Site Specific Sorption/Desorption Measurements for Nitroglycerin and Dinitrotoluene at Camp Edwards , MMR, Cape Cod , Massachusetts
Ian T. Osgerby, PhD PE, USACE
Jay Clausen, USACE/ERDC/CRREL

A Remedial Approach to Chemical Treatment of Nitroaromatic-Explosives Contaminated Soils via Alkaline Hydrolysis
Ronnie Britto, PhD, P.E., Senior Project Manager, Tetra Tech Inc.
Mikael L. Spangberg, P.E., LEP, Senior Project Manager, Tetra Tech
Frank Bogle, Senior Project Manager, Tetra Tech
Larry Tyner, P.E., Senior Project Manager, Tetra Tech
Scott J. Bolton, Commander's Representative, Volunteer Army Ammunition Plant
Doug Webb , Technical Manager, U.S. Army Corps of Engineers

Redox Transformation of Nitroaromatic and Cyclic Nitramine Explosives in Aqueous Environments
Minori Uchimiya , US Army Corps of Engineers

Enzymatic and Bio-geochemical Factors that Affect RDX Degradation
Deborah R. Felt, US Army Engineer Research & Development Center
Anthony Bednar , US Army Engineer Research & Development Center
Clint Arnett , US Army Construction Engineering Research Laboratory

Evaluation and Selection of Technologies for the Removal of RDX from an Industrial Wastewater Stream
David B. Gent, US Army Engineer Research & Development Center
Jared L Johnson, US Army Engineer Research & Development Center
Greg O’Connor, U.S. Army Armament Research, Development and Engineering Center
Deborah R. Felt, US Army Engineer Research & Development Center
Steven L. Larson, US Army Engineer Research & Development Center
Bob Winstead, Ordnance Systems Inc.

Small Arms Range Characterization Using the CRREL Multi-Increment Sampling (MIS) and Analysis by 8330B
Mark R. Koenig, USACE Project Chemist, USACE Project Chemist, US Army Corps of Engineers, New England District, 696 Virginia Road, Concord, MA 01366, Tel: 978-318-8312, Fax: 978-318-8614, E-mail: mark.r.koenig@usace.army.mil
Paul Nixon, Remedial Specialist, Impact Area Groundwater Study Program, 1803 West Outer Road, Camp Edwards, MA 02542, Tel: 508-968-5620, Email: paul.nixon@us.army.mil
Ben Gregson, Remediation Manager, Impact Area Groundwater Study Program, 1803 West Outer Road, Camp Edwards, MA 02542, Tel: 508-968-5821, Email: benjamin.p.gregson@us.army.mil
John Verban, Project Chemist, TetraTech, EC, Inc., 133 Federal Street , 6th Floor, Boston , MA 02110 , Tel: 617-457-8208, Email: john.verban@tteci.com
Brad Chrigwin, HPLC Chemist, Test America Laboratory, 30 Community Drive, Suite 11, South Burlington, VT  05403, Tel: 802-660-1990, Fax: 802-660-1919, Email: brad.chrigwin@testamerica.com
Jim Madison, Project Manager, Test America Laboratory, 30 Community Drive, Suite 11, South Burlington, VT  05403, Tel: 802-660-1990, Fax: 802-660-1919, Email: jim.madison@testamerica.com
Alan Hewitt, Research Scientist, US Army Engineer Research and Development Center, Cold Regions Research Engineering Laboratory (CRREL), 72 Lyme Road, Hanover, NH 03755-1290, Tel: 603-646-4388, Fax: 603-646-4785, Email: Alan. D. Hewitt @ erdc.usace.army.mil
Thomas F. Jenkins, Research Scientist, US Army Engineer Research and Development Center, Cold Regions Research Engineering Laboratory (CRREL), 72 Lyme Road, Hanover, NH 03755-1290, Tel: 603-646-4385, Fax: 603-646-4785, Email: thomas.f.jenkins@erdc.usace.army.mil
Marianne Walsh, Research Scientist, US Army Engineer Research and Development Center, Cold Regions Research Engineering Laboratory (CRREL), 72 Lyme Road, Hanover, NH 03755-1290, Tel: 603-646-4666, Fax: 603-646-4785, Email: marianne.e.walsh@erdc.usace.army.mil

A Multi-Increment Sampling (MIS) approach and modified analytical method 8330B have been recommended for sampling and analysis of explosive compounds by the U.S. Army Corps of Engineers Cold Regions Research and Engineering Laboratory (CRREL).  This method was recently adopted by EPA in their Small Arms range Plans (SAR) Work Plans. The U.S. Army Corps of Engineers, New England District (NAE) has been working closely with CRREL, the Army Environmental Command Impact Area Groundwater Study Program (IAGWSP), MassDEP, EPA, TetraTech, ECI, and Test America Laboratory (TAL) who has implemented the Multi-Increment Sampling (MIS) and mechanical grinding approach and modified analytical method at the Massachusetts Military Reservation (MMR), Camp Edwards, MA. 

