Search

ERDC/CRREL TR-14-23 Strategic Environmental Research and Development Program (SERDP) Dissolution of NTO, DNAN, and Insensitive Munitions Formulations and Their Fates in Soils Cold Regions Research and Engineering Laboratory Katerina Dontsova, Susan Taylor, Rose Pesce-Rodriguez, Mark Brusseau, Jennifer Arthur, Noah Mark, Marianne Walsh, James Lever, and Jiri Šimůnek September 2014 Effects of outdoor weathering and dissolution on three insensitive munitions formulations after 17 days (top) and 1 year (bottom). Approved for public release; distribution is unlimited. The U.S. Army Engineer Research and Development Center (ERDC) solves the nation’s toughest engineering and environmental challenges. ERDC develops innovative solutions in civil and military engineering, geospatial sciences, water resources, and environmental sciences for the Army, the Department of Defense, civilian agencies, and our nation’s public good. Find out more at www.erdc.usace.army.mil. To search for other technical reports published by ERDC, visit the ERDC online library at http://acwc.sdp.sirsi.net/client/default. Strategic Environmental Research and Development Program (SERDP) ERDC/CRREL TR-14-23 September 2014 Dissolution of NTO, DNAN and Insensitive Munitions Formulations and Their Fates in Soils Katerina Dontsova, Mark Brusseau, Jennifer Arthur, and Noah Mark University of Arizona 845 N. Park Avenue Tucson, AZ 85721-0158 Susan Taylor, James Lever, and Marianne Walsh Cold Regions Research and Engineering Laboratory (CRREL) U.S. Army Engineer Research and Development Center 72 Lyme Road Hanover, NH 03755-1290 Rose Pesce-Rodriguez Army Research Laboratory (ARL), Weapons and Materials Research Directorate (WMRD) U.S. Army Research Laboratory Aberdeen Proving Ground, MD 21005-5006 Jiri Šimůnek University of California, Department of Environmental Sciences Riverside, CA 925021 Final Report Approved for public release; distribution is unlimited. Prepared for Strategic Environmental Research and Dev

ERDC/CRREL TR-12-9 ER-1691 Dissolution Rate of Propellant Energetics from Nitrocellulose Matrices Cold Regions Research and Engineering Laboratory Susan Taylor, Katerina Dontsova, Susan Bigl, Colleen Richardson, James Lever, Jonathan Pitt, John P. Bradley, Marianne Walsh, and Jiří Šimůnek September 2012 Approved for public release; distribution is unlimited. Cover: Black and white and color optical images of fired M2 propellant grains and a transmission electron microscope image showing the heated edge of the propellant. ER-1691 ERDC/CRREL TR-12-9 September 2012 Dissolution Rate of Propellant Energetics from Nitrocellulose Matrices Susan Taylor, Susan Bigl, Colleen Richardson, James Lever, and Marianne Walsh Cold regions Research and Engineering Laboratory U.S. Army Engineer Research and Development Center 72 Lyme Road Hanover, NH 03755 Katerina Dontsova Biosphere 2 Earthscience, University of Arizona 845 N. Park Avenue Tucson, AZ 85721-0158 Jonathan Pitt The Pennsylvania State University PO Box 30, Mailstop 3320B State College PA 16804 John P. Bradley Institute of Geophysics and Planetary Physics Lawrence Livermore National Laboratory Livermore, CA 94551 Jiří Šimůnek Department of Environmental Sciences University of California Riverside Riverside, CA 92521 Final report Approved for public release; distribution is unlimited. Prepared for The Strategic Environmental Research and Development Program Under SERDP ER-1691 ERDC/CRREL TR-12-9 ii Abstract: During firing, propellant residues are scattered onto the soil surface where their energetic com-pounds can be dissolved by precipitation. The residues, like the unfired propellants, are com-posed of nitrocellulose imbibed with either 2,4-DNT (single-base), nitroglycerin (NG) (double-base) or NG and nitroguanidine (NQ) (triple-base). Although nitrocellulose is insoluble, 2,4- DNT, NG, and NQ are soluble; and 2,4-DNT and NG are also toxic. Consequently, data on how quickly 2,4-DNT, NG, and NQ are dissolved from propellant

Information is presented on how to collect and process soil samples to quantify explosives, propellants and metals from training range soils. This document outlines how to estimate the average concentration of energetic compounds and metals in soils and determine the error in the estimated concentration.

