna accumulate the compounds or transform them after uptake.
In July 2015, the SERDP and the Environmental Security Technology Certification Program (ESTCP) held a workshop to develop research and demonstration needs to improve management of munitions constituents. Approximately 80 personnel, including representatives from the DoD, federal and state regulators, engineers, researchers, industry representatives, and consultants, attended. A more detailed description of these issues can be found in the report from the workshop. Proposers are strongly encouraged to review the workshop report for additional detail.
The cost and time to meet the requirements of this SON were at the discretion of the proposer. Two options were available:
Standard Proposals: These proposals describe a complete research effort. The proposer should incorporate the appropriate time, schedule, and cost requirements to accomplish the scope of work proposed. SERDP projects normally run from two to five years in length and vary considerably in cost consistent with the scope of the effort. It is expected that most proposals will fall into this category.
Limited Scope Proposals: Proposers with innovative approaches to the SON that entail high technical risk or have minimal supporting data may submit a Limited Scope Proposal for funding up to $200,000 and approximately one year in duration. Such proposals may be eligible for follow-on funding if they result in a successful initial project. The objective of these proposals should be to acquire the data necessary to demonstrate proof-of-concept or reduction of risk that will lead to development of a future Standard Proposal. Proposers should submit Limited Scope Proposals in accordance with the SERDP Core Solicitation instructions and deadlines.