17 - 17 - TR /EL ERDC Strategic Environmental Research and Development Program (SERDP) Review and Synthesis of Evidence Regarding Environmental Risks Posed by Munitions Constituents (MC) in Aquatic Systems Guilherme R. Lotufo, Mark A. Chappell, Cynthia L. Price, October 2017 Mark L. Ballentine, Ashley A. Fuentes, Todd S. Bridges, Robert D. George, Eric J. Glisch, and Geoffrey Carton Environmental Laboratory Environmental 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. Cover Image: Munitions response diver approaching an unexploded 1,000 pound General Purpose Bomb at Bahia Salina del Sur (Island of Vieques, PR). Photo provided courtesy of CH2M Hill Munitions Response and Scientific Dive Teams. SERDP ER-2341 ERDC/EL TR-17-17 October 2017 Review and Synthesis of Evidence Regarding Environmental Risks Posed by Munitions Constituents (MC) in Aquatic Systems Guilherme R. Lotufo, Mark A. Chappell, Cynthia L. Price, Mark L. Ballentine, Ashley A. Fuentes, and Todd S. Bridges Environmental Laboratory U.S. Army Engineer Research and Development Center 3909 Halls Ferry Rd, Building 3270 Vicksburg, MS 39180-6199 Eric J. Glisch U.S. Army Corps of Engineers, New Orleans District 7400 Leake Avenue New Orleans, LA 70118 Robert D. George U.S. Navy, SPAWAR Systems Center Pacific 5622 Hull Street San Diego, CA 92152 Geoffrey Carton CALIBRE Systems 6354 Walker Ln Suite 300, Alexandria, VA 22310. Alexandria, VA 22310 Final report Approved for public release; distribution is unlimited. Prepared for Strategic Environmental Research and Development Program (SERDP) Under Project ER-2341, “Review and Synthesis of Evidence Regarding Environmental Risks Posed by Munitions Constituents (MC) in Aquatic Systems” ERDC/EL TR-17-17 ii Abstract Underwater military munitions (UWMM) may pose a risk to aquatic environments because they typically contain munitions constituents (MC) such as 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5- triazine (RDX). If UWMM become corroded or breaches, the fill material may leak or dissolve into the surrounding environment, which could potentially adversely affecting affect the exposed biota. In large part, because of the high cost and complexity associated with sampling MC at UWMM sites, detailed and reliable information about MC in water, sediment, and biota is available for only a few sites, and therefore temporal and spatial uncertainties persist. Examination of available data indicates that concentrations of MC in water and sediment were largely below detection or were relatively low (e.g., parts per billion), with higher concentrations being highly localized and typically near a point source. These findings were in accordance with predictive modeling and with fate studies. Available toxicity data derived for a variety of freshwater and marine species were compiled and used to derive interim water quality criteria and protective values derived from species sensitivity distributions. Toxicity varied widely across a diversity of MC and species. For most aquatic sites, MC contamination in sediment and in the water- column presents low risk to the resident biota. 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ERDC/EL TR-17-17 iii Contents Abstract .................................................................................................................................... ii Figures and Tables ................................................................................................................viii Preface ................................................................................................................................... xvi Acronyms and Abbreviations .............................................................................................. xvii Unit Conversion Factors ...................................................................................................... xxi Executive Summary ............................................................................................................ xxii 1 Introduction ...................................................................................................................... 1 1.1 Background ........................................................................................................ 1 1.2 Objective............................................................................................................. 2 2 Generic Problem Formulation and Conceptual Model for Underwater Munitions Sites ................................................................................................................ 4 2.1 Underwater munitions in aquatic environments ............................................. 4 2.2 Conceptual site model....................................................................................... 5 2.3 Munitions constituents of potential ecological concern ................................. 7 2.4 Assessment and measurement endpoints ...................................................... 7 3 Overview of munitions constituents .............................................................................. 8 3.1 Nitroaromatics ................................................................................................ 12 3.1.1 2,4,6-trinitrotoluene (TNT) ........................................................................................ 12 3.1.2 1,3,5-trinitrobenzene (1,3,5-TNB) ............................................................................ 13 3.1.3 2,4-and 2,6- Dinitrotoluene (2,4-DNT and 2,6-DNT) ............................................... 13 3.1.4 Tetryl, ammonium picrate (Explosive D), and picric acid ........................................ 14 3.1.5 Cyclic nitramines ....................................................................................................... 16 3.2 Other energetic compounds ........................................................................... 17 3.2.1 Nitroguanidine ........................................................................................................... 17 3.2.2 Nitrate esters: nitroglycerin, nitrocellulose, PETN, and DEGDN (diethylene glycol dinitrate) ....................................................................................................... 18 4 Underwater Munitions Sites Investigated for MC Contamination .......................... 20 4.1 Jackson Park housing complex (WA, USA) .................................................... 20 4.1.1 Site overview ............................................................................................................. 20 4.1.2 Sampling efforts ........................................................................................................ 21 4.1.3 Analytical chemistry .................................................................................................. 22 4.2 Sea disposal site Hawaii (HI-06) “Ordnance Reef” (HI, USA) ....................... 23 4.2.1 Site overview ............................................................................................................. 23 4.2.2 Sampling efforts ........................................................................................................ 25 4.2.3 Analytical chemistry .................................................................................................. 26 4.3 Sea disposal site Hawaii (HI-05) (HI, USA) ..................................................... 27 ERDC/EL TR-17-17 iv 4.3.1 Site overview ............................................................................................................. 27 4.3.2 Sampling efforts ........................................................................................................ 28 4.3.3 Analytical chemistry .................................................................................................. 30 4.4 Isla de Vieques bombing range (PR, USA) .................................................... 30 4.4.1 Site overview ............................................................................................................. 30 4.4.2 Sampling efforts ........................................................................................................ 32 4.4.3 Analytical chemistry .................................................................................................. 33 4.5 Former Seattle Naval Supply Depot piers 90 and 91, Port of Seattle (WA, USA) .................................................................................................................