Wednesday (Group 2) - SERDP-ESTCP - Strategic Environmental ...

Partners in Environmental Technology 

Wednesday (Group 2) Posters 

WEDNESDAY (GROUP 2) POSTERS 

This year, more than 400 posters are on display in the Exhibit Hall, Group 1 on Tuesday and 

Group 2 on Wednesday. These posters, many representing current and recently completed 

SERDP and ESTCP projects, highlight research within the SERDP and ESTCP focus areas 

(Environmental Restoration, Munitions Management, Sustainable Infrastructure, and Weapons 

Systems and Platforms). To help attendees find their areas of interest, posters are grouped to 

keep similar technologies together. In addition to the SERDP and ESTCP Partners in 

Environmental Technology exhibit booth, there are other exhibitors at this event with booths 

representing funding and partnering opportunities or information resources. 

While many SERDP and ESTCP projects are showcased in the Exhibit Hall, more information 

about past and present SERDP and ESTCP research projects is available by visiting our web 

sites (www.serdp.org and www.estcp.org). In addition, both sites enable you to access the 

SERDP/ESTCP Online Library (docs.serdp-estcp.org) where you can search for technical reports 

using criteria such as focus area, sub-focus, contaminant, or other specific environmental 

concerns. 

The Exhibit Hall will be open throughout the Symposium. You are encouraged to tour the 

posters and exhibit booths during the hours noted below when presenters will be available for 

discussion. Technical session breaks on Tuesday and Wednesday will take place in the Exhibit 

Hall. Presenters may be available during these breaks. 

PRESENTER 

ORGANIZATION 

Wednesday Exhibit Hall Hours 

7:30 a.m. – 8:30 a.m. 

12:30 p.m. – 1:45 p.m. 

5:00 p.m. – 7:00 p.m. 

POSTER TITLE POSTER PAGE 

Munitions Management (MM) 

MM: Ground-Based Detection and Discrimination — EMI & Magnetometers / Modeling & Processing 

Bruce Barrow 

Evaluation of Electromagnetic Induction Sensor Noise 

21 G-1 

SAIC, Inc. 

Sources 

Dr. Leonard Pasion 

Sky Research, Inc. 

Dr. Leonard Pasion 


Fridon Shubitidze 


Lawrence Carin 

Signal Innovations Group, Inc. 

Selecting Optimal Models for Inverting EMI Data 22 G-2 

Simultaneous Inversion of UXO Parameters and 

Background Response 

Advanced EMI Models Applied to Next-Generation EMI 

Sensors: Data Processing and UXO Discrimination 

Studies 

Demonstration of Digital Geophysics on Actual UXO 

Sites 

23 G-3 

24 G-4 

25 G-5 

Refer to the Exhibit Hall Floor Plan in the General Info/Maps section for poster locations. 

G-i



PRESENTER 

ORGANIZATION 

Dr. Ben Barrowes 

ERDC-CRREL 

Dr. Ben Barrowes 

ERDC-CRREL 

Larry Deschaine 

SAIC, Inc. 

Dr. Leslie M. Collins 

Duke University 

Thomas Bell 

SAIC, Inc. 

Dr. Dean Keiswetter 

SAIC, Inc. 

Dr. Stephen Billings 





Man-Portable Vector Time Domain EMI Sensor and 

Discrimination Processing 

High Fidelity Electromagnetic Induction Instruments and 

Physically Complete Models 

Increasing the Understanding and Usefulness of Machine 

Learned MEC Discrimination Results Using 

Evolutionary Strategy Tools for Knowledge Discovery 

Statistical Signal Processing for UXO Discrimination for 

Next-Generation Sensor Data 

Position-Independent Processing of Electromagnetic 

Induction Data for Target Classification 

Discrimination Performances of Commercial Sensors at 

APG and YPG 

Shock Demagnetization of Projectiles on Impact with the 

Ground 

38 G-6 

39 G-7 

40 G-8 

41 G-9 

42 G-10 

43 G-11 

44 G-12 

Robust Statistics for UXO Discrimination 45 G-13 


Discrimination at a Challenging Site 46 G-14 


MM: Ground-Based Detection and Discrimination — EMI & Magnetometers / Sensors 

Ted Asch 

Refinements in the ALLTEM UXO Detection and 

47 G-15 

U.S. Geological Survey 

Discrimination System 

Yongming Zhang 

Quasar Federal Systems, Inc. 

Yongming Zhang 

Quasar Federal Systems, Inc. 

Dr. Erika Gasperikova 

Lawrence Berkeley National 

Laboratory 

Dr. Mark Prouty 

Geometrics 

Helicopter Magnetometer Platform Based on Compact 

Induction Sensors 

Tri-Axis Fluxgate-Induction Sensor for Advanced Time- 

Domain UXO Detection and Discrimination 

48 G-16 

49 G-17 

Advances in UXO Discrimination 50 G-18 

MetalMapper: A Multi-Sensor TEM and Magnetic 

Gradiometer System for UXO Detection and 

Classification 

51 G-19 

Dr. Mark Prouty 

Geometrics 

Miniature Total Field Magnetometers 52 G-20 

Dr. Roy Wiegert 

Naval Surface Warfare Center 

Panama City Division 

Daniel Steinhurst 

Nova Research, Inc. 

Sy-Hwang Liou 

University of Nebraska 

Dr. Michael Asten 

Flagstaff Geoconsultants Technology 

Pty Ltd 

Improved Magnetic Star Methods for Real-Time, Pointby-Point 

Localization of Unexploded Ordnance and 

Buried Mines 

MTADS Time-Domain EMI Sensor Systems for UXO 

Classification 

Magnetic Sensors with Picotesla Magnetic Field 

Sensitivity at Room Temperature 

Characterization of Munitions Using EMI with an Array 

of 3-Component B-Field Sensors (BEAMOD) 

66 G-21 

67 G-22 

68 G-23 

69 G-24 


G-ii



PRESENTER 

ORGANIZATION 

Dr. Wes Cobb 

University of Denver Research 

Institute 

Dennis A. Teefy 

U.S. Army Aberdeen Test Center 

Ms. Amy Walker 

USAESCH 


MM: High Explosive Identification 

Operational Evaluation of a New Acoustic Technique for 

UXO Filler Identification 

MM: Planning and Support 

APG Standardized UXO Technology Demonstration Site 

Reconfiguration 

UX-Process Update – Free Software for Digital 

Geophysical Mapping 

Sustainable Infrastructure (SI) 

SI: Facilities Management — Facility Waste 

Dr. Nancy E. Ruiz 

Application of a Bimetallic Solvent Paste Technology for 

NAVFAC Engineering Service Center PCB Removal from Older Structures on DoD Facilities 

Mr. Stephen Cosper 

U.S. Army-CERL 

Jo Ann Ratto 

U.S. Army Natick Soldier Research, 

Development And Engineering Center 

Jo Ann Ratto 

U.S. Army Natick Soldier Research, 

Development and Engineering Center 

Rance T. Kudo 

NAVFAC ESC 

Dr. Chris Schwier 

Metabolix 

Determining Environmental Solubility of Pb from 

Recycled Concrete Aggregate (Poster will not present) 

63 G-25 

64 G-26 

65 G-27 

70 G-28 

71 G-29 

Lightweight, Compostable and Biodegradable Fiberboard 72 G-30 

Nanotechnology Packaging for the Military 73 G-31 

NoFoam System Technology for Aircraft Hangar Fire 

Suppression Foam System 

74 G-32 

PHA Bioplastic Packaging Materials 75 G-33 

Jessica Hsu 

Food and Human Waste Remediation for Navy Ships and 

Clairvoyant Technologies, Inc. Army Base Camps (Poster will not present) 

93 G-34 

SI: Facilities Management — Noise 

Jeffrey S. Vipperman 

Characterization of a Bayesian Classifier to Identify 

University of Pittsburgh 

Military Impulse Noise 

76 G-35 

SI: Natural Resources Management — Threatened and Endangered Species 

Dr. Luke K. Butler 

Physiological and Demographic Effects of Road Density 

Tufts University 

on Endangered Songbird Breeding at Fort Hood 

87 G-36 

Dr. Henriette Jager 

Oak Ridge National Laboratory 

Dr. Joseph M. Szewczak 

Humboldt State University 

Dawn M. Lawson 

NAVFAC Southwest 

Bernd Blossey 

Cornell University 

Dr. Maile C. Neel 

University of Maryland 

Population Viability Analysis of Shortnose Sturgeon 

(Acipenser brevinostrus) in the Ogeechee River, Georgia 

Automated Acoustic Monitoring of Bat and Bird 

Populations 

Evaluating the Effect of Climate Change on Population 

Demographics of Ceanothus Verrucosus 

Naval Facilities Engineering Service Center Multiple 

Stressors: The Role of Worms, Slugs and Deer in 

Shaping Our Forest Plant Communities 

An Ecoinformatic Approach to Developing Recovery 

Goals and Objectives 

88 G-37 

89 G-38 

90 G-39 

91 G-40 

92 G-41 


G-iii



PRESENTER 

ORGANIZATION 

Dr. Anna Pidgeon 

University of Wisconsin, Madison 

Dr. Leslie Ries 


R. Todd Jobe 

The University of North Carolina at 

Chapel Hill 

Anne Trainor 

University of North Carolina 

Dr. Nicole Y. Thurgate 

North Carolina State University 

Mary E. Cablk, Ph.D. 

Desert Research Institute 

Dr. Betsy A. Bancroft 

University of Washington 

Dr. Isabelle-Anne Bisson 

Princeton University 

Marissa Brand 

SPAWAR Systems Center Pacific 

Dr. Rebecca R. Sharitz 

Savannah River Ecology Laboratory 

Jeffrey R. Walters 

Virginia Polytechnic Institute and 

State University 

Chad B. Wilsey, M.S. 


Dr. Carl Qualls 

University of Southern Mississippi 

Dr. Katherine Strickler 

University of Idaho 


Characterizing Loggerhead Shrike Habitat with Local 

and Remotely-Sensed Data 

Understanding the Impacts of Habitat Fragmentation in 

Complex Landscapes 

A Life-History Based Multi-Species Framework for 

Landscape Connectivity Conservation 

Connectivity of Red-Cockaded Woodpecker (Picoides 

Borealis) Habitat in the Sandhills Region of North 

Carolina 

The Effects of Habitat Fragmentation and Connectivity 

on the Movement Behaviors of a Rare Amphibian 

Final Assessment of DTK9 Teams – 2008 Field Testing 

Results 

Forecasting the Effects of Land-Use Change on Red- 

Cockaded Woodpeckers at Fort Benning, Georgia Using 

a Spatially Explicit Individual-Based Model (HexSim) 

Energetic Cost of Simulated Military Training Activities 

in Songbirds 

94 G-42 

95 G-43 

96 G-44 

97 G-45 

98 G-46 

99 G-47 

100 G-48 

111 G-49 

Integration and Validation of Avain Radars (IVAR) 112 G-50 

Conservation of Threatened, Endangered and Sensitive 

Plant Species on Federal Lands in the Southeastern Fall 

Line Sandhills 

A Decision Support System for Identifying and Ranking 

Critical Habitat Parcels on and in the Vicinity of 

Department of Defense Installations 

An Ensemble Approach to Modeling Black-Capped 

Vireo Habitat for Use in a Spatially Explicit Individual- 

Based Model 

Causes of Low Hatching Success of Gopher Tortoise 

(Gopherus polyphemus) Eggs at Camp Shelby, 

Mississippi 

Modeling Population Viability of Species of Concern 

Using Count Data 

Douglas Bruggeman 

When Do We Know Enough to Re-Allocate Listed 

Michigan State University 

Species Habitat 

SI: Natural Resources Management — Maritime Sustainability 

Peter L. Tyack 

A Study on Behavioral Responses of Beaked and Other 

Woods Hole Oceanographic 

Whales to Sonar and Other Sounds 

Institution 

Dr. Adam Fincham 

University of Southern California 

Ocean Sonic Boom Models for Environmental Impact of 

Space Launch Vehicle, Space Reentry and Supersonic 

Overflight 

113 G-51 

114 G-52 

115 G-53 

116 G-54 

117 G-55 

118 G-56 

119 G-57 

120 G-58 


G-iv



PRESENTER 

ORGANIZATION 

Dr. Maxim Gorbunov 

Rutgers University 

Dr. R. Pamela Reid 

University of Miami 

Dr. Patrick Halpin 


Dr. Jay Barlow 

NOAA - Southwest Fisheries Science 

Center 

Dr. Meng-Dawn Cheng 


Dr. K. James Hay 

U.S. Army ERDC-CERL 

Dr. K. James Hay 


Mr. Tom Torres 

Naval Facilities Engineering Service 

Center 

Mr. Jim Tankersley 

Battelle 

Randel Bowman 

Oklahoma City Air Logistics Center 

Glen Baker 

309 AMXG/EN 

Ms. Donna Provance 

NDCEE/CTC 

Mr. Jack Benfer 

NAVAIR 

Peng Wang 

University of Cincinnati 

Dale Schaefer 


Diana Facchini 

Integran Technologies, Inc. 


Application of Variable Fluorescence Technique for 

Assessing Natural and Anthropogenic Stressors at DoD 

Coral Reefs 

High Resolution Landscape Mosaics for Coral Reef 

Monitoring 

Predictive Modeling of Marine Mammals and 

Spatial Decision Support for Naval 

Environmental Compliance 

Predictive Modeling of Marine Mammal 

Density from Existing Survey Data and Model 

Validation Using Upcoming Surveys 

Weapons Systems and Platforms (WP) 

WP: Engine Noise and Emissions 

A Comprehensive Program for 

Characterization of Emissions from Military 

Aircraft 

WP: General Interest 

Toxic Industrial Chemical Database for the Intelligence 

Preparation in the Battlefield Process 

WP: Waste Reduction and Treatment 

121 G-59 

122 G-60 

123 G-61 

124 G-62 

145 G-63 

150 G-64 

Vapor Recovery by Electrothermal Swing Adsorption 151 G-65 

Biological Treatment of Solvent Based Paint 152 G-66 

Progress Report: Qualification, Demonstration, & 

Validation of Compliant Removers for Aircraft Sealants 

and Specialty Coatings 

WP: Surface Engineering and Structural Materials 

153 G-67 

Robotic Laser Coating Removal System 146 G-68 

Ultraviolet (UV)–Curable Coatings for Aerospace 

Applications 

Corn-Hybrid Polymer (CHP) Blasting Benefits Aviation 

Weapon Systems 

Infrared Reflectance Imaging for 

Environmentally Friendly Corrosion Inspection 

Through Organic Coatings 

How Does Silane Enhance the Protective Properties of 

Epoxy Films 

147 G-69 

148 G-70 

149 G-71 

154 G-72 

Can Vanadates Replace Chromates 155 G-73 

Nanocrystalline Cobalt-Alloy Coatings for Chrome 

Replacement Applications 

156 G-74 


G-v



PRESENTER 

ORGANIZATION 

Professor Gerald S. Frankel 

The Ohio State University 

Professor Gerald S. Frankel 


Mark Miller 

Benet Labs 

Mr. Wayne Patterson 

809 MXSS/CLA Science and 

Engineering Laboratory 

Mr. Corey Q. Bliss 

Air Force Research 

Laboratory/RXSSO 

Mr. Wayne Ziegler 

U.S. Army Research Lab 

Professor Michael R. Kessler 

Iowa State University and Ames 

Laboratory 

William Fahrenholtz 

Missouri University of Science and 

Technology 

Adam Goff 

Luna Innovations Incorporated 

Chuck Tomljanovic 

National Defense Center for Energy 

and Environment 

Mr. Robert Fisher 

NDCEE/CTC 

Victor K. Champagne 

U.S. Army Research Laboratory 

Mr. Christopher Joseph 

Air Force Research Lab–Coatings 

Technology Integration Office (CTIO) 

