Characterizing the OB/OD Ground at Hingham Annex Using a Different Approach to Multi-Increment Sampling
Mark R. Koenig, US Army Corps of Engineers, Concord, MA        
Brad Chrigwin, Test America Laboratory, South Burlington, VT
Jim Madison, Test America Laboratory, South Burlington, VT
Alan Hewitt, US Army Engineer Research and Development Center (CRREL), Hanover, NH

Quantum-chemical Predictions of Environmentally Important Physical Properties of Explosives
Yana Kholod, Jackson State University, Jackson, MS
Andrea Michalkova, Jackson State University, Jackson, MS         
Frances Hill, U.S. Army Engineer Research and Development Center (ERDC), Vicksburg, MS
Lerzy Leszczynski, Jackson State University, Jackson, MS

In Situ Chemical Reduction for Organic Explosives in Soil
John Valkenburg, The Adventus Group, DeWitt, MI                                  
Alan Seech, Adventus Americas, Inc. Corona Del Mar, CA
Jim Mueller, Adventus Americas Inc., Freeport, IL 
Fayaz Lakhwala, Adventus Americas, Inc. Union, NJ
David Hill, Adventus Remediation Technologies, Mississauga, ON, Canada

LDI-TOF-MS Studies of the Speciation of Tungsten in Environmental Samples
Adebayo Ogundipe, Stevens Institute of Technology, Hoboken, NJ
Julius Pavlov, Stevens Institute of Technology, Hoboken, NJ
Washington Braida, Stevens Institute of Technology, Hoboken, NJ
Agamemnon Koutsospyros, University of New Haven, West Haven, CT
Gregory O’Connor, US Army, Demilitarization and Environmental Technology Division, Picatinny, NJ

Comparison of Effects of Poly- and Mono-tunsgtates on Plant Growth
Nikolay Strigul, Stevens Institute of Technology, Hoboken, NJ

Immobilization of W, Pb, and Cu in Mixed Munitions Firing Range Contaminated soils by Various Amendments
Antonis Karachalios, Stevens Institute of Technology, Hoboken, NJ
Mahmoud Wazne, Stevens Institute of Technology, Hoboken, NJ  
Juan N. Bentancur, Stevens Institute of Technology, Hoboken, NJ
Christos Christodoulatos, Stevens Institute of Technology, Hoboken, NJ
Washington Braida, Stevens Institute of Technology, Hoboken, NJ
Gregory O’Connor, US Army, Demilitarization and Environmental Technology Division, Picatinny, NJ

Tungsten Toxicity and the Adequacy of the Available Data for Risk Analysis and Exposure Guidelines
Tsedash Zewdie, Massachusetts Department of Environmental Protection, Boston, MA
C. Mark Smith, Massachusetts Department of Environmental Protection, Boston, MA
Carol Rowan West, Massachusetts Department of Environmental Protection, Boston, MA

Characterizing the OB/OD Ground at Hingham Annex Using a Different Approach to Multi-Increment Sampling   

Mark R. Koenig, 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, Email: mark.r.koenig@usace.army.mil.
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

The CRREL Multi-Increment Sampling and Analysis by Method 8330B has been used successfully at CE-NAE District on Small Arms Ranges and Gun and Mortar Positions at the Massachusetts Military Reservation (MMR). However, characterizing the Open Burning and Open Detonation Ground at the Hingham Annex DERP-FUDS site in Hingham, Massachusetts has proven to provide some unique challenges. The Hingham OB/OB Ground is a highly disturbed soil that was pushed around using heavy equipment at depths up to six feet. It is located over a shallow aquifer and several of the existing monitoring wells are contaminated with explosive compounds including, 2,4,6-trinitrotoluene, 2-amino-4,6-dinitrotoluene, 4-amino-2,6-dinitrotoluene, 2,4-dinitrotoluene, 1,3,5-trinitrobenzene, HMX, RDX, TNX, DMX and MNX.

Historical soil data did not indicate many explosive detections based on the Geoprobe soil sampling method. Using a modified MIS approach to characterize the site, MIS where collected on the side-walls of test trenches at 0-3 ft and 0-6 ft intervals and the samples were analyzed for an extended list of explosives compounds by Method 8330B. Air drying, sieving, and mechanical grinding was performed on the soil samples prior to analysis 

The main focus of the presentation will discuss the use of this modified-MIS strategy to characterize and determine if a continuing source of contamination is present in the disturbed Hingham site soils. The MIS soil, sediment, and GW results will be discussed in detail and the conclusion for a path forward will be evaluated. Examples of the co-extracted interferences with target explosives will be provided and a detailed discussion on how usable data was obtained from the dual-column chromatograms, as well as interpretation of Photo-Diode Array (PDA) spectra will be highlighted. PDA spectral confirmation is an additional valuable confirmatory tool to help eliminate and reduce false positives.