The MIS and Method 8330B have been implemented at Small Arms Ranges (SARs) and Gun and Motar (G&M) firing positions and target locations. The successes and lesson-learned on characterizing our Small Arms Ranges will be discussed in detail and analytical results will be reviewed.  The MIS approach has mainly been applied to explosives; however, it has also been used for other analyses including SVOCs by Method 8270C-GC/MS, Metals by Method 6010B-ICP/AES, TOC by Lloyd Khan and perchlorate in soils by Method 6850-LC/MS/MS.

Site Specific Sorption/Desorption Measurements for Nitroglycerin and Dinitrotoluene at Camp Edwards, MMR, Cape Cod , Massachusetts
Ian T. Osgerby, PhD PE, USACE, 696 Virginia Rd., Concord, MA 01742, Tel: 978-318-8631, Fax: 978-318-8614, Email: ian.t.osgerby@usace.army.mil
Jay Clausen, USACE/ERDC/CRREL, 72 Lyme Rd., Hanover, NH 03755, Tel: 603-646-4597, Email: jay.l.clausen@us.army.mil

A study was carried out to investigate the sorption and desoprtion of nitroglycerine (NG) and dinitrotoluene (DNT) from specific site soils from Small Arms Ranges at Camp Edwards (MMR).  The purpose was to evaluate one portion of the multi-component mechanism in which spent propellants mixed/encapsulated with nitro cellulose are distributed on the ground, dissolve/leach into the local soils/organic matter, migrate with precipitation and either are transported into the subsurface soils below or are removed by sorption and/or degradation processes.  Although these processes may be complicated to discern in detail, the preliminary investigation focused on the simpler step of evaluating whether reagent grade chemicals sorbed to soils/organic matter subsequently desorb in an observable time frame or become degraded before the migration/transportation process can occur.  This process was observed in a series of experiments and the results of the investigation are presented.  In addition to testing the (ir)reversibility of the sorption process, limited tests were designed to evaluate desorption of NG/DNT from fired propellant powders collected from firing ranges.  The potential for subsequent degradation of sorbed NG/DNT such as biodegradation was investigated to determine whether they could be permanently removed from the environment.

A Remedial Approach to Chemical Treatment of Nitroaromatic-Explosives Contaminated Soils via Alkaline Hydrolysis
Ronnie Britto, PhD, P.E., Senior Project Manager, Tetra Tech Inc., 800 Oak Ridge Turnpike, Suite A-600, Oak Ridge, TN, 37830, USA, Tel: 901-849-9900, Fax: 865-482-6647, Email: Ronnie.Britto@tetratech.com
Mikael L. Spangberg, P.E., LEP, Senior Project Manager, Tetra Tech, 800 Oak Ridge Turnpike, Suite A-600, Oak Ridge, TN 37830, Tel: 860-461-0189, Email: Mikael.Spangberg@tetratech.com
Frank Bogle, Senior Project Manager, Tetra Tech, 800 Oak Ridge Turnpike, Suite A-600, Oak Ridge, TN 37830,  Tel: 865-483-9900, Email: Frank.Bogle@tetratech.com
Larry Tyner, P.E., Senior Project Manager, Tetra Tech, 800 Oak Ridge Turnpike, Suite A-600, Oak Ridge, TN 37830, Tel: 865-483-9900, Email: Larry.Tyner@tetratech.com
Scott J. Bolton, Commander's Representative, Volunteer Army Ammunition Plant, P.O. Box 22607 , Chattanooga , TN 37422-2607 , Tel: 423-893-5121
Doug Webb , Technical Manager, U.S. Army Corps of Engineers, Mobile District, ATTN: CESAM-EN-GH, 109 St. Joseph Street , Mobile , Alabama 36602 , Tel: 251-690-3476

Disposal of nitroaromatic-explosive contaminated soils can be a costly remedial option.  Several chemical treatment options were evaluated as an alternative remedial approach to disposal at an army ammunition plant in the southeastern United States .  Bench-scale and field-scale tests were performed on soil contaminated with trinitrotoluene (TNT) and dinitrotoluenes (DNTs), followed by on-going full-scale treatment.