Dr. Elizabeth Berman 

Air Force Research Lab/MLSC 

Mr. Steven Brown 

NAWC Aircraft Division 

Dr. Andrew Guenthner 

NAVAIR 

John Player 

Infoscitex Corporation 

Dr. Peter Zarras 

NAWCWD 

Professor Christopher K. Ober 



Development of Ni-Cu-Ru Consumables for Welding of 

Austenitic Stainless Steels 

Scientific Understanding of Non-Chromated Corrosion 

Inhibitors Function 

Chromium Replacement and Erosion Mitigation 

Technology for Medium Caliber Gun Barrels 

157 G-75 

158 G-76 

159 G-77 

Low Temperature Powder Coatings 160 G-78 

Ultraviolet Curable Powder Coatings 171 G-79 

Demonstration/Validation of Tertiary Butyl Acetate for 

DoD Solvent Applications 

Environmentally Benign Repair of Composites Using 

High Temperature Cyanate Ester Nanocomposites: 

Nanofluid Processing and Characterization 

Characterization of Species and Coating Morphology 

Involved in the Corrosion Protection of Rare Earth Based 

Coatings 

Ternary Cadmium Replacement Coatings for High 

Strength Fasteners 

Demonstration of a Lead-Free Surveillance and Detection 

Program to Address RoHS Regulation Lead-Free Risks 

in Weapon Systems and Platforms 

Optimizing CARC Improvements for Army Weapon 

Systems 

Supersonic Particle Deposition Technology for Repair of 

Magnesium Aircraft Components 

Performance Evaluation and Qualification of Magnesium 

Rich Primer for Chrome Free Aerospace Coating 

Systems 

Investigation of Chemical Vapor Deposition of 

Aluminum as a Replacement Coating for Cadmium 

Cadmium Alternatives for DoD and NASA Applications 

– Phase II Testing Results 

New Reactive Diluents for an Environmentally Efficient 

Approach to Composite Repair 

Shelf-Stable Adhesive for Reduction of Composite 

Repair Hazardous Waste 

Validation of Novel Electroactive Polymers as 

Environmentally Compliant Coatings for Replacement of 

Hexavalent Chromium Pretreatments 

Environmentally Benign Multilayer Polymer Coatings 

with Controlled Surface Properties for Marine 

Antifouling Applications 

172 G-80 

173 G-81 

174 G-82 

175 G-83 

176 G-84 

187 G-85 

188 G-86 

189 G-87 

190 G-88 

191 G-89 

192 G-90 

193 G-91 

194 G-92 

195 G-93 


G-vi



PRESENTER 

ORGANIZATION 

Professor Matt O’Keefe 

Missouri University of Science and 

Technology 

Dr. Nese Orbey 

Foster-Miller 

El Sayed Arafat 

NAVAIR 

Dr. John La Scala 

Army Research Laboratory 

Dr. John La Scala 


Mr. Scott Grendahl 


Mr. Shridhar Yarlagadda 

University of Delaware 


Evaluation of Multifunctional UV (MUV) Curable 

Corrosion Coatings on High Strength Aluminum Alloy 

Substrates 

UV Curable Non-Chrome Primer and Advanced Topcoat 

System 

Demonstration/Validation of High Performance 

Corrosion Preventive Compound (CPC) for Interior 

Aircraft Applications 

Environmentally Friendly Coatings Systems for DoD 

Applications 

Demonstration of Composites with Low Hazardous Air 

Pollutant Contents for Military Applications 

Hydrogen Re-Embrittlement Test Method for Cadmium 

Plating Alternatives and Maintenance Chemicals (Poster 

will not present) 

Near-Infrared Radiation Based Composite Repair Using 

Thermoplastics as Adhesives 

Environmental Restoration (ER) 

ER: Chlorinated Solvents — DNAPL Source Zone Remediation 

Dr. Richard Watts 

Mechanism of Base-Activation of Persulfate for In Situ 

Washington State University Chemical Oxidation (ISCO) 

Dr. Robert Siegrist 

Colorado School of Mines 

Carmen A. Lebrón 

Naval Facilities Engineering Services 

Center 



Center 



Center 

Mr. Charles Schaefer 

Shaw Environmental, Inc. 

Megan M. Smith 


Jeff Allen Kai Silva 


Pamela J. Dugan, Ph.D. 

Carus Corporation 

Quantifying Organic Chemicals in Soil Samples: Effects 

of Sampling Method Attributes Under Varied 

Contaminant Characteristics and Environmental 

Conditions 

Development of a Protocol and Screening Tool for 

Selection of DNAPL Source Area Remediation 

Improving Effectiveness of Bioremediation at DNAPL 

Source Zone Sites by Applying Partitioning Electron 

Donors (PEDS) 

DNAPL Removal from Fractured Rock Using Thermal 

Conductive Heating (TCH)—Treatability Study and TCH 

Demonstration Pilot Progress 

DNAPL Dissolution and Dechlorination in Discrete 

Fractures 

Coupling Polymer Floods with Biodegradation and 

Chemical Oxidation Treatment – Techniques to Achieve 

More Effective Groundwater Remediation in 

Heterogeneous Aquifers 

The Addition of Water-Soluble Polymers to Enhance the 

Delivery of In Situ Remediation Agents in 

Heterogeneous Strata 

Coupling Surfactants with Permanganate for PCE 

DNAPL Mass Removal: Coinjection or Sequential 

Application as Delivery Methods 

206 G-94 

207 G-95 

208 G-96 

209 G-97 

210 G-98 

211 G-99 

212 G-100 

26 G-101 

30 G-102 

31 G-103 

32 G-104 

33 G-105 

34 G-106 

35 G-107 

36 G-108 

37 G-109 


G-vii



PRESENTER 

ORGANIZATION 

Robert C. Borden 


Dr. Raymond Ball 

EnChem Engineering, Inc. 

Dr. Rick Johnson 

Oregon Health & Science University 

Ronald Falta 

Clemson University 

Ronald Falta 


Jennifer L. Triplett Kingston 

Haley & Aldrich 

Tamzen Macbeth Ph.D., P.E. 

North Wind, Inc. 

Dr. Rick Johnson 


Dr. Kurt Pennell 

Georgia Institute of Technology 

Mr. David Fleming 

Thermal Remediation Services, Inc. 

Dr. Ralph S. Baker 

TerraTherm, Inc. 

Greg Lowry 

Carnegie Mellon University 

Dr. Tom Sale 

Colorado State University 

Dr. Tom Sale 


Dr. Michael D. Annable 

University of Florida 

Dr. Edward Sudicky 

University of Waterloo 

Linda M. Abriola, Ph.D. 


Naji Akladiss 

Maine Department of Environmental 

Protection 

Lowell Kessel 

G.E.O., Inc. 


Designing Efficient Permanganate Injection Systems in 

Heterogeneous Aquifers 

In Situ “Advanced Mixed Oxidation and Inclusion” 

Technology: Inclusion Behavior of TCE DNAPL and 

Ozone into Clathrates 

Persulfate Persistence Under Thermal Activation 

Conditions 

Contaminant Mass Transfer During Boiling in Fractured 

Geologic Media 

Decision & Management Tools for DNAPL Sites: 

Optimization of Chlorinated Solvent Source and Plume 

Remediation Considering Uncertainty 

A Preliminary Assessment Tool for Use of In-Situ 

Thermal Technologies at DNAPL-Impacted Sites 

Combining Low-Energy Electrical Resistance Heating 

with Biotic and Abiotic Reactions for Treatment of 

Chlorinated Solvent DNAPL Source Areas 

Hydraulics of In-Situ Electrical Resistance Heating at 

Sub-Boiling Temperatures 

Reactivity of Chlorinated Ethenes During Thermal 

Treatment 

Remediation of DNAPL and LNAPL Using Electrical 

Resistance Heating at U.S. Military Bases 

Dominating Processes During DNAPL Removal from the 

Saturated Zone Using Thermal Wells 

Effect of Aggregation, Hydrogeochemistry, and Clay on 

NZVI Emplacement in the Subsurface 

Field Applications of ZVI-Clay Technology for 

Chlorinated Solvent Source Zones 

Decision Guide for Managing Chlorinated Solvents 

Releases 

Predicting DNAPL Source Zone and Plume Response 

Using Site-Measured Characteristics 

Computational and Experimental Investigation of 

Contaminant Plume Response to DNAPL Source Zone 

Architecture and Depletion in Porous and Fractured 

Media 

Assessment of Reactive Iron Particle Delivery 

Approaches for Treatment of DNAPL Source Zones 

ITRC’s Technical and Regulatory Guidance for 

Bioremediation of Chlorinated Ethene DNAPLs 

Case Study: Use of Refrigerated Condensation for SVE 

Off-Gas Treatment Remediation for Contaminated 

Sediments 

53 G-110 

54 G-111 

55 G-112 

56 G-113 

57 G-114 

58 G-115 

59 G-116 

60 G-117 

61 G-118 

62 G-119 

78 G-120 

79 G-121 

80 G-122 

81 G-123 

82 G-124 

83 G-125 

84 G-126 

85 G-127 

86 G-128 


G-viii



PRESENTER 

ORGANIZATION 

Jack Parker 

University of Tennessee 

Dr. Mark l. Brusseau 

University of Arizona 

Ryan Ekre 

Arizona State University 

Dr. Richard Watts 

Washington State University 

Susanne Borchert, P.G. 

CH2M HILL, Inc. 

Dr. Robert Siegrist 


Dr. Myron Kuhlman 

MK Tech Solutions, Inc. 

Professor Donna Fennell 


Kimberly A. Wilson 

South Carolina Department of Health 

and Environmental Control 

Mark Widdowson 

Virginia Polytechnic Institute and 

State University 

Marc Deshusses 

University of California, Riverside 

and Duke University 

Thomas A. Krug 

Geosyntec Consultants, Inc. 

Ms. Sheri L. Knox, P.E. 

Solutions-IES, Inc. 

Eberhard Morgenroth 

University of Illinois at Urbana- 

Champaign 


Practical Cost-Optimization of Characterization and 

Remediation Decisions 

Impact of Source-Zone Architecture and Flow-Field 

Heterogeneity on Reductions in Mass-Flux 

Assessment of the Natural Attenuation of DNAPL 

Source Zones and Post-Treatment DNAPL Source Zone 

Residuals 

ER: Chlorinated Solvents — Dissolved Phase Remediation 

Treatability Study Results for the Peroxygen ISCO 

Demonstration/Validation at MCRS Cherry Point, SC 

Challenges with an ISCO Application in the Unsaturated 

Zone 

In Situ Chemical Oxidation for Groundwater 

Remediation: Responses to Project Managers— 

Frequently Asked Questions 

Simulation of Laboratory In Situ Thermal Desorption of 

DNAPLs 

Biological and Physical-Chemical Approaches for 

Degradation of 4-Chloroaniline and Aniline 

Decision Flowchart for the Use of Monitored Natural 

Attenuation and Enhanced Attenuation—Chlorinated 

Organics 

Verification of Methods for Assessing the Sustainability 

of Monitored Natural Attenuation 

ER: Perchlorate 

Laboratory Studies on Applications of Different 

Amendments for Perchlorate Degradation 

Semi-Passive Electron Donor Addition for Enhanced In 

Situ Bioremediation of Perchlorate-Impacted 

Groundwater 

A Tiered Approach for Evaluating Perchlorate Natural 

Attenuation 

Continuous and Sequencing Batch Operations of a 

Hydrogen Based Moving Bed Biofilm Reactor to 

Achieve Very Low Effluent Perchlorate Concentrations 

104 G-129 

105 G-130 

106 G-131 

27 G-132 

28 G-133 

29 G-134 

77 G-135 

101 G-136 

102 G-137 

103 G-138 

107 G-139 

108 G-140 

109 G-141 

110 G-142 

Paul Hatzinger, Ph.D. 


Determining the Origin of Perchlorate Using 

Stable Isotope Analysis 125 G-143 

Dr. Martina M. Ederer 


David Lippincott, P.G. 


Comparison of Genes Involved in Perchlorate 

Biodegradation 

Field-Scale Bioremediation of Perchlorate in 

Groundwater Utilizing an Active-Passive Treatment 

Approach 

126 G-144 

127 G-145 


G-ix



PRESENTER 

ORGANIZATION 

John Coates 

University of California, Berkeley 

Yuehe Lin 

Pacific Northwest National 

Laboratory 

Young-Soo Han 

The University of Michigan 

Andrew Henderson 

University of Michigan 

Dr. Mary F. DeFlaun 


Amy L. Hawkins 

NAVFAC ESC 

Afrachanna Butler 

U.S. Army Engineer Research and 

Development Center 

Dibakar Goswami 

Interstate Technology and Regulatory 

Council 

Yuehe Lin 

Pacific Northwest National 

Laboratory 

Karla Harre 

Naval Facilities Engineering Service 

Center 

Charles J. Newell, Ph.D., P.E., 

D.E.E. 

GSI Environmental, Inc. 

Robert Kelley 

Regenesis 

Dr. Smita Siddhanti 

EnDyna, Inc. 

Professor Mark N. Goltz 

Air Force Institute of Technology 

Dr. Bart Chadwick 


Dr. Stuart Strand 



Using Perchlorate Reductase from Dechloromonas 

Agitata Str CKB to Detect Perchlorate in the PPB Range 

Novel Electrochemical Process for Treatment of 

Perchlorate in Waste Water 

ER: Heavy Metals 

Impact of Dissolved Si on Uptake of As(III) by FeS- 

Coated Sand Under Anoxic Conditions 

Interaction of FeS and ZVI PRBs with Calcium, 

Carbonate, and Nitrate 

128 G-146 

129 G-147 

132 G-148 

133 G-149 

Field Demonstration of Arsenic Sequestration 134 G-150 

Soil Metal Bioavailability Adjustment 135 G-151 

Effectiveness of Grasses to Stabilize Metal Transport 

from Small Arm Target Berms 

Attenuation Processes for Metals and Radionuclides: A 

Survey of State and Federal Regulators and Stakeholders 

ER: Site Characterization, Monitoring, and Process Optimization 

Nanoparticles-Based Immunosensors for Sensitive 

Detection of Explosives, PCB, and PAHs 

Adaptive Long-Term Monitoring at Environmental 

Restoration Sites 

136 G-152 

137 G-153 

130 G-154 

131 G-155 

Sustainability Tool for Environmental Remediation 138 G-156 

Geophysical Imaging for Investigating the Delivery and 

Distribution of Amendments in the Heterogeneous 

Subsurface of the F.E. Warren AFB 

Adaptive Risk Assessment Modeling System: 

Evaluation and Tech Transfer 

An Evaluation and Implementation Guide for 

Groundwater Contaminant Mass Flux Measurement 

Methods 

Integrated Compliance Model for Predicting Water 

Quality Standards for Copper Compliance in DoD 

Harbors – Complementing a Fate and Effects Model with 

a Biotic Ligand Model for Seawater 

ER: Energetics 

The Genes for Bacterial Degradation of RDX Are on a 

Plasmid 

139 G-157 

140 G-158 

141 G-159 

166 G-160 

142 G-161 


G-x



PRESENTER 

ORGANIZATION 

Laura B. Brentner 

The University of Iowa 

Neil C. Bruce 

University of York 

Andy Martin 

USACE-ERDC 

Dr. Mark E. Fuller 


Dr. Roger Babcock, Jr. 

University of Hawaii 

Ghalib K. Bardai, MSC. 

McGill University 

Sylvie Rocheleau 

Biotechnology Research Institute 

Geoffrey I. Sunahara, Ph.D. 