Quantum-chemical Predictions of Environmentally Important Physical Properties of Explosives 

Yana Kholod, Ph.D. Graduate Student,  Interdisciplinary Nanotoxicity CREST Center,  Department of Chemistry , Jackson State University, Jackson, MS 39217, Tel: 601-979-3979
Andrea Michalkova, Ph.D., Research Associate, Interdisciplinary Nanotoxicity CREST Center,  Department of Chemistry , Jackson State University, Jackson, MS 39217, Tel: 601-979-1041
Leonid Gorb, Ph.D.,  Senior Scientist, SpecPro Ltd, Vicksburg, MS 39180,USA, Tel 601-634-3863
Frances Hill, Ph.D., Research Chemist, U.S. Army Engineer Research and Development Center (ERDC), Vicksburg, MS 39180, Tel: 601-634-4661
Lerzy Leszczynski, Ph.D., Professor of Chemistry, Director of Interdisciplinary Nanotoxicity CREST Center, Department of Chemistry, Jackson State University, 39217, Jackson, MS, Tel: 601-979-1221 

We will present the results of three years of extensive computational simulations   of environmentally important physical properties for such classes of explosives as nitroaromatics, nitroamines and nitrogen rich compounds. These studies were performed at the Environmental Laboratory of the US Army Corps of Engineers, ERDC, Vicksburg, MS and at the Interdisciplinary Nanotoxicity Center at Jackson State University. Both quantum-chemical methods and a variety of QSAR techniques have been used in this study. The physical properties that will be discussed and compared with available experimental data include vapor pressure, Henry’s law constants, water solubility, octanol-water partition coefficients, reduction potentials and soil-water desorption coefficienst (log(Kd)). Chemical solubility and interactions of chemicals with soil are major components that influence the migration of chemicals in the environment, and their ultimate environmental fate. Thus, a major part of this study has been the development of accurate methods to predict these properties. In particular, the temperature dependence of explosive solubilities and the dependence on the salinity of water have been predicted at the quantum-chemical level and compared with ones obtained by QSAR-based methods.  It will be shown that the COSMO-RS approximation, a method which does not require a training set, provides the same accuracy as QSAR approaches, which are training set dependent.  Methodologies to predict soil-water desorption coefficients log(Kd) have been developed at the quantum-chemical level. A variety of approximate thermodynamic formulas have been analyzed, and results from those methods that provide the closest correspondence with available experimental data will be presented.

In Situ Chemical Reduction for Organic Explosives in Soil

John Valkenburg, Adventus Americas, Inc. 1493 West Pratt Road, DeWitt, MI 48820, Tel: 517-669-5400, Fax: 517-669-5455, Email: John.Valkenburg@AdventusGroup.com
Alan Seech, Adventus Americas, Inc. 3334 E. Coast Highway, Suite 114, Corona Del Mar, CA 92625, Tel 949-788-1269, Fax 815.235.3506, Email: Alan.Seech@AdventusGroup.com
Jim Mueller, Adventus Americas Inc., 2871 W. Forest Road, Suite #2, Freeport, IL  61032, Tel: 815-235-3503, Email: jim.mueller@adventusgroup.com
Fayaz Lakhwala, Adventus Americas, Inc. 1435 Morris Avenue, 2nd Flr., Union, NJ 07083, Tel: 908-688-8543, Fax: 908-688-8563, Email: Fayaz.Lakhwala@AdventusGroup.com   
David Hill, Adventus Remediation Technologies, 1345 Fewster Drive, Mississauga, ON, Canada, L4W2A5, Tel: 905-273-5374, Fax: 905-273-4367, Email: David.Hill@AdventusGroup.com

The project objective was treatment of 10,000 yards of TNT and RDX impacted soil resulting from past practices at Tooele Army Depot (TEAD). Soil concentrations of TNT and RDX were as high as 2,500 and 1,000 mg/kg, respectively, with remediation goals (RGs) of 86 mg/kg TNT and 31 mg/kg RDX. The scope was to treat the TNT and RDX impacted soils to RGs and thereby eliminate TEAD site worker inhalation risks as well as remove the groundwater impact threat. About 2,500 people depend on wells within 3 miles of the site as a source of drinking water. Initial treatability and feasibility analyses identified conventional composting as the most cost-effective soil treatment alternative, utilizing organic amendments at 70 weight percent (wt %) of total compost mass, and treating in seven batches over twelve months’ time. Because of changes in project economics, an alternate form of treatment (using organic carbon with zero valent iron at a 3.5 wt % dosing) was used to reduce costs and make it possible for the project to be completed within budget. The project consultant and the Army Corps accepted this alternative following the completion of pilot-scale soil treatment that met the site remediation goals. Full-scale soil treatment to RGs was effected in a single application cycle and treatment was completed in three cycles over five months instead of a projected seven cycles over 12 months (with conventional composting). Pilot scale treatability testing identified and reinforced the need for control of key bioremediation process parameters, which were managed during full-scale remediation. The presentation will highlight these ‘lessons learned’, along with identifying full-scale operational challenges, and summarizing the process used for treatment. Both pilot and full-scale results will be shown, along with showing how the field approach was implemented. 