The bench-scale test consisted of soil pan tests to evaluate various chemical amendments/quantities to test chemical oxidants and alkaline hydrolysis.  The four-week study demonstrated that alkaline hydrolysis using a strong alkaline agent, sodium hydroxide, has the ability to degrade percent levels of TNT as well as the more recalcitrant DNTs to clean up goals of 55 mg/kg and 27 mg/kg respectively within a 7-day period.  During this bench-scale study, nitrites appeared to be the major end product, with all other intermediate organic products destroyed.  As a result, a denitrification bench-scale study was also performed to demonstrate the feasibility of using biotreatment on the resulting nitrite contamination.  Citric acid was applied to the soil following nitroaromatic-explosives remediation.  Within two weeks, nitrites decreased to ND, indicating that citric acid is an effective additive to aid in the denitrification process.

The results and estimated chemical quantities from the bench-scale tests were used to perform a field demonstration of alkaline hydrolysis using approximately 300 cubic yards of excavated soil.  Chemicals were mixed into the soil and water was periodically added   to ensure saturation conditions.  The field test demonstrated that alkaline hydrolysis can be very successfully implemented in the field.  Analytical results showed that TNT and DNT concentrations could be reduced to well below the clean-up goals within two weeks. 

This technology is now being implemented on a full-scale basis, with remediation occurring in multiple on-site excavated stockpiles of soil estimated at 50,000 to 60,000 cubic yards when remediation is completed.

Redox Transformation of Nitroaromatic and Cyclic Nitramine Explosives in Aqueous Environments
Minori Uchimiya, US Army Corps of Engineers, Engineer Research and Development Center, Environmental Laboratory, 3909 Halls Ferry Road, Vicksburg, MS 39180, USA, Tel: 601-634-4820, Fax: 601-634-2742, Email: Minori.Uchimiya@usace.army.mil

Explosives such as nitroaromatics (NACs) and cyclic nitramines are ubiquitous aquatic contaminants.  Unique reduction potential (E) corresponding to the half reaction for a given explosive (R-NO₂) and its one-electron reduction product (R-NO₂●^-) describes the susceptibility of the explosive towards reduction.  This study investigates the redox chemistry of explosives with abundant redox-active constituents in soils, most notably iron: 

Fe(OH)₃(s, amorphous)  +  3H⁺  +  e^-  =  Fe²⁺(aq)  +  3H₂O      E = 0.059 volts

    (pH 7, excess Fe(OH)₃(s, amorphous), 125 mM Fe²⁺(aq))

Under the conditions used for calculating the E value, an explosive having E > 0.059 volts is thermodynamically capable of oxidizing Fe(II) to Fe(III).  Presence of naturally-occurring iron-coordinating ligands such as citrate and oxalate, and metal (hydr)oxides impacts the E value of iron half-reaction.  In addition, there are additional environmentally relevant reductants with known E values such as hydroquinones.  We will explore the potential of these environmentally important reductants to reduce a wide range of explosives: NACs (including dinitroanisoles, DNAN), cyclic nitramines (RDX and HMX), and caged cyclic nitramines (CL20).  Rates of reduction will determined as function of pH, ligand concentration (for Fe(II) as a reductant), and metal (hydr)oxides (e.g., magnetite) loading.  Determined rates will be compared with calculated E values of the reductant to predict the fate of explosives under a wide range of redox conditions encountered in aqueous environments.  

Enzymatic and Bio-geochemical Factors that Affect RDX Degradation
Deborah R. Felt, US Army Engineer Research & Development Center, 3909 Halls Ferry Road, Vicksburg, MS, 39180, USA,  Tel: 601-634-3576, Fax: 601-634-3518, Email: Deborah.Felt@usace.army.mil
Anthony Bednar, US Army Engineer Research & Development Center, 3909 Halls Ferry Road, Vicksburg, MS, 39180, USA  Tel: 601-634-3652, Email: Anthony.J.Bednar@usace.army.mil
Clint Arnett, US Army Construction Engineering Research Laboratory, PO Box 9005 , Champaign , IL 61826-9005 , USA Tel: 217-398-5507, Email: Clint.Arnett@usace.army.mil

It is essential to military preparedness to continue training activities while maintaining environmental stewardship of grenade and small arms firing ranges and the surrounding communities.  A fundamental obstacle to the use of an in situ approach for the treatment of RDX contaminated soils and groundwater is the lack of information concerning the biogeochemical factors that influence transformation.  This research compares paired (biotic and poised abiotic systems) RDX degradation experiments in which Eh-pH spaces conducive to RDX degradation are established through abiotic and biotic means.