Dr. Roman Kuperman 

U.S. Army Edgewood Chemical 

Biological Center 

Alan D. Hewitt 

U.S. Army ERDC-CRREL 

Elly P.H. Best 

U.S. Army Engineer Research and 

Development Center, Environmental 

Laboratory 

Dr. Baohua Gu 


Dr. Brandy J. White 

Naval Research Laboratory 

Sonia Thiboutot 

Defence Research and Development - 

Valcartier 

Dr. Sylvie Brochu 

Defence Research and Development 

Canada - Valcartier 

Dr. Mark S. Johnson 

U.S. Army Center for Health 

Promotion and Preventive Medicine 


U.S. Navy-SPAWAR-SSC 


U.S. Navy-SPAWAR-SSC 


Feasibility of Using Forage Grasses for the Containment 

of 2,4,6-Trinitrotoluene and 1,3,5-Trinitro-1,3,5- 

Triazacyclohexane at Eglin Air Force Base, Florida 

Engineering Transgenic Grasses for In Situ Treatment of 

RDX and TNT 

Open Burn/Open Detonation (OB/OD) Management 

Using Lime for Explosives Transformation 

Reducing Transport of Energetic Compounds at Live Fire 

Ranges 

Bioremediation and Phytoremediation of RDX and HMX 

in Tropical Soils 

Use of the Japanese Quail Embryo to Study the 

Developmental Toxicity of Nitroglycerin (NG) 

Toxicity of Nitroglycerin and Selected 

Aminodinitrotoluenes to Terrestrial Plants 

Assessing the Bioaccumulation Potential of RDX and 

HMX in Soil Invertebrates and Plants 

Toxicity of Nitroglycerin and Aminodinitrotoluenes to 

Potworm Enchytraeus Crypticus in a Sandy Loam Soil 

Implementation Status of Multi-Increment Sampling and 

Method 8330B 

Capacities of Candidate Herbaceous Plants for 

Phytoremediation of Soil-Based TNT and RDX on 

Ranges 

Development of a Portable Fiberoptic Surface Enhanced 

Raman Sensor 

Imprinted Nanoporous Organosilicas for Selective 

Adsorption of Nitroenergetic Targets 

Deposition of Nitroglycerine from the Live Firing of 

M72 A5 66-mm Rockets 

Assessment of Gaseous and Particulate Propellant 

Residues Resulting from Small Arms Live Firing 

Development of Toxicity Data for Munition 

Compounds to Support Toxicity Reference 

Value Derivations for Wildlife 

ER: Sediments 

Review of Enhanced Monitored Natural Recovery at 

Contaminated Sediment Sites 

Monitoring Plan Design for Validation of Enhanced 

Monitored Natural Recovery of Contaminated Sediment 

143 G-162 

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161 G-164 

162 G-165 

163 G-166 

164 G-167 

165 G-168 

168 G-169 

169 G-170 

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177 G-172 

178 G-173 

179 G-174 

184 G-175 

185 G-176 

186 G-177 

167 G-178 

180 G-179 


G-xi



PRESENTER 

ORGANIZATION 

Dr. Victor Magar 

ENVIRON International Corporation 

Philip Gschwend 

Massachusetts Institute of Technology 

Jim Leather 

Navy Spawar Systems Center 

Dr. Y. Meriah Arias-Thode 

SPAWAR Systems Center, Pacific 

Nicholas Fisher 

Marine Sciences Research Center 

Dr. Danny Reible 

University of Texas 

Dr. G. Allen Burton 


Dr. David Nakles 

ENSR 

Upal Ghosh 

University of Maryland Baltimore 

County 

Professor Max Haggblom 


Dr. Valdis Krumins 


Joong-Wook Park 


Dr. Celia Chen 

Dartmouth College 

Dr. Richard G. Luthy 

Stanford University 

Joel Baker 

University of Washington, Tacoma 

Dr. Anna S. Knox 

Savannah River National Laboratory 

Dr. Anna S. Knox 


Hui Liu 



Guidance for Monitored Natural Recovery at 

Contaminated Sediment Sites 

Using Performance Reference Compounds to Calibrate 

Polyethylene Passive Samplers for Measuring Mixtures 

of Hydrophobic Organic Compounds (HOCs) in 

Sediment Porewaters 

Integrated Forensics Approach to Fingerprint PCB 

Sources Using Rapid Screening Characterization and 

Advanced Chemical Fingerprinting 

181 G-180 

182 G-181 

183 G-182 

Benthic Community Response to Sediment Amendments 196 G-183 

Geochemical and Physiological Influences on Metal 

Accumulation in Deposit-Feeding Polychaetes 

Assessing Bioavailability and Bioaccumulation with 

Field Deployable SPME 

In Situ-Based Monitoring Approach for Improved Risk 

Assessment of Contaminated Sediments 

The Determination of Sediment Polycyclic Aromatic 

Hydrocarbon (PAH) Bioavailability Using Direct Pore 

Water Analysis by Solid-Phase Microextraction (SPME) 

Evaluation of Multifunctional Amendments for 

Simultaneous Bioavailability Reduction of PCBs and 

Heavy Metals in Sediment 

Quantifying Enhanced Microbial Dehalogenation 

Impacting the Fate and Transport of Organohalide 

Mixtures in Contaminated Sediments 

Sustained Enhancement of Dechlorinator Populations and 

Reductive Dechlorination Activity in PCB- and 

Chlorinated Pesticide-Contaminated Sediment 

Molecular Phylogenetic Analysis of Anaerobic 

Dechlorination of Polychlorinated Compounds 

Mercury Bioaccumulation and Trophic Transfer in 

Resident Estuarine Food Webs 

Measurement and Modeling of Ecosystem Risk and 

Recovery for In Situ Treatment of Contaminated 

Sediments 

Application of Tools to Measure PCB Microbial 

Dechlorination and Flux into Water During In-Situ 

Treatment of Sediments 

Methods for Evaluating the Life Span of Biopolymers 

Used for Contaminant Sequestration and Erosion Control 

Active Caps for Remediation of Sediment Contaminants 

and Resistance to Erosion 

Developing Methods to Stimulate Dechlorination of 

Historical Polychlorinated Dibenzo-p-Dioxins and 

Dibenzofurans in Contaminated Sediment 

197 G-184 

198 G-185 

199 G-186 

200 G-187 

201 G-188 

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203 G-190 

204 G-191 

205 G-192 

213 G-193 

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217 G-197 


G-xii



PRESENTER 

ORGANIZATION 

Amanda Hughes 


Yan Xu 


Dr. Jeanne M. Vanbriesen 


Kevin Gardner 

University of New Hampshire 

Gregory A. Tracey, Ph.D. 

SAIC, Inc. 

Amy L. Hawkins 

NAVFAC ESC 

Dr. Patrick Mclaren 

Geosea Consulting 

Dr. Joseph Gailani 

USACE ERDC-CHL 


Dechlorination Pattern Augmentation and Bayesian 

Modeling of Polychlorinated Biphenyl (PCB) 

Dechlorination in Sediment 

Bacterial Communities Analysis with Q-PCR in PCB- 

Contaminated Sediment Core 

Congener Tracker-Pair Analysis for Evaluation of 

Reductive Dechlorination of Polychlorinated Biphenyls 

(PCBs) in River Sediments 

Evaluation of Sorbents and Geotextile Materials for 

Reactive Capping of Contaminated Sediments 

Reactive Capping Mat Development and Evaluation for 

Sequestering Contaminants in Sediment 

218 G-198 

219 G-199 

220 G-200 

221 G-201 

222 G-202 

In Situ Wetland Remediation Demonstration 223 G-203 

Sediment and Contaminant Transport Associated with 

the Lac Saint Pierre Experimental Firing Range 

Develop Accurate Methods for Characterizing and 

Quantifying Cohesive Sediment Erosion Under 

Combined Current-Wave Conditions 

224 G-204 

225 G-205 

Dr. Richard G. Luthy 

Field Testing of Activated Carbon Mixing and In Situ 

226 G-206 


Stabilization of PCBs in Sediment 

ER: Chlorinated Solvents — Site Characterization, Monitoring, and Processing 

Matt Shurtliff, CHMM 

Non-Invasive Plume Delineation Using Tree Coring Recently 

G-207 

The Forrester Group Inc. 

Analysis 

Added 


G-xiii


Poster Number 21 – Wednesday 

Ground Based Detection and Discrimination — EMI & Magnetometers / Modeling & Processing 

A 

EVALUATION OF ELECTROMAGNETIC INDUCTION 

SENSOR NOISE SOURCES 

BRUCE BARROW 

SAIC, Inc. 

1225 South Clark Street, Suite 800 

Arlington, VA 22202 

(703) 413-0500 

bruce.j.barrow@saic.com 

CO-PERFORMERS: Jonathan Miller (SAIC, Inc.); Dan Steinhurst (Nova Research) 

number of controlled measurements were taken with standard electromagnetic induction 

sensors (EM61 MkII and GEM-3) to evaluate the sources of noise that limit the detection 

and inversion of UXO signals. The noise sources considered were: external, inherent, motion 

related, and location errors. The largest source of noise was determined to be motion related. 

This noise source had two separate causes: noise generated as the receive coil changes its 

orientation in the earth’s field and noise generated as the coil changes height and orientation 

relative to the ground. Both sources have been physically modeled and given the sensor’s motion 

can be predicted. The second limiting factor was location error. Even with high quality GPS 

positioning, other factors such as timing and the lever arm from the GPS antenna to the sensor 

were found to be major sources of error. The results from all of these sources were used to 

develop a Monte Carlo simulation of an EM61 mounted on a typical cart. Model based signals 

were embedded in realistic levels of noise and inverted. The resulting spread in fitted parameters 

was consistent with what is observed from field data. Given the general characteristics of 

platform motion and soil properties at a particular site, the simulation can be used to predict both 

detection and discrimination performance. 

This project has been supported under ESTCP MM-0508. 

G-1




U 

SELECTING OPTIMAL MODELS FOR INVERTING EMI DATA 

DR. LEONARD PASION 


2386 East Mall, Suite 112A 

Vancouver, BC V6T1Z3 CANADA 

(541) 552-5186 

len.pasion@skyresearch.com 

CO-PERFORMER: Dr. Douglas Oldenburg (UBC-GIF) 

XO discrimination is achieved by extracting parameters from geophysical data that reflect 

characteristics of the target that generated the measured signal. Model-based parameters are 

estimated through data inversion, where the optimal parameters are those that produce acceptable 

agreement between observed and predicted data and satisfy any prior information we have about 

the target. These parameters are then used as inputs to statistical classification methods to 

determine the likelihood that the target is, or is not, a UXO. 

In recent years, various parametric modeling methods have been advocated for simulating Time 

Domain Electromagnetic (TEM) data from UXO and clutter. These physics-based 

representations include surfaces of magnetic charges and decaying electromagnetic dipoles. 

When using a dipole model, targets with cylindrical symmetry can be effectively modeled using 

2 polarizations and geometrically more complex items require 3 polarizations. In addition, a 

decision must be made on how to parameterize the time decay (or frequency responses) of the 

polarizations. If two or more targets are close together then they may need to be modeled as 

multiple objects using a 2- or 3-polarization representation. Therefore, the model-based methods 

for TEM data processing require not only the estimation of a vector of real-valued parameters 

but also the selection or evaluation of one forward model over another. 

The goal of this research is to delineate the circumstances for which a particular type of 

modeling should be chosen, and to generate methodologies and software that would allow the 

user to more efficiently extract meaningful parameters from the data and thus improve 

discrimination. In this presentation we will summarize preliminary results when comparing the 

effectiveness of different forward models of the TEM response. We will present preliminary 

results from comparing a single dipole representation to multiple dipoles or charges. We will 

present techniques for processing overlapping targets. If an EMI anomaly is deemed to represent 

a pair of targets, we will determine the best model, either: (a) Simultaneous inversion of a pair 

of dipole models using all the available data, or (b) segmenting the data into two regions with a 

dipole model fit to each segmented region. We will also compare parameter estimation and 

library-based methods of discrimination. 

This project has been funded under SERDP MM-1637. 

G-2




T 

SIMULTANEOUS INVERSION OF UXO PARAMETERS 

AND BACKGROUND RESPONSE 

DR. LEONARD PASION 




(541) 552-5186 

len.pasion@skyresearch.com 

CO-PERFORMER: Dr. Douglas Oldenburg (UBC-GIF) 

he task of discriminating UXO from non-UXO items is more difficult when sensor data are 

collected at sites where an electromagnetically active host contributes a large signal. In 

general, approaches to UXO discrimination assume that the object of interest is in free-space. 

Any influence of the background medium is assumed to have been removed by filtering the data. 

Spatial variations of the background signal can be the same size as UXO anomalies. These signal 

variations can result from small scale topography (due to bumps or dips in the surface), changes 

in the orientation and height of the sensor relative to the ground, and spatial variations in the 

electromagnetic properties of the soil (i.e., conductivity and magnetic susceptibility). A high pass 

filter to remove the geologic signal is often unable to remove smaller scale spatial variations. In 

addition, this filtering step can introduce artifacts that can bias estimates of the target parameters. 

In SERDP project MM-1573, we are developing an approach to processing data collected at sites 

with magnetic geology. Instead of relying on filtering to remove the background response, we 

use instrument position and orientation information to model the sensor response due to soils. 

Computational routines and techniques to simultaneously invert for the parameters of the buried 

object and the response of the background have been developed. For magnetic data, we will 

study the effectiveness of an equivalent layer for modeling the geologic response. An equivalent 

layer is a fictitious distribution of dipolar sources that lie at or below the observation surface and 

which can potentially reproduce any magnetic field. We simultaneously invert for the equivalent 

layer and the dipolar parameters of any embedded metallic objects. For electromagnetic data, we 

simultaneously invert for geologic properties of the background response in addition to the 

target’s dipole parameters. The response of the magnetic geology is calculated by using an 

approximate multi-dipole representation of the transmitter. We present results of processing both 

simulated and field data for the Geonics EM63 time domain electromagnetic sensor and the 

newly developed Man Portable Vector time domain electromagnetic sensor. Finally, to quantify 

the effect of topography on the EMI signal we use numerical modeling of Maxwell’s equations. 

We will present initial results comparing measured and modeled data for different sized bumps 

and trenches. 

G-3




ADVANCED EMI MODELS APPLIED TO NEXT-GENERATION EMI SENSORS: 

DATA PROCESSING AND UXO DISCRIMINATION STUDIES 

FRIDON SHUBITIDZE 


445 Dead Indian Memorial Road 

Ashland, OR 97520 

(541) 552-5160 

fridon.shubitidze@skyresearch.com 

CO-PERFORMERS: Benjamin Barrowes (USACE ERDC Cold Regions Research and 

Engineering Laboratory); Irma Shamatava (Sky Research, Inc.); Kevin O’Neill (Thayer School 

of Engineering, Dartmouth College) 

R 

ecently, next generation, relatively sophisticated, ultra wideband EMI sensors with novel 

waveforms, multi-axis or vector receivers, have been developed operating either in the time 

domain or in the frequency domain. Among these emerging technologies are: (a) NRL timedomain 

EMI sensor array. The system consists of 25 transmit/receive pairs arranged in a 5 x5 

grid, each with a 35-cm diameter transmitter loop and a 25-cm receiver loop. The sensor 

activates the transmitter loops in sequence, one at a time, and for each transmitter all receivers 

receive, measuring the complete transient response over a wide dynamic range of time ranging 

approximately from 100 µs to 25 ms and distributed in 123 time gates. The sensor thus provides 

625 spatial data points at each location, with unprecedented positional accuracy and (b) the new 

man portable vector time-domain (MPV TD) sensor which has five tri-axial cubic receivers 

located around two 75-cm diameter transmitter coils. The positions of the transmitter coils are 

determined using a laser positioning system, and (c) Berkley UXO Discriminator (BUD) system 

that has multiple transmitters and/or multiple receiver coils. The combination of spatial diversity 

in the measurements, with full vector definition of signals from a variety of observation points 

over an extremely wide time range, offers unprecedented data quality for discriminationprocessing 

algorithms. To take advantage of the data diversity that this instrument provides, 

(1) an advanced, physically complete EMI forward model, such as the normalized surface 

magnetic source models (NSMS), (2) a data inversion scheme, that uses the newly developed 

HAP method to estimate the location and orientation of the target, and (3) a discrimination 

processing approach based on the statistical signal processing algorithm, have been adapted to 

the new generation EMI sensors data. In this work the applicability of the NSMS algorithm is 

demonstrated by comparing the modeled data against to the EMI data that these sensors provide. 

The different sets of EMI data are inverted and the total NSMS are calculated. Finally, based on 

the estimated the total NSMS for each target, a statistical classification tool is developed that 

provides accurate UXO discrimination. 

This project has been supported under SERDP MM-1572. 

G-4




A 

DEMONSTRATION OF DIGITAL GEOPHYSICS ON ACTUAL UXO SITES 

LAWRENCE CARIN 

Signal Innovations Group, Inc. 