LDI-TOF-MS Studies of the Speciation of Tungsten in Environmental Samples

Adebayo Ogundipe PhD, Stevens Institute of Technology, Castle Point on Hudson, Hoboken, NJ 07030, Tel: 201-216-5593, Fax: 201-216-8303, Email: adebayo.ogundipe@stevens.edu
Julius Pavlov, Stevens Institute of Technology, Castle Point on Hudson, Hoboken, NJ 07030, Tel: 201-216-8987, Fax: 201-216-8303, Email: jpavlov@stevens.edu
Washington Braida PhD, Stevens Institute of Technology, Castle Point on Hudson, Hoboken, NJ 07030, Tel: 201-216-5681, Fax: 201-216-8303, Email: washington.braida@stevens.edu
Agamemnon Koutsospyros PhD, University of New Haven, West Haven, CT 06513, Tel: 203-932-7398, Fax: 203-932-7158, Email: AKoutsospyros@newhaven.edu
Gregory O’Connor, US Army, Demilitarization and Environmental Technology Division, Picatinny, NJ 07806, Tel: 973-724-5008, Email: gregory.j.oconnor@us.army.mil 

Tungsten has recently been classified as an emerging pollutant by the Environmental Protection Agency. While the toxicity of tungsten has not established, research indicates that different species of tungsten in solution induce different toxic responses. However, current analytical protocols only measure total tungsten. Moreover, most toxicity studies have been conducted using the monomeric species, while research has established the presence of monomeric and polymeric species in environmental samples. Laser-Desorption Ionization (LDI) has shown promising results in the qualitative and semi-quantitative analysis of tungsten species in environmental samples.

Many tungsten-bearing compounds and materials are amenable to laser-desorption ionization (LDI). A time-of-flight mass spectrometer (TOF-MS) can be used to separate and detect the ablated ions, producing particularly rich mass spectra of tungsten species. Minimum sample preparation is required, and a minuscule amount of analyte is necessary for a successful analysis (typically one works with the evaporated residue of a 1 µL drop of 50-100 ppm solution). The technique is also useful in monitoring the course of reactions, such as aging or pH transformations of tungsten species, and for corrosion studies.; Furthermore, the technique has a considerable potential for characterization of tungsten speciation. We show examples of these applications of LDI-TOF-MS to elucidate tungsten speciation in firing range soil samples, and discuss some implications to its environmental chemistry.

Comparison of Effects of Poly- and Mono-tunsgtates on Plant Growth

Nikolay Strigul, Center for Environmental systems, Stevens Institute of Technology, Hoboken, NJ, 07030, USA, Tel: 201-9524260, Email: nstrigul@stevens.edu 

Tungsten is a widely used metal for which only limited information on toxicological and environmental effects exists. Tungsten anions may polymerize (depending on concentration, pH, and aquatic geochemistry) in environmental systems. It was shown that dissolution of tungsten metallic particles in soil is accompanied by acidification that should facilitate tungsten polymerization (Strigul et al. 2005). This polymerization/condensation reaction results in the development of several types of stable polyoxoanions with Anderson, Keggin, and Dawson structures. Certain unique chemical properties (in particular redox and acidic properties) differentiate these polyanions from monotungstates. Recently we have shown (Strigul et al. 2009, Strigul et al., submitted) that polyoxotungstates are significantly more toxic than monotungstates to fish, plants, daphnia, algae, and redworms. Similar results we obtained in experiments on aquatic ecosystems (Strigul et al. 2009). Here we will present the new experimental results on the effects of tungsten speciation on plant growth. In particular, we have conducted a series of plant growth experiments with the following species: Sorghum saccharatum, Lepidium sativum, Sinapis alba, and Quesrcus rubra. Polytungstates were significantly more toxic (in, at least, 10 times when expressed in tungsten mg/kg of soil) than monotungstates for all species tested. We conclude that polytungstates are more toxic than monotunsgtates to a variety of terrestrial and aquatic organisms.