Ubiquitous soil bacteria from the genera Desulfovibrio, Pseudomonas and Geobacter possess the unique ability to degrade RDX utilizing one of two proposed pathways under anaerobic conditions. One pathway involves the sequential reduction of the nitro functional groups and the second involves the hydrolytic substitution of the nitro functional groups and subsequent ring destabilization and cleavage.  The dynamics which influence the degradation pathway followed under environmentally relevant terminal electron accepting processes (TEAP) are not well understood and the role redox potentials play in the process are unknown. RDX degradation could be enhanced and/or stimulated if the enzymatic and bio-geochemical factors that regulate this process could be determined and/or controlled.

Degradation of RDX under iron reducing conditions was studied in biological and poised chemical systems.  The redox conditions created by the biological systems were simulated by poised chemical systems in order to compare RDX transformation.  The poised chemical systems combined iron with a catechol solution, creating an iron-ligand complex that achieved the proper Eh values.  RDX degraded in both the biological and chemical systems and final reaction solutions from both systems were analyzed to determine which degradation pathway was followed.  We contend that the biological processes of iron reducing bacteria create redox conditions not only conducive to various enzymatic transformations of RDX, but also to sympathetic degradation.  

Evaluation and Selection of Technologies for the Removal of RDX from an Industrial Wastewater Stream
David B. Gent, US Army Engineer Research & Development Center, 3909 Halls Ferry Road, Vicksburg, MS, 39180, USA, Tel: 601-634-4822, Fax: 601-634-3518, Email: David.B.Gent@usace.army.mil
Jared L Johnson, US Army Engineer Research & Development Center, 3909 Halls Ferry Road, Vicksburg, MS, 39180, USA  Tel: 601-634-3050, Fax: 601-634-3518,Email: Jared.L.Johnson@usace.amry.mil
Greg O’Connor, U.S. Army Armament Research, Development and Engineering Center, Building 355, Picatinny, NJ 07806-5000 Tel: 973-724-5008, Fax: 601-634-3518, Email: gregory.j.oconnor@us.army.mil
Deborah R. Felt, US Army Engineer Research & Development Center, 3909 Halls Ferry Road, Vicksburg, MS, 39180, USA  Tel: 601-634-3576, Fax: 601-634-3518, Email: Deborah.Felt@usace.army.mil
Steven L. Larson, US Army Engineer Research & Development Center, 3909 Halls Ferry Road, Vicksburg, MS, 39180, USA  Tel: 601-634-3431, Fax: 601-634-3518, Email: Steven L Larson@usace.army.mil
Bob Winstead, Ordnance Systems Inc., Holston Army Ammunition Plant, 4509 West Stone Drive, Kingsport, TN 37660, Tel:423-578-6253, Fax 423-578-6132, Email: bobwinstead@baesystems.com

This study examined multiple technologies for removing hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) from the process waste stream at Holston Army Ammunition Plant.  RDX is the primary constituent in the explosive munitions that are produced at this plant.  This study is part of a modernization effort for the 66 year old plant and includes the goal of zero RDX discharge to the facility industrial wastewater treatment plant.  The treatment technologies evaluated included granular activated carbon (GAC), anoxic biotreatment, zero-valent iron (ZVI), alkaline hydrolysis, ultra-violet oxidation, and electrochemical decomposition  

Evaluated criteria included capital and operating cost as well as effectiveness in transforming RDX to nontoxic end products.  Based on laboratory assessments using site water, alkaline hydrolysis and electrochemical treatment were selected for pilot scale evaluation.  RDX removal half-lives for the selected technologies were on the order of 0.25 hours with decomposition of RDX from 10,000 µg/L to less than 20 µg/L.  Bench-scale reactors provided reaction rate coefficients to design pilot-scale sequential batch and plug flow reactors capable of treating 200 gallons per day.  The reaction rate coefficients from the pilot-scale reactors were used to design a full-scale pilot treatment plant that will be demonstrated at the munition production facility.

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