1009 Slater Road 

Suite 200 

Durham, NC 27703 

(919) 475-2151 

lcarin@siginnovations.com 

CO-PERFORMERS: Levi Kennedy and Xiangyang Zhu (Signal Innovations Group, Inc.) 

dvanced digital geophysics technology are being demonstrated on actual UXO sites. In this 

poster we will report on the underlying technology, and show results for the Sibert study, as 

well as preparation for the San Luis Obispo study. The technology is based on advanced 

techniques from machine learning and statistics. For example, information-theoretic measures 

are employed to define the expected information content one may accrue by excavating an item 

for the purpose of learning its label. This is termed active learning, and it is characterized by two 

excavation stages. In the first, it is assumed that no labeled (training) data exists, and excavation 

is performed with the purpose of learning labels on most-informative signatures. Here “most 

informative” means that these labels, if acquired, will most reduce uncertainty in a classifier 

design. This first phase of excavation continues until the algorithm indicates no more 

information will be accrued by further excavation. Then, using the labeled data acquired in the 

first phase, a classifier is designed, from which a prioritized dig list is specified for the second 

(more traditional) excavation phase, which has the purpose of excavating all UXO and leaving 

non-UXO items behind. We examine this process in both a supervised and semi-supervised 

setting. 


G-5




M 

MAN-PORTABLE VECTOR TIME DOMAIN EMI SENSOR AND 

DISCRIMINATION PROCESSING 

DR. BEN BARROWES 

ERDC-CRREL 

72 Lyme Road 

Hanover, NH 03768 

(603) 646-4822 

benjamin.e.barrowes@usace.army.mil 

CO-PERFORMERS: Dr. Kevin O’Neill (ERDC-CRREL); Dr. Fridon Shubitidze, 

Dr. Pablo Fernandez, and Ms. Irma Shamatava (Dartmouth College) 

etallic clutter contaminates most if not all UXO remediation sites and presents a difficult 

impediment to the accurate detection and discrimination of UXO. We investigated a 

physics based clutter suppression algorithm based on upward continuation to process 

magnetometer or electromagnetic induction (EMI) sensor data so that UXO discrimination 

processing UXO can be enhanced. Our approach is directly tied to the fact that it relies on the 

governing physics and not on signal processing stratagems divorced from that physics or 

idealizing it unduly. We used a plane of equivalent sources to reproduce the entire EMI response 

from target combinations and then used these sources to calculate the magnetic field above the 

actual measurement region. We show that the response from smaller, often shallower clutter 

decreases more rapidly than the response from larger items, thus minimizing the contribution of 

clutter and from noise. In this way, we are able to partially isolate the contribution of the larger 

target on the EMI response. Coverage, equivalence, and noise tolerance issues are investigated. 

We acquired bistatic EMI data over emplaced target/clutter combinations from the GAP 

Geophysics survey system at Aberdeen Proving Grounds. A 155mm projectile was emplaced 

surrounded by various arrangements of substantial clutter items. Preliminary analysis of this data 

indicates that upward continuation is a viable technique for the suppression of clutter responses 

from the overall EMI signal. Even when a clutter signal more than twice the strength of the UXO 

signal was embedded directly in the target’s response, the method succeeded in calculating 

largely uncluttered data for higher sensor elevations. We plan to adapt this method to monostatic 

data as acquired by most current sensors. 


G-6




HIGH FIDELITY ELECTROMAGNETIC INDUCTION INSTRUMENTS AND 

PHYSICALLY COMPLETE MODELS 

DR. BEN BARROWES 

ERDC-CRREL 

72 Lyme Road 


(603) 646-4822 

benjamin.e.barrowes@usace.army.mil 

CO-PERFORMERS: Dr. Kevin O’Neill (ERDC-CRREL); Dr. Fridon Shubitidze, Dr. Pablo 

Fernandez, and Ms. Irma Shamatava (Dartmouth College) 

W 

e have developed two advanced, man portable EMI instruments in both the frequency and 

time domains intended for queued interrogation of anomalies. The Man Portable Vector 

(MPV) time domain EMI instrument (MM-1443) has a single 75 cm diameter primary coil and 

five triaxial cubic receivers that measure the secondary vector magnetic field. Initial testing of 

the MPV instrument is complete, and we have an extensive data sets collected at the ERDC 

teststand, at CRREL, and at Ashland Oregon with Sky Research. Data were collected in both 

static mode (MPV stationary) and dynamic mode (MPV moving). We have adapted our 

physically complete high fidelity models, the SEA and the NSMC models, to the MPV. The 

ArcSecond system provides subcentimeter geolocationing for the MPV. With its high SNR, high 

fidelity, high diversity data acquisition capabilities, the MPV provides quality data for UXO 

discrimination models. 

The GEM 3 D + (MM-1537) is a frequency domain EMI instrument adapted from a GEM 3 from 

Geophex. Transverse receivers were added to the GEM 3 to provide the capability of measuring 

a vector magnetic field in the frequency domain. Acquiring the transverse components of the 

magnetic field offers several advantages including data diversity and partial immunity to 

geological noise. The GEM 3 D + also incorporates an advanced geolocationing system. This 

positioning system is based on using the instruments own primary field to locate and orient the 

primary coil of the instrument. This “beacon” positioning system has an accuracy on the order of 

a centimeter when the instrument is within the 3 m of the positioning receiver coils. We have 

adapted our physically complete SEA and NSMC models to the GEM 3 D + and will present 

inversion results from both statically and dynamically acquired data. 

G-7




T 

INCREASING THE UNDERSTANDING AND USEFULNESS OF MACHINE 

LEARNED MEC DISCRIMINATION RESULTS USING EVOLUTIONARY 

STRATEGY TOOLS FOR KNOWLEDGE DISCOVERY 

LARRY DESCHAINE 

SAIC, Inc. 

35 Varden Drive, Suite F 

Aiken, SC 29803 

(706) 951-2750 

Larry.m.deschaine@saic.com 

CO-PERFORMERS: Frank D. Francone, Dean A. Keiswetter, Thomas R. Battenhouse, Jr., 

Melissa C. McKay, Robert T. Weatherly, and Stanley K. Wong (SAIC, Inc.) 

he objective of our work is to continually improve the accuracy, reliability and 

understandability of MEC discrimination algorithms and approaches. Since 2001, SAIC, 

RMLT & Chalmers University of Technology have researched and developed a suite of tools 

now known MecFinder and LGP Discrimination. The tool kit is currently being validated in the 

ESTCP program under project MM-0811. The approach consists of a synergistic blend of MEC 

discrimination physics with techniques from statistics, information theory, signal processing, 

topology, medical imagery analysis and machine learning. During the development, the tool set 

has been successfully tested on data from JPG-IV, JPG-V and the FE Warren AFB. As part of 

MM-0811, the tool is being tested using data from Camp Sibert. Discoveries during the work 

have been demonstrating the advanced power of machine learning tools; specifically, the linear 

genetic programming (LGP) paradigm used as the core machine learning engine. The LGP is 

able to uncover and auto-derive recognizable and known physics equations from data. Other 

discoveries demonstrate the LGP is able to extend physics based equations to include 

information in data sets not yet leveraged by the general physics equations. This accuracy leads 

to improved discrimination and stop-digging decisions using principled and understandable 

approaches. These findings are illustrated using clear examples, as are the results to date on the 

ESTCP MM-0811. Next steps for knowledge discovery in understanding robust MEC 

discrimination is discussed. 

G-8




STATISTICAL SIGNAL PROCESSING FOR UXO DISCRIMINATION FOR 

NEXT-GENERATION SENSOR DATA 

DR. LESLIE M. COLLINS 


ECE Department 

Room 130 Hudson Hall, Box 90291 

Durham, NC 27708-0291 

(919) 660-5260 

lcollins@ee.duke.edu 

CO-PERFORMERS: Dr. Stacy Tantum, Dr. Chandra Throckmorton, Dr. Jeremiah Remus, and 

Dr. Lawrence Carin (Duke University); Dr. David Wright (USGS); 

Dr. Erika Gasperikova (LBL) 

U 

ntil recently, detection algorithms could not reliably distinguish between buried UXO and 

clutter, leading to many false alarms. Over the last several years modern geophysical 

techniques have been developed that merge more sophisticated sensors, underlying physical 

models, and statistical signal processing algorithms. These new approaches have dramatically 

reduced false alarm rates, although for the most part they have been applied to data collected at 

sites with relatively benign topology. To address these problems, SERDP and ESTCP have been 

supporting efforts to develop a new generation of UXO sensors that will produce data streams of 

multi-axis vector or gradiometric measurements. The focus of the research that we will present 

here is on development of new physics-based signal processing approaches applicable to the 

problem in which vector data is available from such sensors. 

Specifically, we will present modeling and processing results obtained using state of the art 

multi-axis sensors developed by LBL and USGS. First, we demonstrate that utilization of the 

phenomenological models developed during this program for data inversion results in improved 

discrimination performance over inversion strategies that use simplified models. We also 

consider the impact of relaxing the assumption of a symmetric object in the inversion process, 

and demonstrate improved classification results. We carefully consider options for the inversion 

process, and demonstrate that careful data selection can impact performance quite significantly. 

In addition, we also report on new classifier work. Results are presented for test stand data from 

the ALLTEM system and Camp Sibert data for the BUD system. Both calibration and blind 

results are presented for the BUD system. 

This research was supported by the Strategic Environmental Research and Development 

Program (SERDP) under Project MM-1442. 

G-9



Ground-Based Detection and Discrimination — EMI & Magnetometers / Modeling & Processing 

T 

POSITION-INDEPENDENT PROCESSING OF ELECTROMAGNETIC 

INDUCTION DATA FOR TARGET CLASSIFICATION 

THOMAS BELL 

SAIC, Inc. 

1225 S. Clark Street, Suite 800 

Arlington, VA 22202 

(703) 413-0500 

bellth@saic.com 

raditional approaches to target classification and discrimination using electromagnetic 

induction (EMI) data are based on principal axis polarizabilities calculated by inverting 

spatially mapped EMI data collected over the target. The inversion process is very sensitive to 

errors in the data and is especially sensitive to errors in the relative locations of the sensor 

readings. Using simple parametric representations for the EMI signals, we demonstrate that the 

EMI responses of typical UXO and clutter items follow distinctive trajectories in parameter 

space as the sensor is moved about over the item. These characteristic trajectories can be used for 

target classification and discrimination. We also find that by exploiting this characteristic 

behavior, the shapes of the principal axis polarizability curves can be calculated directly from the 

EMI data without using any sensor location information. We demonstrate that satisfactory 

representations of the principal axis responses can be obtained using only a half-dozen or so 

good measurements of the EMI signal over the target. 


G-10




T 

DISCRIMINATION PERFORMANCES OF COMMERCIAL SENSORS AT APG 

AND YPG 

DR. DEAN KEISWETTER 

SAIC, Inc. 

120 Quade Drive 

Cary, NC 27513 

(919) 454-3212 

keiswetterd@saic.com 

CO-PERFORMERS: Mr. Levi Kennedy (Signal Innovations Group, Inc.); 

Dr. Leslie Colins (Duke University) 

he objective of SERDP Project MM-1505 is to determine the level to which data acquired at 

Aberdeen Proving Ground and Yuma Proving Ground using commercial electromagnetic 

induction and magnetic sensors support feature-based discrimination decisions. As part of this 

study, we are evaluating discrimination performances for various models, classifiers, and training 

data. Three fundamental issues are being investigated: namely, the model used during 

characterization and the impact that classifier selection and training has on performance. The 

UXO Standardized Test Sites in Aberdeen Maryland and Yuma Arizona represent real world 

scenarios. They are rich in data, ground truth, near-surface conditions, and target diversity. 

Because of this, they present an unprecedented opportunity to systematically examine the 

importance of models, classifiers, and training data. The near-surface conditions vary and the 

buried targets of interest range from 20mm projectiles to 500 lb bombs. 

We selected five data sets based on data quality, type, signal-to-noise, and availability at 

appropriate intermediate processing stages. The datasets include time-domain EM61 (man-towed 

single sensor and vehicle-towed array), time-domain EM63, frequency-domain GEM-3 (vehicle 

towed array), and magnetic data (array). The models being investigated include a standard dipole 

(expressed using polarizabilities, an ellipsoidal representation, and empirical fits), joint 

frequency-time domain, and singular expansion models. The classifiers being investigated 

include: the Generalized Likelihood Ratio Test, Support Vector Machines, Relevance Vector 

Machine, and K-nearest neighbor. Various levels of training data are being extracted using 

ground truth labels from the calibration, blind grid, and portions of the open field areas. 

Results of our analysis indicate that the nominal dipole fit error is in excess of 20%. This 

combined with the facts that (i) the TOI range from 20mm projectiles to 500 lb bombs and 

(ii) the non-TOI target is typically medium to large in size and thick walled, significantly limited 

discrimination performances. If we assume that the objective is to discriminate all UXO from all 

non-UXO at these sites, very little if any discrimination capability is observed. If we restrict the 

TOI class to specific sizes of UXO, however, such as small, medium, or large UXO which is 

often the case for live sites, performance improves significantly. 

G-11




S 

SHOCK DEMAGNETIZATION OF PROJECTILES ON IMPACT 

WITH THE GROUND 

DR. STEPHEN BILLINGS 




(541) 552-5185 

stephen.billings@skyresearch.com 

ERDP Project MM-1380 is focused on understanding the physical basis behind changes in a 

UXO or shrapnel’s remanent magnetization when it is subjected to shock. If rounds are 

shock-demagnetized on impact, one can develop a very promising discrimination method with 

magnetic data based on estimating an item’s remanent magnetization. The remanence magnetic 

discrimination method developed at the University of British Columbia/Sky Research has proven 

successful at sites in Montana, resulting in false-alarm rates between 1 and 5 non-UXO for each 

excavated UXO item. In the magnetic remanence method, the amount of remanent magnetization 

in recovered dipole moments of collected magnetic data is estimated and a prioritized dig-list is 

developed based on the assumption that items with lower remanence are more likely to be UXO. 

We describe a field deployment at Aberdeen Test Center where we measured the remanent 

magnetization before and after firing sixty-five 81 mm mortars. The tests were conducted over a 

9 day period in late May/ early June. During the first days on site we measured the initial 

remanent magnetization and found that only one of the sixty-five mortars had significant 

remanence (comparable to the induced magnetization). Fortunately, the Non-Destructive- 

Evaluation equipment at ATC was readily able to impose a remanent magnetization on the 81 

mm mortars. We left some mortars in a demagnetized state and imposed medium and large 

remanences on either the axial or transverse axes of the remaining items. The remanence was 

again measured just prior to firing. We fired one third with no charge increment (low velocity of 

impact, the mortars were sticking out of the ground), one third with one charge increment 

(mortars buried to 2 feet depth) and the one-third with two charge increments (mortars buried to 

5 to 8 feet depth). The rounds were carefully excavated (except the two-charge increment 

mortars where we had to use an excavator), and their depth and orientation was recorded before 

the remanence was again measured. 

The data were then processed and analyzed. Shock demagnetization definitely occurred, but for 

the charge 0 and 1 mortars, there was still a significant amount of residual magnetization. This 

means that we can't rely on shock demagnetization if impact velocities are low. What was 

particularly interesting was that rounds that had very low remanent magnetization before firing 

actually had a larger remanence after firing and impact. The shock of impact erases some of the 

existing magnetization but allows a new magnetic remanence to be established in the direction of 

the ambient magnetic field. 

In the abstract we also describe our efforts to develop a quantitative model of the effect of stress 

on the magnetization of an impacting ordnance item. 

G-12




ROBUST STATISTICS FOR UXO DISCRIMINATION 





(541) 552-5185 


CO-PERFORMERS: Laurens Beran and Douglas Oldenburg (University of British Columbia) 

T 

he objective of SERDP MM-1629 is to provide more statistically rigorous solutions to the 

inversion problems that occur as integral parts of any UXO discrimination scheme. 

Experience from demonstration projects has shown that inversion of TEM data with low SNR is 

susceptible to outlying data, so that the global minimum of the misfit does not provide a model 

which can be reliably used for discrimination. This problem can be addressed by using a misfit 

function which is less sensitive to outliers, or by iteratively updating data uncertainties so that 

data which cannot be fit are downweighted during inversion. In the former approach, L1 type 

norms replace the conventional L2 misfit. This introduces additional nonlinearity to the inverse 

problem, and the resulting algorithm in fact requires iterative reweighting of data uncertainties. 

Hence robust norms can be regarded as equivalent to iterative update of an L2 norm. We have 

investigated the latter approach by developing a formal Bayesian technique to updating data 

uncertainties. Application to real data reduced the effect of outliers on the inversion process, and 

resulted in improved parameter estimates. 