Immobilization of W, Pb, and Cu in Mixed Munitions Firing Range Contaminated soils by Various Amendments

Antonis Karachalios, Stevens Institute of Technology, Castle Point on Hudson, Hoboken, NJ 07030, Tel: 201-216-8432, Fax: 201-216-8212, Email: akaracha@stevens.edu
Mahmoud Wazne PhD, Stevens Institute of Technology, Castle Point on Hudson, Hoboken, NJ 07030, Tel: 201-216-8993, Fax: 201-216-8212, Email: mwazne@stevens.edu
Juan N. Bentancur, Stevens Institute of Technology, Castle Point on Hudson, Hoboken, NJ 07030, Tel: 201-216-8993, Fax: 201-216-8303
Christos Christodoulatos PhD, Stevens Institute of Technology, Castle Point on Hudson, Hoboken, NJ 07030, Tel: 201-216-5675, Fax: 201-216-8303, Email: christod@stevens.edu
Washington Braida PhD, Stevens Institute of Technology, Castle Point on Hudson, Hoboken, NJ 07030, Tel: 201-216-5681, Fax: 201-216-8303, Email: washington.braida@stevens.edu
Gregory O’Connor, US Army, Demilitarization and Environmental Technology Division, Picatinny, NJ 07806, Tel: 973-724-5008, Email: gregory.j.oconnor@us.army.mil 

The aim of this study is to assess the stabilization of metals in contaminated firing range soils using various amendments. A total of eight soil samples representative of soil compositions used at firing ranges in the United States were characterized and amended with nine different additives. The selected amendments included Granulated Ferric Oxide (GFO), Granulated Titanium Dioxide (GTD), Pahokee Peat Soil (PPS), Gascoyne Leonardite Soil (GLS), Elliot Silty Loam Soil (ESLS), Diammonium Phosphate (DAP), Calcium Phosphate Monobasic (CPM), Potassium Phosphate (KP), and Apatite II^TM. The amended soils were evaluated in batch and flow through leaching tests to immobilize Cu, Pb, and W. GFO and GTD were applied at dosages of 10g/kg, 50g/kg and 100g/kg, organic materials were applied at a dosage of 100g/kg, whereas the phosphate sources were applied initially at a dosage of 1g/kg as phosphorous (P) and then at various dosages in order to normalize the molar ratio of (P/Pb) at 1.8. The experimental results indicated that GFO at a dosage of 100 g/kg (10%) was superior to all the other materials used for stabilizing Cu, Pb and W during the leaching tests. Flow-through column tests were conducted using GFO at 10% to test the effectiveness of GFO to immobilize Cu, Pb, and W. This blend was selected because it gave the best performance among all other blends. The two soil samples with the highest Cu and Pb concentrations were used in these tests. The concentrations of the Cu, Pb, and W were significantly reduced in the effluent of the amended soil columns as compared to the control soil columns.

Tungsten Toxicity and the Adequacy of the Available Data for Risk Analysis and Exposure Guidelines

Tsedash Zewdie Ph.D. Massachusetts Department of Environmental Protection, Office of Research and Standards, 1 Winter Street, Boston, MA, Tel: 617-292-5842, Email: Tsedash.Zewdie@state.ma.us
C. Mark Smith Ph.D., S.M. Massachusetts Department of Environmental Protection, Office of Research and Standards, 1 Winter Street, Boston, MA, Tel: 617-292-5509, Email: C.Mark.Smith@state.ma.us
Carol Rowan West MPH. Massachusetts Department of Environmental Protection, Office of Research and Standards, 1 Winter Street, Boston, MA, Tel: 617-292-5510, Email: Carol.Rowanwest@state.ma.us.

In recent years concerns have been raised about the toxicity of tungsten metal because of the identification of a cancer cluster – specifically acute lymphoblastic leukemia – among a group of children who reside in Fallon, Nevada which is an area with high levels of tungsten.  Since there is a paucity of data on tungsten toxicity the Center for Disease Control nominated tungsten as a priority toxic for testing under the National Toxicology Program in 2002. Tungsten has been detected in various environmental media at the Massachusetts Military Reservation (MMR) on Cape Cod, and is assumed to have originated from the use of small arms ammunition (“green bullets”). Because of lack of federal or state standards to regulate tungsten, the Office of Research and Standards (ORS) has reviewed the available toxicity data for this metal.   The health effects of tungsten depend on the type of tungsten (soluble or insoluble) and on the route of exposure (ingestion, inhalation or skin contact).  Studies conducted in animals exposed to soluble tungsten by ingestion suggest that this compound can cause adverse effects on reproduction (affecting duration of pregnancy) and development (decreased growth), as well as effects on the kidneys, blood, nervous and gastrointestinal systems. There is not enough information to determine whether exposure to tungsten can cause cancer in humans. In this presentation, ORS will provide an overview of the toxicity of tungsten and adequacy of the database for deriving a drinking water guideline.  Based on this information, ORS will describe an approach and selection of data to derive a chronic drinking water guideline.

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