This manual gives guidance on how to collect and process soil samples to quantify explosives, propellants, and metals from nonoperational ranges under remedial investigation. This document outlines how to estimate the average concentration of energetic compounds and metals in soils and determine the error in the estimated concentration. Since this guidance is for a remedial investigation, we assume that the Site Investigation has identified areas that need further study., PDF updated 28 Mar 2013.

Explosive compounds, including known toxicants 2,4,6-trinitrotoluene (TNT) and hexahydro- 1,3,5-trinitro-1,3,5-triazine (RDX), are loaded to soils during military training. Their fate in soils is ultimately controlled by soil mineralogical and biogeochemical processes. We detonated pure mineral phases with Composition B, a mixture of TNT and RDX, and investigated the fate of detonation residues in aqueous slurries constructed from the detonated minerals. The pure minerals included Ottawa sand (quartz and calcite), microcline feldspar, phlogopite mica, muscovite mica vermiculite clay, beidellite (a representative of the smectite clay group), and nontronite clay. Energydispersive X-ray spectrometry, X-ray diffraction and gas adsorption surface area measurements were made of the pristine and detonated minerals. Batch slurries of detonated minerals and deionized water were sampled for 141 days and TNT, RDX and TNT transformation products were measured from the aqueous samples and from the mineral substrates at day 141. Detonated samples generally exhibited lower gas adsorption surface areas than pristine ones, likely from residue coating, shockinduced compaction, sintering, and/or partial fusion. TNT and RDX exhibited analyte loss in almost all batch solutions over time but loss was greater in vermiculite, beidellite, and phlogopite than in muscovite and quartz. This suggests common phyllosilicate mineral substrates could be used on military training ranges to minimize off-site migration of explosive residues. We present a conceptual model to represent the physical and chemical processes that occurred in our aqueous batches over time.

The Cold Regions Research and Engineering Laboratory and the Defence Research and Development Canada Valcartier have partnered to improve the understanding of the distribution and fate of propellant residues on military training ranges. Field studies were conducted to estimate the propellant residue mass deposited per round fired from various munitions as well as residues from the field disposal of excess propellants. Experiments were conducted to measure the rate of release of energetic compounds after deposition. Training ranges were examined to determine the mass and distribution of residue accumulation. Profile sampling was conducted to document the depth to which these residues had penetrated the ground. Column studies were conducted with propellants to document transport rates for solution-phase propellant constituents and to develop process descriptors for use in models to enable prediction of fate and transport for constituents of concern. Gaps were filled in other areas of energetics residues impacts in an effort to describe all aspects of energetics impacts on range environments. Testing of propellant burn structures was begun, and we continue to promote and refine the multi-increment sampling protocol for energetics. Major accomplishments are presented for the final year and the total of Environmental Restoration Project 1481, Phase II., Strategic Environmental Research and Development Program ER-1481. Prepared in collaboration with the Defence Research and Development Canada Valcartier. The original document contains color images.