Discrimination requires estimation of features which provide information regarding target size, 

shape or composition. Inversion of TEM data extracts useful features which can then be used to 

make discrimination decisions. However, parameters estimated in the inversion process are not 

point estimates but have an associated uncertainty which is a function of the uncertainty in the 

data and the curvature of the misfit function at its minimum. For example, when the model 

parameters are well constrained (i.e., have a small uncertainty), the misfit function will have a 

high curvature at the final model. For a nonlinear inverse problem, the posterior distribution of 

the final model can then be approximated as a Gaussian distribution with covariance inversely 

proportional to the curvature of the misfit. To investigate the utility of including parameter 

uncertainty in discrimination, we have developed a “Gaussian product” classifier which uses 

feature vectors and their associated uncertainties to make discrimination decisions. The classifier 

discounts parameters that are highly uncertain from the discrimination process. For example, 

when applied to TEM data from Camp Sibert, we found that the decay of the primary 

polarization had a large uncertainty relative to the amplitude of the polarization. Consequently, 

the Gaussian product classifier made discrimination decisions based primarily upon the 

amplitude of the polarization. 

G-13




T 

DISCRIMINATION AT A CHALLENGING SITE 





(541) 552-5185 


CO-PERFORMERS: Kevin Kingdon and Len Pasion (Sky Research, Inc.); 

Laurens Beran and Douglas Oldenburg (University of British Columbia) 

he ESTCP Project MM-0504 “Practical Discrimination Strategies for Application to Live 

Sites” addresses the need to reduce false-alarm rates at UXO sites by improving access to 

advanced modeling and discrimination capabilities. Electromagnetic sensors are a promising 

technology for detecting UXO, but they tend to detect many other non-hazardous metallic items. 

Statistical and rule-based classification techniques for UXO discrimination, when calibrated with 

good training data, have been shown at numerous test sites to be effective. This project is 

developing the software and protocols required to apply advanced discrimination techniques to 

live sites. 

In April 2008, we deployed a Geonics EM63 in a cued-interrogation mode to a difficult wooded 

portion of Fort McClellan, Alabama. In total we collected data over 401 anomalies on the site, 16 

items in the GPO and 21 items in a test-pit (3 orientations for 7 ordnance items). We then 

processed the data (stacking, background removal, drift correction) and then fit polarizationtensor 

models to all anomalies. We are currently waiting for anomaly validation and release of 

that ground-truth information and will report on the full results in December. In the meantime we 

have done some initial comparisons of feature vectors from the GPO and test-pits with the clutter 

from Camp Sibert. We will most likely use the same features as at Camp Sibert: one related to 

the size and the other to the time-decay of the primary polarization. The ordnance with caliber > 

60 mm cluster in one part of that feature space (large size, slow time-decay), with the 37’s and 

60’s cluster in another region of feature space (smaller size, faster decay). Overlaying the 

unknown feature vectors reveals that there may be a large number of the larger caliber ordnance 

items but not many 37's and 60's. The MKII grenades may be difficult to discriminate, although 

we have found that a feature space that combines mid and late-time decays does result in a 

distinct clustering of the grenades. 

G-14



Ground Based Detection and Discrimination — EMI & Magnetometers / Sensors 

REFINEMENTS IN THE ALLTEM UXO DETECTION 

AND DISCRIMINATION SYSTEM 

TED ASCH 

U.S. Geological Survey 

Denver Federal Center 

Building 20, MS-964 

Denver, CO 80225 

(303) 236-2489 

tasch@usgs.gov 

CO-PERFORMERS: David Wright, Craig Moulton, and Trevor Irons (U.S. Geological Survey) 

A 

n advanced multi-axis electromagnetic induction system, ALLTEM, was specifically 

designed for detection and discrimination of unexploded ordnance (UXO) with funding 

from SERDP Project MM-1328. Refinement of the acquisition electronics, survey platform and 

system orientation, and interpretation and analysis software is continuing with funding from 

ESTCP Project MM-0809. ALLTEM uses a continuous triangle-wave excitation that measures 

the target step response rather than the more common impulse response. An advantage of using a 

triangle-wave excitation is that the responses of ferrous and non-ferrous metal objects have 

opposite polarities. The system multiplexes through all three orthogonal (H x , H y , and H z axes) 

transmitting loops and records a total of 19 different transmitting (Tx) and receiving (Rx) loop 

combinations. ALLTEM data acquisition is dynamic with a spatial data sampling interval of 15 

cm to 20 cm at a constant 100 kilosamples/s rate with 24-bit precision. Using an early-time pick 

of 275 μs, late enough that the step response of an analog low-pass filter has settled, amplitude 

difference data and maps are produced. These data are almost free of ground response and 

system drift effects while retaining good sensitivity to UXO. The improvement in the signal-tonoise 

ratio greatly enhances the ability to detect small or deep targets. The new ALLTEM 

platform is a cart made of composite fiberglass and plastic that will substantially reduce the 

weight of the cart. The electronics have been redesigned to be more compact and more energy 

and heat efficient. The Crown amplifier that has been the backbone of the system has been 

replaced with Class D amplifiers. This has resulted in an increased current output from +/- 8 

Amps to +/- 11 Amps with much less heat put off by the amplifier. The ALLTEM data analysis 

has now been incorporated into the Oasis Montage platform. This includes basic data processing, 

system noise analysis, automated target selection, orientation analysis, and calls to an inversion 

algorithm that has been developed and refined over the last year. The algorithm uses a physicsbased 

forward model and non-linear inversion. While GPS position errors and additional errors 

from cart roll, pitch, and yaw were often small enough that previous survey inversions still 

provided good estimates of target position, depth, and orientation, and reasonable and 

reproducible values for dipole moments of these targets, the addition of an AHRS unit should 

reduce some of these errors. A demonstration at the Yuma Proving Ground is scheduled for 

winter 2009. 

G-15




C 

HELICOPTER MAGNETOMETER PLATFORM BASED ON 

COMPACT INDUCTION SENSORS 

YONGMING ZHANG 

QUASAR Federal Systems, Inc. 

5754 Pacific Center Blvd., Suite 202 

San Diego, CA 92121 

(858) 200-2229 

yongming@quasarfs.com 

CO-PERFORMERS: Matt Steiger (QUASAR Federal Systems); 

Dave Wright (Sky Research, Inc.) 

ollaborating with Sky Research, a 6" long, 3-axis induction sensor was deployed on the 

helicopter platform with limited flight tests. The 3-axis main sensor was mounted in the 

center of the boom and a singal-axis reference sensor was mounted in the far right side of the 

boom. The three-axis induction sensor was operated in a passive mode on the moving platform 

flying at 10 to 20 meters per second at 2 meters above ground. The moving platform converts the 

DC magnetic signature from a UXO target into an AC signature with frequency components 

determined by the target size and orientation, as well as the speed and height of the moving 

platform. The measured noise floor during these flight tests was 500x higher than the sensor 

noise floor, approximately 10 nT/rtHz at 1 Hz. The post processed data gave an in-flight noise 

floor of approximately 3 nT/rtHz at 1 Hz and was able to achieve a signal to noise ratio of about 

13 for the largest target (100 lb bomb). Some cancellation of motion-induced noise was possible 

with data from the off axis sensor data in the 3-axis assembly. 

Post-flight experiments were carried out to compare a lash-up induction sensor gradiometer to 

the original induction sensor magnetometer. The gradiometer, aligned to the Earth’s field, 

showed a factor of 10x lower noise than the induction sensor. We conclude that a noise floor of 1 

nT/rtHz at 1 Hz is possible to achieve during flight. A more carefully constructed gradiometer 

would have a higher degree of coherence than the lash-up prototyp. A 3-axis gradiometer and a 

rotation sensor, would allow more cancellation of motion-induced noise. It is possible to achieve 

an in-flight noise floor of approximately 100 pT/rtHz at 1 Hz; a factor of 10 lower than the noise 

floor achieved with Cs-vapor magnetometers. 


G-16




TRI-AXIS FLUXGATE-INDUCTION SENSOR FOR ADVANCED TIME-DOMAIN 

UXO DETECTION AND DISCRIMINATION 

YONGMING ZHANG 

QUASAR Federal Systems, Inc. 

5754 Pacific Center Boulevard, Suite 202 


(858) 200-2229 

yongming@quasarfs.com 

CO-PERFORMERS: Matt Steiger and Dr. Andrew D. Hibbs (QUASAR Federal Systems); 

Dr. Robert Grimm (South West Research Institute) 

W 

e have developed a tri-axial dual-mode magnetic sensor that operates both as a fluxgate to 

sense DC magnetic fields and as an induction sensor to sense AC magnetic fields. The 

fluxgate shares the same magnetic core, sensing coil and preamplifier as the induction sensor. 

The result is a sensor system that is capable of collecting DC magnetic and AC electromagnetic 

data in a single sweep; reducing scanning time by 50% and eliminating the need for coregistration 

of multiple sensors. 

In this presentation, we will describe the development on the tri-axial dual mode fluxgateinduction 

sensor system. We will show the ability of using the dual-mode sensor to characterize 

target size, shape, and location for a standard 37 mm shell. The performance of the vertical axis 

of the sensor was compared to single axis commercial sensors (Geonics EM63 induction sensor, 

MEDA mMag001 fluxgate). The performance of the tri-axial QUASAR sensor was compared to 

that of the (single) vertical axis. The induction sensor data was analyzed with a three axis time 

domain dipole model. The fluxgate data is modeled as a single dipole. In the single axis 

comparison, the dual-mode sensor gave similar performance to the commercial sensors, in both 

induction sensor and fluxgate modes. Both the QUASAR induction sensor and EM63 were able 

to recover a quasi-cylindrical shape for a vertically aligned shell. The fluxgate data yielded the 

same target position, to within approximately 1 cm. The three axis induction sensor outperformed 

the single axis induction sensor in its ability to characterize target shape. The three 

axis sensor returns quasi-cylindrical shapes for both vertically and horizontally aligned shells. 

We will also discuss our recent results on the system trade study of the 3-axis dual mode sensor. 

The magnetic moment of the transmitter has been increased from 180 A-m 2 to 480 A-m 2 . Data 

for standard targets and “canonical objects” (i.e., disks, spheres, cylinders) will be presented. 


G-17




B 

ADVANCES IN UXO DISCRIMINATION 

DR. ERIKA GASPERIKOVA 

Lawrence Berkeley National Laboratory 

One Cyclotron Road 

MS:90R1116 

Berkeley, CA 94720 

(510) 486-4930 

egasperikova@lbl.gov 

CO-PERFORMERS: J. T. Smith, K. Kappler, H. F. Morrison, and A. Becker (Lawrence 

Berkeley National Laboratory) 

erkeley UXO Discriminator (BUD) is an optimally designed active electromagnetic system 

that not only detects but also characterizes UXO. The system incorporates three orthogonal 

transmitters and eight pairs of differenced receivers. BUD is mounted on a small cart to assure 

system mobility. System positioning is provided by state-of-the-art RTK GPS receiver. The 

system operates either in a search mode, in which the system moves along a profile and 

exclusively detects targets in its vicinity providing target depth and horizontal location or in a 

discrimination mode, in which the system, stationary above a target, from a single position, 

determines three discriminating polarizability responses together with the object location and 

orientation. Field survey results from various test sites clearly show that BUD can resolve the 

intrinsic polarizabilities of a target, and that there are very clear distinctions between symmetric 

intact UXO and irregular scrap metal. While UXO objects have a single major polarizability 

coincident with the long axis of the object and two equal transverse polarizabilities, scrap metal 

has three different principal polarizabilities. 

Until recently accurate estimates of probability responses were achievable only if the object was 

a single UXO. That means that, in the case of non-UXO response, one was unable to 

discriminate a single piece of scrap from a combination of scrap and UXO. We have developed a 

new approach in which multiple objects are considered, and its performance is illustrated on data 

acquired at various test sites. Furthermore, to discriminate multiple objects or to get accurate 

estimates of location, depth and properties of large objects close to the system we developed a 

scheme where multiple measurements in the vicinity of the anomaly are used for the 

polarizability responses estimation. This approach has also produced encouraging results. 

This research was funded by the U.S. Department of Defense under SERDP/ESTCP projects 

MM-1225 and MM-0437. 

G-18




METALMAPPER: A MULTI-SENSOR TEM AND MAGNETIC GRADIOMETER 

T 

SYSTEM FOR UXO DETECTION AND CLASSIFICATION 

DR. MARK PROUTY 

Geometrics 

2190 Fortune Drive 

San Jose, CA 95131 

(408) 428-4212 

markp@mail.geometrics.com 

CO-PERFORMERS: Dr. D.D. “Skip” Snyder (Snyder Geoscience); 

Dave George (G&G Sciences) 

he objective of this project is to commercialize advanced technology emerging from recent 

ESTCP, SERDP, and NAVEODTECHDIV funded EM research. The project draws heavily 

from AOL (Advanced Ordnance Locator) technology developed by G&G Sciences with funding 

from NAVEODTECHDIV. We use target parameter extraction software developed by Lawrence 

Berkeley National Laboratory under the BUD (Berkeley UXO Discriminator – MM-0437) 

project. With this technology, we have assembled and demonstrated a field prototype of 

advanced electromagnetic induction (EMI) instrument for detection and characterization of UXO 

that performs substantially better than existing commercially available instruments. The 

instrument includes, as an option, the ability to simultaneously acquire both EMI and magnetic 

gradient data (Dual Mode Acquisition). The project was funded late in FY06. During the past 

year, we completed the development and assembly of a field prototype hardware system together 

with Windows-based data acquisition and interpretation software to support it. Our interpretation 

software (MM/RMP) is based on a robust algorithm for UXO model parameterization developed 

by T. Smith at LBL. The prototype MetalMapper system has completed a short “shake-down” 

demonstration at the Standardized UXO Technology Demonstration Site at Yuma Proving 

Grounds (YPG) in June 2008 and a more comprehensive demonstration at the test site in 

Aberdeen Proving Grounds (APG) that was completed in October 2008. This paper describes the 

prototype MetalMapper system and presents data acquired during the demonstrations at YPG and 

APG. 

This project has been funded under ESTCP MM-0603. 

G-19




MINIATURE TOTAL FIELD MAGNETOMETERS 

DR. MARK PROUTY 

Geometrics 

2190 Fortune Drive 

San Jose, CA 95131 

(408) 428-4212 

markp@mail.geometrics.com 

CO-PERFORMERS: Dr. John Kitching (NIST); Dr. Darwin Serkland (Sandia National Labs) 

M 

agnetometers are one of the basic instruments used for the detection and discrimination of 

unexploded ordnance (UXO). Cesium vapor atomic magnetometers are commonly used 

since their readings are independent of the orientation of the sensor, which eliminates the noise 

problems due to rotation or even vibration of other types of sensors. In order to better 

discriminate UXO from clutter or scrap, a high spatial density of readings is desirable. In order to 

efficiently make such measurements, and to position such measurements accurately, arrays of 

sensing elements would be highly desirable. However, existing cesium vapor sensors are 

extremely large and consume a lot of power. Under two SERDP funded projects Geometrics, 

along with partners at the National Institute for Standards and Technology (NIST) and Sandia 

National Laboratories, have developed a miniature total field sensor, consuming a small fraction 

of the power of existing commercial sensors. Such sensors are well on their way towards 

commercialization. In continuing work, we are extending those techniques by pursuing methods 

of operating at wide bandwidths. Such sensors could replace inductive coils currently used in 

EM devices for UXO detection and discrimination. In addition to their small size, measuring the 

magnetic field instead of its rates of change, as an inductive coil does, has considerable 

advantages. In this poster, we will present extremely exciting results of our work prototyping and 

testing actual atomic magnetometers with components no larger than a grain of rice. Measured 

performance of better than 10 pT per root Hz under actual field conditions will be shown. Power 

consumption is a small fraction (less than 10%) of that used in existing systems. We will also 

show results of our work at different cell temperatures, measuring the feasibility of working at 

higher bandwidths. This work will extend the MEMS technologies, allowing for a single sensor 

capable of making both a DC magnetic field measurement as well as a high frequency 

measurement for use in a time domain EM system. Significantly progress is also being made 

towards commercializing these devices. Our design requires straightforward MEMs techniques, 

which are much less complicated, in fact, than some devices in commercial production today. 

Geometrics is working with commercial partners to begin producing such devices in the near 

future. 


G-20




IMPROVED MAGNETIC STAR METHODS FOR REAL-TIME, POINT-BY-POINT 

T 

LOCALIZATION OF UNEXPLODED ORDNANCE AND BURIED MINES 

DR. ROY WIEGERT 

Naval Surface Warfare Center Panama City Division 

110 Vernon Avenue 

Code HS12 

Panama City, FL 32407-7001 

(850) 234-4142 

Roy.Wiegert@navy.mil 

CO-PERFORMERS: Dr. Kwang Lee and Dr. John Oeschger 

here is a pressing need for a practical and effective magnetic sensing technology that can be 

deployed onboard highly maneuverable sensing platforms and used for real-time, point-bypoint 

detection, localization and classification (DLC) of magnetic targets such as ferrous 

unexploded ordnance (UXO) (e.g., bombs, artillery shells and buried mines). Therefore, the 

Strategic Environmental Research and Development Program (SERDP) has supported research 

and development by Naval Surface Warfare Center Panama City Division (NSWC PCD), of a 

novel man-portable Magnetic Scalar Triangulation and Ranging (i.e., “STAR” and/or 

“MagSTAR”) technology for DLC of UXO. The STAR concept uses motion-noise-resistant 

scalar magnitudes of magnetic gradient tensors to perform point-by-point triangulation of the 

location of magnetic targets. The magnitudes are analogous to central potential-type functions 

and they can provide true point-by-point DLC capabilities for sensing platforms in general, 

unconstrained motion. 

A prototype man-portable STAR Gradiometer was designed and constructed at NSWC PCD to 

provide a completely portable and user-friendly technology for real-time DLC of magnetic UXO. 

The prototype STAR Sensor comprises: (a) a cubic array of eight fluxgate magnetometers, and 

(b) a 24-channel data acquisition/signal processing system. In field tests the man-portable sensor 

has demonstrated very robust, motion-noise-resistant DLC performance against isolated dipole 

type targets. 

This paper describes work that is ongoing to enhance the performance of the MagSTAR 

Technology. In particular, two improved algorithms for solving the “STAR Equations” are 

described: (1) A directional derivative (DD) method based on the fact that the gradient of a 

central potential field is a vector that points toward the target/source of the locally strongest 

gradient. (2) A least-squares-fit (LSF) method that iteratively calculates a magnetic target’s 

location and magnetic signature. The DD method is being developed for better discrimination 

between multiple targets but for isolated targets it is more susceptible to sensor noise than the 

LSF method. The initial LSF method applies primarily to DLC of isolated dipole targets. Thus, 

the methods preferably should be used concurrently as complementary DLC modalities in 

environments that may be magnetically complex. These improved methods should help facilitate 

the transition of the STAR Technology from man-portable applications to applications using 

highly maneuverable autonomous sensing platforms for real-time “on the fly” DLC of magnetic 

targets such as UXO and buried mines. This project has been supported under SERDP 

MM-1511. 

G-21




MTADS TIME-DOMAIN EMI SENSOR SYSTEMS FOR UXO CLASSIFICATION 

W 

DANIEL STEINHURST 

Nova Research, Inc. 

1900 Elkin Street, Suite 230 

Alexandria, VA 22308 

(202) 767-3556 

dan.steinhurst@nrl.navy.mil 

CO-PERFORMERS: Glenn Harbaugh (Nova Research); David George (G&G Sciences); 

James Kingdon and Thomas Bell (SAIC, Inc.) 

e have designed and constructed a new time-domain EMI sensor for the purpose of UXO 

classification with the support of ESTCP under projects MM-0601 and MM-0807. The 

sensor is composed of a 35-cm diameter transmit (Tx) loop and a 25-cm receive loop. The 

secondary (induced) field decay can be measured from 0.04-25 milliseconds using fully digital 

electronics. This sensor has formed the core of three separate UXO classification systems. A 

vehicle-towed, 2m x 2m array of 25 sensors has been recently demonstrated for cued 

classification of UXO from clutter. The array would be used as part of a two-step process for 

identifying and classifying buried metal targets where the anomalies for cued investigation were 

previously identified with a survey system. The position and orientation of the array are also 

determined to high precision by an array of GPS antennae. The resultant data (625 bi-static pairs) 

therefore have near-perfect spatial correlation and no motion-induced noise. 

For sites which are not amenable to the deployment of a towed-array system, we have designed 

and begun development of two adjunct systems with enhanced mobility. A handheld, singlesensor 

system has been designed and built for use with a template in a gridded data collection 

mode. A wheeled, 2H2 (four elements total) array has been designed for man-portable operations 

using the same backpack electronics package. The man-portable system is envisioned to operate 

in one of two modes: (1) Detection survey with a 1m square outer Tx loop, or (2) static target 

classification. A prototype of the system has been assembled and used to demonstrate the 2x2 

array in the static data collection mode. 

Target features (principal axis polarizabilities or βs) are estimated by inversion from the data 

using a standard point dipole EMI response model. The inversion process is robust to the 

number of array elements included in processing, retaining good results for shallow targets even 

with only 4 sensor elements (10 bistatic pairs). The process methodology allows for interactive 

data selection to mitigate the effects of overlapping target signatures. 

G-22




MAGNETIC SENSORS WITH PICOTESLA MAGNETIC FIELD SENSITIVITY 

AT ROOM TEMPERATURE 

SY-HWANG LIOU 

University of Nebraska 

Department of Physics and Astronomy and 

Nebraska Center for Materials and Nanosciences 

364 Behlen 

Lincoln, NE 68588-0111 

(402) 472-2405 

sliou@unl.edu 

CO-PERFORMERS: Stephen E. Russek, L. Yuan, Sean T. Halloran, F. C. S. Da Silva, John 

Moreland, and David P. Pappas (National Institute of Standards and Technology, Boulder, CO) 

W 

e present a design of a low power, compact, magnetoresistive sensor. The key features of 

the design are (1) decreasing the noise by the use of a 64 element bridge, (2) reducing the 

magnetic noise by annealing of MTJ in high magnetic field and a hydrogen environment, and 

(3) increasing signal by the use of external low-noise magnetic flux concentrators. The field 

noise of our prototype magnetic sensor are approximately 1 pT/Hz 1/2 at 1 kHz, 5 pT/Hz 1/2 at 10 

Hz, and 50 pT/Hz 1/2 at 1 Hz at room temperature. The magnetic sensor only dissipates 15 mW of 

power while operating. 

This project has been supported under MM-1569. 

G-23




CHARACTERIZATION OF MUNITIONS USING EMI WITH AN ARRAY OF 

3-COMPONENT B-FIELD SENSORS (BEAMOD) 

W 

DR. MICHAEL ASTEN 

Flagstaff GeoConsultants Technology Pty Ltd 

337A Lennox Street, Suite 2 

P.O. Box 2236 

Richmond South, Victoria 3121 AUSTRALIA 

+61 3 8420 6240 

michaelasten@flagstaff-geoconsultants.com.au 

CO-PERFORMERS: Duncan, Sam Fogarty, and Gary Hooper (Flagstaff GeoConsultants 

Technology Pty Ltd); Dr. Stephen Billings, Dr. Len Pasion, and 

Dr. Dave Sinex (Sky Research, Inc.) 

e have developed an operational prototype of an EMI system for UXO detection using a 

single transmitter coil of moment 180 A.m 2 , and three 3-component fluxgate sensors 

(B-field Electromagnetic Array for Munitions and Ordnance Detection – BEAMOD). 

We have trialed three software tools for extracting maximum target information from the 

instrument bandwidth and configuration. 

1. Transformation of gridded images of z-component response to the principal components 

of 25-channel data, yields images which show first-pass discrimination between UXO 

type, independent of depth of burial on a seeded test range. The discrimination is superior 

to that attainable from time-constant calculations on noisy moving-platform data. 

2. BEAMOD profiles across buried munitions with and without a pseudo-random surface 

distribution of scrap metal show that the second derivative of the horizontal transverse 

component of the EMI field is a powerful discriminator of scrap versus buried-target 

responses. 

3. After extension of the UXOLAB software package to utilize an array of vector sensors. 

The BEAMOD profiles across buried munitions invert to yield dipole parameters of three 

orthogonal dipoles. Parameter variance decreases as the multiple receivers and multiple 

components are added to the basic single-component profiles, verifying self-consistency 

between the multiple sensors and components, and demonstrating that higher resolution is 

attainable when using the array of sensors. The standard deviation on recovered 

polarizations when using the array of vector sensors is typically a factor of five reduced 

from that obtained when using profiles acquired with a single vertical-component sensor 

only. 

The project has been supported by SERDP as Project MM-1598. 

G-24


High Explosive Identification 


P 

OPERATIONAL EVALUATION OF A NEW ACOUSTIC TECHNIQUE 

FOR UXO FILLER IDENTIFICATION 

DR. WES COBB 

University of Denver Research Institute 

2050 E. Iliff Avenue 

Denver, CO 80208 

(303) 871-3140 

wcobb@du.edu 

ersonnel who must remediate Department of Defense sites need better tools to discriminate 

between unexploded ordnance (UXO) and non-hazardous items. Although great effort has 

been made to detect and localize UXO in the ground and underwater, there are currently few 

devices that can inspect and identify the filler materials. The ability to make a quick and safe 

filler identification would significantly lower the risks to personnel and the cost of remediation. 

This project utilizes acoustic waves to identify the materials inside sealed UXO. Small sensors 

clamped to the outside of the ordnance send low-energy acoustic waves through the container 

walls and filler. The received signals are analyzed to determine the characteristic acoustic 

properties of the filler material. To identify the filler, these measured properties are compared to 

a database of properties for known explosive and inert filler materials. 

This talk describes an ongoing project to demonstrate and validate new technology for 

identifying the filler material in UXO. This technology, developed under the Strategic 

Environmental Research and Development Program (MM-1382), correctly identified important 

inert filler types in demonstrations on actual ordnance at several DoD laboratory and range 

facilities. In the current ESTCP project, key field tests have been conducted at a controlled DoD 

site (Aberdeen Test Center) to confirm accurate identification for fired ordnance. The talk will 

report on validation testing of the acoustic technique at a controlled site (Navy EOD Technology 

Division) and at an active UXO response site. 


G-25


Planning and Support 


A 

APG STANDARDIZED UXO TECHNOLOGY DEMONSTRATION SITE 

RECONFIGURATION 

DENNIS A. TEEFY 

U.S. Army Aberdeen Test Center 

400 Colleran Road 

TETD-AT-SLE 

Aberdeen Proving Ground, MD 21005 

(410) 278-4062 

dennis.teefy@us.army.mil 

CO-PERFORMERS: Kimberly Watts (USAEC); William Burch and Rickey Fling (ATC); 

Patrick McDonnell (BAH) 

dvancements in Unexploded Ordnance (UXO) detection and discrimination technologies 

are necessary to support the sustained operation, restoration, and transfer of the DoD’s 

ranges. The Aberdeen Proving Ground (APG) and Yuma Proving Ground (YPG) Standardized 

UXO Technology Demonstration Sites provide the UXO Community the ability to evaluate the 

detection and discrimination capabilities of UXO sensor systems. This ability has been 

augmented at the APG Standardized Site as a result of a third generation reconfiguration. During 

the two previous reconfigurations, ground truth items were removed, shuffled, and reburied. 

Traditionally the open field area of the site was configured to represent a common, mixed use 

impact area. A fundamental philosophical shift occurred during this reconfigurations and areas 

simulating both Direct and Indirect Fire training ranges would be developed in the open field. 

The sub areas have ordnance and clutter emplaced that mimic the expected size, type, and 

distribution of targets found in their respective fire impact areas. 

System performance is evaluated for response and discrimination stages by reporting probability 

of detection, probability of false positive, background alarm rate, and ROC curves. Several 

improved scoring metrics are now available to expand the understanding of system performance. 

Scoring has been modified to determine the impact of overlapping halos due to grouped 

ordnance and clutter. Detection within these overlapping halos is now reported in three ways: 

groups found (any item within a group is matched to an anomaly on a demonstrator’s list), 

groups identified (multiple items within a composite halo are matched to anomalies on a 

demonstrator’s list) and groups covered (measures the demonstrator’s accuracy in determining 

the number of anomalies within a group). In addition, demonstrators are now provided all 

scoring information based not on the depth of the item buried but rather the depth compared to 

the diameter of the target. 

These modifications to the APG Standardized Site will continue to support the advancement in 

UXO sensor technologies. A portion of the open field area remains in the previous generation’s 

configuration. This allows the program to compare results to previously completed 

demonstrations at both APG and YPG. No modifications have been made at the YPG 

Standardized Site at this time. 

The APG and YPG sites are currently open for testing of handheld, man-portable and towed 

array detection systems. This project has been supported under ESTCP MM-0103. 

G-26


Planning and Support 


F 

UX-PROCESS UPDATE – FREE SOFTWARE FOR DIGITAL GEOPHYSICAL 

MAPPING 

MS. AMY WALKER 

USAESCH 

ATTN: ED-CS-G 

4801 University Square 

Huntsville, AL 35816 

(256) 895-1604 

amy.n.walker@usace.army.mil 

CO-PERFORMERS: Nick Valleau and Elizabeth Baranyi (Geosoft, Inc.) 

or the last several years, supported by ESTCP funding under Project MM-0131, the 

Huntsville Center has worked with Geosoft, Inc. to develop an extensive suite of freely 

available software tools for the industry to assist with specialised requirements for UXO 

detection and discrimination. The project provides a standardized tool set to assess data quality, 

helps improve data processing and analysis, and provides a standard software platform for 

sharing analysis algorithms. 

The software package, named UX-Process, operates within Geosoft’s commercial Oasis 

Montaj data processing environment and currently contains over 70 menu items. UX-Process 

has been supported and applied in the field for several years, with updated versions released 

annually. It is available at no cost for U.S. government UXO personnel and their contractors, and 

existing Oasis Montaj license holders. Requests for this free license can be submitted at: 

http://www.geosoft.com/pinfo/industry/uxo/uxprocess.asp 

The UX-Process tools, currently used on UXO projects by contractors and government 

personnel, improve the utilization of field data by identifying and correcting instrument and 

acquisition errors and providing documentation of the data quality. In addition, UX-Process 

provides a consistent and logical structure for adding new target analysis and discrimination 

capabilities, as they become available. The standard tests and tools developed under this project 

enable the contractors tasked with collecting, processing and analyzing the data to be more 

effective in meeting U.S. government data quality standards, and allow the U.S. government to 

be more efficient in assessing and documenting the quality of the product delivered. 

This poster will focus on the new developments and updates in the latest release. 

G-27


Facilities Management — Facility Waste 


APPLICATION OF A BIMETALLIC SOLVENT PASTE TECHNOLOGY FOR PCB 

REMOVAL FROM OLDER STRUCTURES ON DOD FACILITIES 

DR. NANCY E. RUIZ 

NAVFAC Engineering Service Center 

1100 23rd Avenue EV411 

Port Hueneme, CA 93043 

(805) 982-1155 

nancy.ruiz@navy.mil 

CO-PERFORMERS: Dr. Jacqueline Quinn (NASA); Dr. Christian Clausen, Dr. Cherie Geiger, 

and James Captain (University of Central Florida); Suzanne O’Hara and Thomas Krug 

(Geosyntec Consultants) 

R 

esearchers from the Naval Facility Engineering Command Engineering Service Center 

(NAVFAC ESC), the NASA-Kennedy Space Center (NASA), the University of Central 

Florida (UCF) and Geosyntec are working on an ESTCP-funded technology demonstration 

project (SI-0610) to demonstrate the efficacy of a Bimetallic Treatment System (BTS) to remove 

and rapidly degrade polychlorinated biphenyls (PCB) found in structural coatings. 

The BTS technology, which consists of elemental magnesium coated with a small amount of 

palladium in a solvent solution capable of hydrogen donation, has two functions: (1) to extract 

PCBs from weathered, decades-old coating material such as paint and (2) to rapidly degrade the 

extracted PCBs. Prior to 1979, PCBs were extensively used in industrial paints, caulking material 

and adhesives, as their properties enhanced structural integrity, reduced flammability and 

boosted antifungal properties. Researchers from NASA and UCF previously demonstrated rapid 

and complete dechlorination of PCBs in aqueous/solvent systems containing Aroclors 1254, 

1260, and 1268 (specific PCB mixtures). Significant, if not complete, PCB extraction and 

degradation from paint chips with total PCBs as high as 11,000 ppm has been achieved with as 

little as 48 hours of exposure. The solvent in BTS is used to open but not destroy the polymeric 

lattice structure of the paint, allowing pathways for PCB movement out of the paint and into the 

solvent. BTS formulation properties that must be addressed for each site-specific application 

include viscosity and stability. 