ERDC/CRREL TR-11-15 Guidance for Soil Sampling of Energetics and Metals Cold Regions Research and Engineering Laboratory Susan Taylor, Thomas F. Jenkins, Susan Bigl, Alan D. Hewitt, Marianne E. Walsh and Michael R. Walsh October 2011 Approved for public release; distribution is unlimited. DEDICATION: We dedicate this report to our late colleague Alan Hewitt. He worked tirelessly to develop sampling methods and protocols for evaluating energetic residues on military training ranges. He also passionately shared what he had learned with audiences large and small. This document would not have been possible without his research contributions. We miss you Alan. ERDC/CRREL TR-11-15 October 2011 Guidance for Soil Sampling of Energetics and Metals Susan Taylor, Thomas F. Jenkins, Susan Bigl, Alan D. Hewitt, Marianne E. Walsh and Michael R. Walsh Cold regions Research and Engineering Laboratory U.S. Army Engineer Research and Development Center 72 Lyme Road Hanover, NH 03755 Final report Approved for public release; distribution is unlimited. Prepared for U.S. Army Environmental Command ERDC/CRREL TR-11-15 ii Abstract: Information is presented on how to collect and process soil samples to quantify ex-plosives, propellants and metals from training range soils. This document outlines how to esti-mate the average concentration of energetic compounds and metals in soils and determine the error in the estimated concentration. DISCLAIMER: The contents of this report are not to be used for advertising, publication, or promotional purposes. Citation of trade names does not constitute an official endorsement or approval of the use of such commercial products. All product names and trademarks cited are the property of their respective owners. The findings of this report are not to be construed as an official Department of the Army position unless so designated by other authorized documents. DESTROY THIS REPORT WHEN NO LONGER NEEDED. DO NOT RETURN IT TO THE ORIGINATOR. ERDC/CRREL TR-11

The Cold Regions Research and Engineering Laboratory and Defence Research and Development Canada Valcartier have partnered to improve the understanding of the distribution and fate of propellant residues on military training ranges. Field studies were conducted to estimate the propellant residue mass deposited per round fired from various munitions as well as residues from the field disposal of excess training propellants. Experiments were conducted to measure the rate of release of nitroglycerin and dinitrotoluenes after deposition. United States and Canadian installations were examined to determine the mass and distribution of residue accumulation. Profile sampling was conducted to document the depth to which these residues had penetrated the ground. Column studies were conducted with nitroglycerin, nitroguanidine, potassium perchlorate, and diphenylamine from intact and expended propellants to document transport rates for solution-phase propellant constituents and to develop process descriptors for use in models to enable prediction of fate and transport for these constituents.

Field observations of weathering Comp B (RDX/TNT 60/40) residue were made on a live-fire training range over four years. The Comp B residue was formed by low-order detonations of 120-mm mortar projectiles. Physical changes were the disaggregation of initially solid chunks into masses of smaller diameter pieces and formation of red phototransformation products that washed off with rain or tidal flooding. Disaggregation increased the surface area of the residue, thereby increasing the potential for dissolution. The bulk of the mass of Comp B was in the craters, but solid chunks were scattered asymmetrically up to 30 m away., Published in Chemosphere, v78 p467-473, 2010. Prepared in collaboration with Envirostat, Inc., Fort Collins, CO. The original document contains color images.

Military live-fire training utilizes energetic materials that are never completely consumed. In February 2010, tests were conducted at Fort Richardson, Alaska, to determine the propellant residues deposition rates related to the firing of 40-mm grenades from an Mk19 machine gun. Two test pads were constructed, with 127 Mk281 (BA12) training rounds containing F15080 propellant (9.1% nitroglycerin-NG) fired over one and 144 M430 (B542) high-explosive rounds containing M2 propellant (19.5% NG) fired over the other. Replicate multi-increment samples were collected from the snow surface downrange of the firing positions in three sampling units on each pad. Samples were analyzed and results composited to derive an estimate of the unreacted energetics mass. The total estimated per-round deposition rate for the M430 high-explosive cartridge is 76 mg/round, 8.4% of the original NG load. The deposition rate for the Mk281 cartridge is 2.2 mg/round, 0.59% of the original NG load. Energet-ics deposition rates for the M430 rounds were between those for mortar projectiles and shoulder-fired rockets, which also utilize double-based propellants, are medium-velocity projectiles, and are fired from short-barreled guns. The Mk281 cartridges, with their NG-impregnated propellant grains, had a much lower NG deposition rate but a greater mass of unconsumed propellant., The original document contains color images.