This project addresses pre-demonstration laboratory testing conducted at two of the 

demonstration sites and field testing conducted at these demonstration sites, the Vertical 

Integration Building (VIB), Cape Canaveral, Florida and Badger Army Ammunition Plant, 

Wisconsin. Pre-demonstration laboratory testing evaluated the concentrations of PCBs in the 

various materials tested at each facility, including paint metal, wood and concrete and to 

determine which BTS formulation would work best for each material. Variables evaluated in the 

demonstration include the substrates on which the PCB coatings have been applied; age of the 

coatings; adhesion, appearance, and repeat application of BTS; and substrate condition on 

removal of the BTS and PCB coating. In addition, tests were conducted to evaluate the effect of 

temperature on the BTS stability and performance. The demonstration goal is to reach PCB 

concentrations below the Toxic Substances Control Act limit of 50 parts per million (ppm) in the 

paint on all structures tested. Details of the results from the field demonstration at the VIB and 

Badger will be presented. 

G-28




T 

DETERMINING ENVIRONMENTAL SOLUBILITY OF PB FROM RECYCLED 

CONCRETE AGGREGATE 

MR. STEPHEN COSPER 

U.S. Army-CERL 

2902 N. Newmark 

Attn: CEERD-CN-E 

Champaign, IL 61822 

(217) 398-5569 

stephen.cosper@us.army.mil 

CO-PERFORMERS: Howard Weinick (Concurrent Technologies Corporation); 

Gary Bordson (Illinois Sustainable Technology Center) 

(Sorry—due to a last minute cancellation, this poster will not be presented.) 

he DoD has very active construction programs under several different initiatives, including 

military construction, realignment, closures, and facility reduction. Many of the structures 

demolished to make way for the new construction are Cold War-era concrete buildings with 

some level of lead-based paint (LBP) coatings. Under most scenarios, the debris resulting from 

these demolitions can be landfilled (i.e., in a construction and demolition, nonhazardous waste 

landfill) because the overall lead concentration is below Resource Conservation and Recovery 

Act (RCRA) thresholds. However, this is a wasteful practice as the concrete could be reused by 

the installation for many construction purposes, such as fill, road-base, or trails. Filling 

government-owned landfills with concrete is also unnecessary and wasteful, especially when 

considering the long-term maintenance and monitoring responsibilities associated with landfills. 

For the Army, Assistant Chief of Staff for Installation Management (ACSIM) policy requires 

fifty percent waste diversion for all construction projects. 

The SON, to which the project responds, implies that LBP coated demolitions debris is often 

disposed in a hazardous waste landfill. According to the Construction Materials Recycling 

Association (http://www.cdrecycling.org/) there is a growing industry in concrete recycling. 

Sometimes, construction project managers are hesitant to utilize recycled concrete aggregate 

with any LBP content because of uncertainty regarding environmental regulations or effects. 

This project will attempt to answer one of the main concerns voiced: leachability of Pb from the 

painted surfaces into the environment. 

The approach in this project is to follow a real world example—from demolition, to recycling, to 

material reuse at a military installation. Researchers will characterize the construction materials 

pre-demolition, sample the processed material, and then conduct an environmental leaching 

experiment to replicate field conditions. 

To date, researchers have: characterized the source building; sampled the crushed concrete 

product; analyzed for total Pb content; and developed and tested a column based extraction 

technique, designed to mimic rain events. 

This work is funded by SERDP Project SI-1549. 

G-29




T 

LIGHTWEIGHT, COMPOSTABLE AND BIODEGRADABLE FIBERBOARD 

JO ANN RATTO 

U.S. Army Natick Soldier Research, Development and Engineering Center 

Kansas Street 

Natick, MA 01760 

(508) 233-5315 

joann.ratto.ross@us.army.mil 

CO-PERFORMERS: Jason Niedzwiecki, Jeanne Lucciarini, and Christopher Thellen 

(NSRDEC); Xin Li, Susan Sun, and Donghai Wang (Kansas State University); 

Darin Richman and Richard Farrell (University of Saskatchewan) 

he SERDP project (SI-1479) “Lightweight and Compostable Packaging for the Military” is 

in its final year of developing environmentally-friendly, lightweight biodegradable 

fiberboard that can be converted to a valuable byproduct, compost. The project will help to 

reduce the amount of solid waste for the military. Meal, Ready-to-Eat (MRE) shipping 

containers fabricated from fiberboard are necessary to transport and store food and other military 

items in various climatic extremes while protecting the contents from insect and rodent 

infestation. Although the shipping containers are effective and meet the myriad of operational 

and functional requirements, there are numerous disadvantages in producing this type of 

fiberboard for the military: the process is costly; uses cellulose and hazardous chemicals; 

depletes natural resources in our environment; and creates harmful waste. The goal of this 

project is to develop lightweight biodegradable fiberboard that can be used for ration packaging 

while meeting all operational requirements. 

A novel fiberboard is being developed using a soy protein adhesive and natural fillers to reduce 

either density or thickness while maintaining needed mechanical properties and water resistance. 

Fiberboard manufacturing procedures were investigated with effects of resin coating and press 

conditions on fiberboard density and mechanical properties. Experiments were performed on 

introducing other fibers such as chicken feather fibers, cheese clothe, straw fibers, and 

commercially available pulp fibers to further reduce density and enhance strength. 

An alternative approach is to develop coated corrugated fiberboard that has comparable 

performance to the existing military shipping containers. Several designs and coating 

formulations have been developed and testing of burst strength, compression and stacking 

strength at wet and dry conditions have been performed. The results are promising with 

reductions in weight, fiber content and cost from the existing MRE containers. 

The compostability of fiberboard is being assessed with both laboratory (respirometer and weight 

loss tests) and field components. Most of the samples tested by respirometer methods had greater 

than 60% percent mineralization after 180 days with cellulose as the positive control. Weight 

loss results for the samples are in the range of 15-20% weight loss after 6 weeks of testing. 

G-30




T 

NANOTECHNOLOGY PACKAGING FOR THE MILITARY 

JO ANN RATTO 

U.S. Army Natick Soldier Research, Development and Engineering Center 

Kansas Street 

Natick, MA 01760 

(508) 233-5315 

joann.ratto.ross@us.army.mil 

he environmental problem of solid waste generated by the Army is being addressed in this 

Environmental Security Technology Certification Program (ESTCP) demonstration/ 

validation program. The amount of packaging waste generated per Meal, Ready-to-Eat (MRE) 

ration is 0.36 lb (22.9% of total weight of ration). The average procurement for MRE rations is 

over 43 million rations per year which contributes to over 14,000 tons of packaging waste. With 

the rising costs of transportation and disposal, there is the need to investigate alternative 

materials for combat ration packaging applications. The objective of this three year effort is to 

demonstrate and validate new nanocomposite packaging for the military which has been 

achieved through earlier Environmental Quality Basic Research (EQBR) and Strategic 

Environmental Research and Development Program (SERDP) projects. Industry-based 

developments in the area of nanocomposite packaging films that have matured into commercially 

available products were leveraged as well. Nanocomposite packaging for the Meal Bag, nonretort 

and retort pouches will be demonstrated and evaluated to reduce DoD specific waste 

problems through the development of recyclable military ration packaging which also meet 

combat ration operational requirements. 

The first year of this ESTCP project has focused on producing the nanocomposite Meal Bags and 

food pouches. Several nanocomposite technologies are being implemented in this program. A 

variety of polymer combinations and nanoparticles are targeted for the different MRE packaging 

components. After production of the film and pouches, quality control and characterization work 

will be performed. The pouches will then be filled with MRE food products and packed into 

solid fiberboard cases and pallet loads. The nanocomposite packaged items will undergo storage 

studies, sensory testing, airdrop, transportation and field testing. 

Overall, the goal is to transition this mature nanotechnology to material converters and 

demonstrate manufacturability, producibility and, ultimately, durability of these nanocomposite 

packaging structures within the military logistics system. 


G-31




S 

NOFOAM SYSTEM TECHNOLOGY FOR AIRCRAFT HANGAR FIRE 

SUPPRESSION FOAM SYSTEM 

RANCE T. KUDO 

NAVFAC ESC 

1100 23rd Avenue, EV-421 

Port Hueneme, CA 93043-4370 

(805) 982-4976 

rance.kudo@navy.mil 

erious environmental concerns have arisen from aircraft hangar fire suppression foam system 

discharge tests. These concerns stem from hundreds of thousands of gallons of aqueous film 

forming foam (AFFF) wastewater that is generated during testing. As a result of these 

environmental concerns, foam discharge checks are not being performed and this has a negative 

impact on the facility mission readiness. As a result, the Navy has developed a real time 

evaluation NoFoam System that tests the aircraft hangar fire suppression system without 

releasing AFFF to the environment. This technology allows the activity to test the fire 

suppression foam system. 

The Naval Facilities Engineering Command (NAVFAC) Engineering Service Center (ESC) are 

demonstrating and validating the NoFoam System for aircraft hangar fire suppression foam 

system. This is being done with the sponsorship of the Environmental Security Technology 

Certification Program (ESTCP) and NAVFAC, under Project SI-0525. The NoFoam System 

hardware is installed inline with the hangar fire suppression foam system, and uses water (or an 

environmental benign dye-water) to provide a valid foam nozzle discharge array test that 

eliminates AFFF release. The technology provides real-time online measurements discharge 

rates and requires no specially trained personnel to interpret the resulting data. Validations will 

be conducted at Arizona Air National Guard, Arizona (Tucson); Marine Corps Base Hawaii, 

Kaneohe; and Naval Air Station Lemoore, California. 

DoD cost savings will be accrued from eliminating AFFF wastewater collection and disposal and 

replenishment of spent AFFF concentrates during annual and maintenance discharge checks. 

DoD activities and mission readiness will not be jeopardized. 

G-32




PHA BIOPLASTIC PACKAGING MATERIALS 

DR. CHRIS SCHWIER 

Metabolix 

650 Suffolk Street, Suite 100 

Lowell, MA 01854 

(978) 513-1830 

schwier@metabolix.com 

CO-PERFORMER: Dr. Jo Ann Ratto (U.S. Army Natick Soldier Research, Development and 

Engineering Center) 

P 

lastic packaging materials represent a significant portion of the world plastics consumption, 

estimated in excess of 340 billion lbs in 2007. In North America alone, consumption of 

plastic shrink/stretch film was over 1.5 billion lbs/year in 2006, and foamed product 

consumption is estimated at 8.5 billion lbs/year in 2006. While these packaging materials are 

low-cost and effective, the logistics of managing packaging waste is becoming increasingly 

problematic and costly. Military operations in remote areas and/or foreign countries face serious 

logistic hurdles dealing with large volumes of packaging waste. 

PHA Natural Plastics are produced by Metabolix from renewable agricultural resources. 

Because they are biodegradable in marine and soil environments, products made with PHAs can 

be disposed of easily and without any adverse environmental impacts. PHA Natural Plastics are 

considered well-suited for use in packaging application due to the range of physical properties 

attainable, water resistance, heat resistance, strength, and barrier properties. Other biodegradable 

materials, particularly starch based materials, do not have the required water resistance, 

temperature resistance, or range of properties required for many film and foam packaging 

applications. 

The objective of this project is to demonstrate the applicability of biodegradable PHA Natural 

Plastics for foamed packaging and stretch/shrink film applications. PHA foams have been 

produced and tested for functional performance and biodegradability. Key sciences and 

technologies have been developed for material designs and foam processing, including branching 

and selection of environmentally-friendly blowing agents. A potential commercial foam 

development partner has been established. 

For pallet wrap products, which are typically stretch or shrink film, PHA formulations have been 

developed for film processing. Evaluations of processibility and properties are in progress. 


G-33




FOOD AND HUMAN WASTE REMEDIATION FOR NAVY SHIPS AND ARMY 

N 

BASE CAMPS 

JESSICA HSU 

Clairvoyant Technologies, Inc. 

1107 D Street, SE 

Washington, DC 20003 

(202) 629-1831 

jessica@clairvoyanttechnologies.com 

CO-PERFORMERS: Adam J. Baron and Mauricio Boada (Biogreen Energies); 

Jennifer Hsu (Clairvoyant Technologies, Inc.) 


avy ships can remain at sea for months and generate large amounts of waste that requires a 

method of environmentally-safe disposal. According to estimates from the Navy, each 

person aboard a ship generates between three to four pounds of solid waste per day. Therefore, 

an aircraft carrier with 6,000 personnel can remain at sea for 90 days and generates 826 tons of 

solid waste. This yield cannot be stored on board until the ship docks, so often it is disposed 

overboard. Additionally, studies have shown that a typical maneuver Army battalion is 

comprised of 550 soldiers will produce about 2,000 lbs of solid waste per day. 

Biodigestion technology has been around for thousands of years and can be used to rapidly 

convert food and human waste into useful energy and non-hazardous residuals that can be safely 

disposed on-site. The biodigester system does not emit objectionable odors, and does not require 

electrical power to run. The use of solar panels will maintain the digester temperature at 

acceptable operation levels. This facilitates implementation in remote military base locations and 

aboard navy ships at sea. The system is relatively inexpensive to own and operate, compared to 

the alternative of waste-to-energy gasification. 

Biodigesters can be installed with customizable interfaces to existing kitchen and toilet systems 

to provide a composting system, a garbage disposal, and a converter of waste to clean energy. 

The energy is produced from anaerobic digestion in the form of an odorless biogas, which can be 

used for cooking, lighting, combustion engine driving, and even fueling pumps and electric 

generators. This methane-based gas is converted to mostly CO 2 and water when burned, making 

it a comparatively nonpolluting gas. The system essentially prevents the natural decomposition 

of the wastes where methane escapes to the atmosphere or pollutes the water, which causes more 

harm than carbon emissions. Therefore, the process is carbon negative, and each digester can 

generate approximately on the order of 100 carbon credits per year, which is equivalent to a 

reduction in 100 tons of carbon dioxide emissions. 

G-34


Facilities Management — Noise 


CHARACTERIZATION OF A BAYESIAN CLASSIFIER TO IDENTIFY MILITARY 

T 

IMPULSE NOISE 

JEFFREY S. VIPPERMAN 

University of Pittsburgh 

531 Benedum Hall 

3700 O’Hara Street 

Pittsburgh, PA 15261 

(412) 624-1643 

jsv@pitt.edu 

CO-PERFORMERS: Brian Bucci and Matthew Rhudy (University of Pittsburgh) 

o facilitate a better relationship between military installation and their surrounding civilian 

population, the function of military installations impulse noise monitoring stations needs to 

be improved. The monitoring stations currently in service suffer numerous false positive 

detections, (which are believed to originate from wind noise), and also do not detect many 

significant impulse events. Most of the previous work within this effort has focused on defining 

metrics to identify military impulse noise and processing these metrics with artificial neural 

networks and Bayesian classifiers. More recent work has also been directed towards identifying 

military impulse noise from direct temporal processing of the recorded waveforms. This previous 

work, while successful, had focused largely on achieving maximal overall accuracy, without 

much regard for the nature of the inevitable misclassifications (false positive detections and false 

negative rejections). In an actual implementation of these algorithms, the nature of the 

misclassifications would be of great concern to the user. To this end, this new effort focused on 

characterizing the Bayesian classifier. The purpose of this project is to find the optimal number 

of multi-Gaussian fits for each class of noise that would produce the classifiers with the 

following characteristics: (1) maximal overall accuracy, (2) maximal accuracy with no false 

positive detections, and (3) maximal accuracy with no false negative rejections. Additionally, it 

is desired to determine the prior probabilities of each noise source that correspond to these 

characteristics and the range of prior probabilities that produce classifiers which operate within 

the optimal range (maximal accuracy with no false positive detections to maximal accuracy with 

no false negative rejections). When the classifiers are evaluated on testing data, the maximal 

accuracy is 99.8%, the maximal accuracy with no false negative rejections is also 99.8%, and the 

maximal accuracy with no false positive detections is 98.4%. 