The U.S. Department of Defense (DoD) and U.S. Environmental Protection Agency (USEPA) both have programs tasked with determining if military training and testing facilities present a risk to human health and the environment. The DoD has established the Military Munitions Response Program (MMRP) and Operational Range Assessment Program (ORAP) (DoD Directive 4715.11) that have requirements to perform site investigations. The USEPA has become involved in the characterization of energetic residues on military training ranges and the potential for off-site migration through ongoing investigations of the Massachusetts Military Reservation (MMR) (USEPA 2000). The objectives of this demonstration/validation project were to promote scientifically defendable sampling and sample-processing protocols for the characterization of energetic residues on military training ranges. The principal mechanism for meeting this objective has been to inform potential users of the sampling and sample processing protocols developed under the Strategic Environmental Research and Development Program (SERDP) Environmental Restoration (ER) projects ER-1155 and ER-1418., Prepared in collaboration with Defence Research and Development Canada-Valcartier (DRDC-Val), Quebec, Canada.

Military live-fire training missions utilize a variety of energetic materials that are never completely consumed during firing. In March 2009, tests were conducted at Fort Richardson, Alaska, to determine the residues related to the firing of AT4 anti-armor shoulder-fired rockets. Six rockets were fired from the same firing position on the snow-covered range. Replicate multi-increment samples were collected from the snow surface behind and downrange of the firing point in each of eight decision units. Samples were analyzed and results composited to derive an estimate of the mass of unreacted energetics. Total estimated per-round deposition rate of nitroglycerin (NG) for the M136 AT4 rocket is 95 g/round, or 73% of the original NG load. This indicates that the propellant burn efficiency for the AT4 is poor, with much propellant not consumed during firing. In subsequent May 2009 samples, we found approximately one-third of the NG had leached out of the propellant fragments since March. Large propellant strip segments collected in May contained 67% of the nominal NG of the original propellant, and we hypothesize that even more had leached from the more numerous, smaller segments. Canadian tests of the similar Carl Gustav rocket also indicate high rates (> 14%) of unburned propellants., The original document contains color images.

Military live-fire training missions utilizing mortars and howitzers frequently generate excess propellant charges. Disposal of this propellant is often done on-site and is referred to as expedient disposal. Investigations into energetics residues resulting from expedient disposal of propellants began in 2002 with the collection of residues inside and outside a propellant burn structure. These residues contained very high concentrations of 2,4-Dinitrotoluene, an indication that the burning process was not complete. Other informal tests were conducted, indicating the same results. In 2006 and 2008, a series of tests were conducted on snow using propellants from various mortar cartridges. In one test, 10 charges of mortar propellant were burned on snow and the residues collected and analyzed. Over 15% of the original nitroglycerin content was recovered. In 2008, two series of tests were conducted, one involving winter disposal of mortar propellants, the other summer disposal of howitzer propellants. These tests, conducted under controlled conditions, indicate that the environmental setting and climatic conditions can influence the efficiency of expedient propellant disposal by three orders of magnitude., Sponsored in part by USAG-AK.

The Military maintains sustainability and environmental stewardship responsibilities for training ranges. One of the environmental challenges is to monitor the surface loading of energetic residues. Method 8330B, which was developed to assist in this task, recommends the use of a MULTI INCREMENT(registered trademark) sampling strategy and total sample processing prior to subsampling and analysis. This demonstration/validation project evaluated scientifically defensible sampling and sample-processing protocols used for the characterization of energetic residues on military training ranges. This project also specifically assessed the scientific uncertainty involved with the now-common practice of splitting a sample in the field and subsampling it prior to processing the entire laboratory sample. To address the cost aspect, this study then evaluated the cost benefits of coupling MULTI INCREMENT sampling methodology with recently developed sample handling and processing protocols designed to address the unique attributes of energetic residues. Consequently, the authors recommend that MULTI INCREMENT sampling and the U.S. Environmental Protection Agency (USEPA) Method 8330B be used for future characterization activities on military training ranges., The original document contains color images.

Military training with howitzers and mortars produces excess propellant that is burned on the training range and can result in point sources containing high concentrations of unreacted propellant constituents. Propellants contain energetic compounds such as nitroglycerin (NG) and 2,4-dinitrotoluene (2,4-DNT), both of which are found at firing positions and propellant disposal areas. To quantify the mass of residue remaining from the field-expedient disposal of propellants, two mortar propellants and one howitzer propellant were burned under different field conditions. These conditions included burning on a snow pack, at the bottom of a snow pit, and in a pan surrounded by snow for the mortar propellants and on dry and wet sand for the howitzer propellant. For the mortar propellant, the energetics (NG) remaining after burning in the bowl, on frozen ground, and on snow were 0.21%, 5.2% and 18%, respectively. For the howitzer propellant, the difference in energetics (2,4-DNT) remaining after disposal on wet and dry sand was <0.1%, with the overall residue rate of around 1%, similar to that for the mortar propellant burned in an open container. These tests demonstrate that environmental factors, especially in winter, can play a significant role in the effectiveness of field-expedient disposal of propellants., Published in Jnl. of Hazardous Materials, v173 p115-122, 2010. ISSN: 0304-3894.

Over the past two years, the U.S. Army Engineer Research and Development Center and the Defence R&D Canada Valcartier have partnered to develop an improved understanding of the distribution and fate of propellant residues on military training ranges in SERDP Project ER-1481. As a portion of this work, field studies have been conducted to estimate the mass of propellant residues deposited per round fired from various munitions. This research included artillery, mortars, small arms, shoulder-fired rockets, and several large missiles. Particles of the propellant residues deposited have been collected and studied, and initial experiments conducted to measure the rate of release of nitroglycerin (NG) and 2,4-dinitrotoluene (DNT) after deposition. Field studies have been conducted at a number of U.S. and Canadian installations to determine the mass and distribution of residue accumulation from different types of munitions. Depth profiling has been accomplished to document the depth to which these residues have penetrated the shallow subsoil. Laboratory column studies have been conducted with NG, nitroguanidine, and diphenylamine to document transport rates for solution phase propellant constituents and develop process descriptors for use in mathematical models to enable prediction of fate and transport for these constituents. Subsequent column studies have utilized intact propellants. The major accomplishments from these field and laboratory studies are presented., The original document contains color images. Prepared in collaboration with Defence R&D Canada-Valcartier, Quebec, Canada; Institut National de la Recherche Scientifique, Quebec, Canada; EnviroStat, Inc., Fort Collins, CO; and Defence R&D Canada-Toronto, Toronto, Canada.

Fourteen 120-mm high-explosive mortar projectiles were fired into the Eagle River Flats (ERF) impact area in June 2007 to determine physical disturbance of the mudflat when it is not covered by ice. Currently, ERF is used only when it is covered by ice that prevents disturbance of the underlying sediment. Thirteen of the projectiles functioned normally and produced high-order detonations. The high order detonation craters averaged 2.7 m in diameter and 0.7 m in depth, and no high-explosives residues from the Comp B filler were detected in the sediments in and around the craters. One projectile partially detonated. The crater was 1.7 m in diameter and 0.7 m in depth. Residues of TNT, RDX, and HMX were detected at tens of parts per million concentrations on the day of the detonation. None of the detonations exposed white-phosphorus-contaminated sediments or unexploded ordnance. Water draining off the mudflats immediately adjacent to areas with explosives residues on the surface had detectable concentrations of RDX, but water within the gully system had energetic concentrations of < 0.06 g/L. At the firing points, the propellant residue expelled from the mortar consisted of partially consumed grains that had nearly the same proportion of nitroglycerin as in the unfired propellant. Surface soils at the firing points had NG concentrations (around 10 g/g) similar to those observed during previous sampling events., The original document contains color images. Prepared in cooperation with Colorado State University, 1490 Campus Delivery, Fort Collins, CO.