G-35


Natural Resources Management — Threatened and Endangered Species 


PHYSIOLOGICAL AND DEMOGRAPHIC EFFECTS OF ROAD DENSITY ON 

ENDANGERED SONGBIRD BREEDING AT FORT HOOD 

DR. LUKE K. BUTLER 


Department of Biology 

Medford, MA 02155 

(617) 627-4036 

luke.butler@tufts.edu 

CO-PERFORMERS: Dr. Leslie Ries (University of Maryland); Dr. Isabelle-Anne Bisson and 

Dr. Martin Wikelski (Princeton University); Dr. Timothy J. Hayden (ERDC-CERL); 

Dr. L. Michael Romero (Tufts University) 

T 

he Golden-cheeked Warbler (Dendroica chrysoparia) is an endangered migratory songbird 

with a large breeding population at Fort Hood, Texas, where military training involving 

vehicles along roads is common and widespread. Therefore, it is important to understand any 

effects of roads on the sustainability of Golden-cheeked Warbler populations at Fort Hood. 

Previous work (Peak 2007: Condor 109: 628-637) showed that Golden-cheek nests were more 

likely to be taken by predators in territories with high road density, suggesting that roads may 

negatively affect Golden-cheek breeding success. We used physiological and demographic 

measures to test the hypothesis that road density may also affect survival of adults. We compared 

the ages of territorial males across a range of road density categories to test the prediction that 

younger males would be more common in areas with more roads, suggesting those areas were 

less preferred by older, more dominant males. We also compared road density to body mass and 

the stress-related hormone corticosterone in breeding adults, to test the prediction that adults 

breeding in areas with high road density would be in worse physiological condition than adults 

breeding in areas with low road density. 


G-36




POPULATION VIABILITY ANALYSIS OF SHORTNOSE STURGEON (ACIPENSER 

BREVINOSTRUS) IN THE OGEECHEE RIVER, GEORGIA 

DR. HENRIETTE JAGER 


P.O. Box 2008, Mail Stop 6036 

Oak Ridge, TN 37922 

(865) 574-8143 

jagerhi@ornl.gov 

CO-PERFORMERS: Dr. Mark Bevelhimer (Oak Ridge National Laboratory); Dr. Doug Peterson 

and Daniel Farrae (University of Georgia); Roy King (Fort Stewart) 

R 

ivers and estuaries along the Atlantic coast support both military installations and 

populations of the federally endangered shortnose sturgeon (Acipenser brevirostrum). This 

project focuses on the population in the Ogeechee River system, near Fort Stewart. Three goals 

of this research are: (1) to quantitify and partition the influences on shortnose sturgeon recovery 

under the control of the military from those that are not; (2) to prioritize recovery efforts; and 

(3) to quantify population thresholds. This project integrates field and modeling efforts. In the 

field, river depth and width was characterized for the area of interest. Water quality monitoring 

began in winter and continued through early fall. Temperature and dissolved oxygen showed 

seasonal, but not longitudinal variation. Salinity increased downstream, but showed little 

seasonal variation. These data will be used to calibrate the water quality model, which we will 

use to simulate episodes of poor water quality in summer. We conducted a survey of shad fishing 

effort during late winter-early spring, which will help us to quantify the risk of capture as bycatch. 

A sister telemetry study tagged over 100 individuals, three of which were tagged in the 

Altamaha River. On the modeling front, an individual-based and spatially explicit population 

viability model was developed for the shortnose sturgeon. This model will be used to evaluate 

the number of individuals needed to sustain a viable population. 


G-37




AUTOMATED ACOUSTIC MONITORING OF BAT AND BIRD POPULATIONS 

F 

DR. JOSEPH M. SZEWCZAK 

Humboldt State University 

Department of Biological Sciences 

1 Harpst Street 

Arcata, CA 95521 

(707) 826-4132 

joe@humboldt.edu 

CO-PERFORMER: Dr. Stuart Parsons (University of Auckland, New Zealand) 

ederal regulations require the monitoring and management of sensitive species on public 

land jurisdictions and for many species this work necessitates specialized and expensive 

personnel. In addition, the rarity of most sensitive species typically obligates greater survey 

effort (and higher cost) to acquire reliable data compared to more common species, particularly 

over the extensive landscapes of U.S. military installations. Fortunately, species that emit 

acoustic signals facilitate automated monitoring that can provide a cost-effective solution to 

confidently assess activity and confirm presence or absence. Automated acoustic monitoring can 

also provide consistency by eliminating variability in the skill level of monitoring personnel, 

operate continuously to better detect rare species that intermittent survey efforts may miss, and 

transmit data remotely from personnel-restricted areas. 

Automated acoustic monitoring entails (1) autonomous field recording hardware, (2) software to 

automate detection and classification of signals based on, (3) a comprehensive library of 

reference recordings from target and sympatric species to cover their range of signals under field 

conditions. Our SERDP supported team (under Project SI-1394) has completed these tasks to 

deploy a functioning automated monitoring and classification system. 

Calibrating species classification depended upon acquiring a reliable library of known species 

recordings from free-flying bats. This presented a considerable challenge because: (1) many 

sympatric species emit echolocation calls overlapping in many acoustic characteristics; (2) bats 

exhibit considerable plasticity in their calls; and (3) unlike birds that can be identified at a 

distance while recording, most bats require capture to determine species. We captured bats and 

tracked them with light-tags to acquire free-flight recordings. Our field crews acquired in excess 

of 10,000 recordings from 34 species in 23 states. We then developed robust novel algorithms 

including an adaptive fast Fourier transform (FFT) method that automatically optimizes FFT 

parameters to signal characteristics, an innovative method to attenuate echo distortion, and 

intelligent signal tracing routines. This enabled the extraction of several million data points from 

the reference library to calibrate and generate regional classification modules to automatically 

classify unknown bats from field recordings. By using a variety of machine learning methods 

and ensembles of machine learning methods, we have met or exceeded a target correct 

classification rate of 90% for most species, including the federally listed Indiana bat (Myotis 

sodalis) and gray bat (M. grisescens). 

G-38




EVALUATING THE EFFECT OF CLIMATE CHANGE ON POPULATION 

DEMOGRAPHICS OF CEANOTHUS VERRUCOSUS 

DAWN M. LAWSON 

NAVFAC Southwest 

1220 Pacific Highway 


(619) 726-5684 

dawn.lawson@navy.mil 

CO-PERFORMERS: Dr. Helen M. Regan (University of California, Riverside); 

Dr. Paul H. Zedler (University of Wisconsin, Madison); Dr. Janet Franklin (California State 

University, San Diego) 

C. 

verrucosus, a shrub species restricted to the coastal chaparral and sage scrub of southern 

California, is considered vulnerable to both very long and short fire intervals. Fire kills 

adult plants and the population re-establishes from soil seed banks which are not restocked to 

replacement levels for several decades after a fire. In addition to shifts to the species’ 

distribution, climate change poses risks to this species due to both potential effects on vital rates 

and increases in fire frequency. We consider two scenarios evaluated under the U.S. Climate 

Sciences Program. One predicts a warmer and wetter climate while the other a warmer and drier 

climate for southern California. Under both scenarios the probability of extreme wet and dry 

events increase in the future and the probability of fire could increase as well. We use a spatially 

explicit stochastic matrix model to evaluate the direct effects of changes in temperature and 

precipitation on population dynamics by considering likely changes in the means and variances 

of vital rates and fire frequencies. Our model is age structured with a two-year time step and 

includes seeds for a total of 48 stages. As was expected, increasing the variance increases the risk 

of extinction. Based on data from other obligate post-fire seeding Ceanothus species, C. 

verrucosus is expected to experience relatively high mortality from predation and drought stress 

in its first few years and then density dependent thinning through 15 to 20 years. After this time, 

based on ring counts from dead standing C. verrucosus, mortality drops to very low levels. 

Changes in vital rates resulting from predicted changes in mean temperature and precipitation 

and their variances are expected to disproportionately affect survival of the younger plants 

competing for moisture where the model is most sensitive. Our model shows that for both 

climate projections the risk of extinction increases. This work is a part of SERDP Project 

SI-1473, which will integrate population viability analyses, habitat suitability models, and a 

landscape level model to identify parcels and management actions necessary to maintain stable 

metapopulations of targeted species in a fragmented landscape. 

G-39




D 

NAVAL FACILITIES ENGINEERING SERVICE CENTER 

MULTIPLE STRESSORS: THE ROLE OF WORMS, SLUGS AND DEER IN 

SHAPING OUR FOREST PLANT COMMUNITIES 

BERND BLOSSEY 


Department of Natural Resources 

Fernow Hall 

Ithaca, NY 14853 

(607) 255-5314 

bb22@cornell.edu 

CO-PERFORMERS: Dr. Evan Cooch (Cornell University); 

Victoria Nuzzo (Natural Area Consultants) 

ramatic changes in eastern forests have caused many plant species to exist in small or 

isolated populations that are considered to be threatened, endangered, or of special concern 

(TES). Threats to their long-term survival include habitat loss and fragmentation, invasive plants, 

animal diseases, nutrient deposition, and climate change. Management of these plant populations 

should be guided by an analysis of the severity of threats caused by various stressors and their 

response to management efforts. 

This SERDP-funded project, SI-1475, is researching the role of slugs and earthworms in the 

germination and recruitment of native species and evaluating how native white-tailed deer affect 

the demography of rare and endangered plant species. Large deer enclosures have been 

established at West Point Military Academy to follow long-term trends in herbaceous vegetation 

(both native and introduced) in the absence of deer herbivory. 

Certain plants may evolve invasiveness after their introduction into a new range (evolution of 

increased competitive ability hypothesis), and there is evidence that the introduction and spread 

of introduced earthworms may be the leading cause for plant invasions, at least in forest 

ecosystems in the Northeast. Browsing by an overabundant deer population on adult plants may 

lead to a collapse of the herbaceous layer, and introduced slugs and weevils may prevent any 

recruitment from the seed bank. There is abundant evidence for the “ecosystem engineering” 

ability of deer and slug herbivory, plant or earthworm invasions, as well as nutrient deposition, 

and this work combines an assessment of these different stressors into a single study and model. 

Our working hypothesis postulates that a reduction of the deer herd will prevent the decline of 

many native plant species (or allow their recovery), leading to a reduced need for invasive plant 

management. 

G-40




AN ECOINFORMATIC APPROACH TO DEVELOPING RECOVERY 

GOALS AND OBJECTIVES 

DR. MAILE C. NEEL 


Department of Plant Science and Landscape Architecture & Department of Entomology 

2116 Plant Sciences Building 

College Park, MD 20742 

(301) 405-9780 

mneel@umd.edu 

CO-PERFORMERS: Dr. Bill Fagan, Sara Zeigler, and David Luther (University of Maryland) 

A 

lack of data hinders managers’ abilities to set scientifically defensible recovery goals and 

criteria for all but a few species. Our objective is to develop methods that will help quantify 

scientifically defensible recovery goals for federally listed species on DoD-managed lands via 

sophisticated comparison of endangered species with a diverse set of well-studied species. We 

will build explicit links between established recovery goals of listed species and their biological 

traits and extrinsic threats. To date, we have focused on developing databases for life history and 

recovery information for federally listed species as well as life history information and 

conservation recommendations for well-studied species. 

We have compared the number of populations required for recovery of plant species on the U.S. 

Endangered Species list with the current number of populations and historic number of 

populations. The plant dataset comprises the 642 taxa covered in one of the 262 recovery plans 

approved as of December 2007. Recovery plans provided numbers of historical populations for 

407 taxa, ranging from 1 to 284 populations (mean=15.8; median=8). Numbers of extant 

populations were available for 596 taxa and ranged from 0 to 175 populations (mean=10.9; 

median=4). The percentage of populations remaining (n=404) ranged from 0%-100% and 

averaged 66.5%. Qualitatively we know that 446 taxa have lost whole populations, 378 have 

reduced population size, and 285 species for which data were available had both types of losses. 

Based on U.S. Fish and Wildlife Service (USFWS) statements in recovery plans, we evaluated 

the potential for delisting plant taxa as ‘not possible’ for 136 species, ‘may not be possible’ for 

an additional 265 species, and ‘possible’ for 240 species. When recovery plans are categorized 

by year of approval (prior to 1992, between 1992 and 1998, and after 1998), the percentage of 

species for which delisting is considered ‘not possible’ has declined over time, as has the number 

of species for which delisting is considered ‘possible’. Thus, uncertainty has increased. The 

overwhelming reason given for inability to delist is lack of information. The number of 

populations deemed necessary for delisting ranged from 1 to 115 and averaged 10.7 populations. 

Percentages of populations required for recovery represented 11.2%-800% of historical numbers 

(n=284 species) and 12.0%-1,500% of current numbers (n=383 species). At least all current 

populations were required for 72.1% of taxa and numbers equivalent to all current and historical 

populations were required for 53.5% of taxa. On average, recovery objectives required 247.5% 

of current populations per taxon and 154.5% of all current and historical occurrences combined, 

indicating need for restoration actions. 


G-41




C 

CHARACTERIZING LOGGERHEAD SHRIKE HABITAT WITH LOCAL AND 

REMOTELY-SENSED DATA 

DR. ANNA PIDGEON 

University of Wisconsin, Madison 

Department of Forest and Wildlife Ecology 

1630 Linden Avenue 

Madison, WI 53706 

(608) 262-5628 

apidgeon@wisc.edu 

CO-PERFORMER: Veronique St-Louis (University of Wisconsin, Madison) 

onservation planning for animal species of concern frequently involves use of habitat 

models. Throughout a region, both abundance of a species and measures of its fitness (e.g., 

survival, reproductive success) may be unevenly distributed, often due to gradients in habitat 

quality. Thus selecting both the environmental factors that characterize abundance and fitness, 

and the ecologically relevant scales at which to measure them, are goals of habitat modeling. In 

this project we developed habitat models for the Loggerhead Shrike (Lanius ludovicianus) in the 

northern Chihuahuan Desert (Fort Bliss, New Mexico). We examined abundance during the 

breeding season using point counts. Measures of individual bird fitness (e.g., clutch size, nest 

success, and proportion of nestlings that fledged) obtained from the survey of 73 nests were used 

as surrogates for habitat quality. Habitat was measured at three spatial scales: (1) Local, 

characterized by foliage height diversity and shrub density in the vicinity of the nest or point 

count location; (2) Intermediate, characterized by image texture of the Normalized Difference 

Vegetation Index in an 11H11 window around each nest or point; and (3) Broad scale, 

characterized by proportion of grasslands, grassland/shrubland edge density, and patch richness 

within a 1 km buffer around each nest or point count location. We found that intermediate-scale 

variables were best for explaining patterns of habitat use (abundance, number of nests), perhaps 

because they quantify habitat heterogeneity within Shrike territories. We also found that the 

measures of habitat use we examined failed to distinguish habitat quality (i.e., fitness measures) 

for this species. These results broaden our understanding of the spatial scale at which habitat 

selection occurs in the Loggerhead Shrike in semi-arid ecosystems. 


G-42




H 

UNDERSTANDING THE IMPACTS OF HABITAT FRAGMENTATION IN 

COMPLEX LANDSCAPES 

DR. LESLIE RIES 



College Park, MD 20742 

(301) 405-0865 

lries@umd.edu 

CO-PERFORMERS: Thomas D. Sisk (Northern Arizona University); 

Emma Goldberg (University of Maryland) 

abitat fragmentation and local land-use decisions are two of the major factors driving 

habitat quality for threatened and endangered species. Over the past several decades, a 

significant body of theory has been developed to help managers and researchers understand 

conceptually how different landscape structures may impact habitat quality. However, the 

practical application of these principles is complicated by a theoretical and empirical body of 

work that is focused on highly simplified landscape structures. Simplified landscapes have 

practical value in trying to tease out ecological dynamics within complex systems, but then fail 

when trying to apply the principles in most real landscapes. This problem is well-illustrated by 

decades of research with hundreds of scientific reports on how organisms respond to the 

presence of habitat edges. The vast majority of these studies are designed to understand edge 

responses along “ideal” edges, which are straight, extend in both directions beyond the range of 

edge influence, and have two distinct habitat types on either side of the edge. In real landscapes, 

patches have convoluted, complex shapes where many different habitat types converge, and the 

distance to the nearest edge may not be a good measure of edge influence. There have been only 

a handful of studies addressing the effects of complex patch geometry, partly due to a lack of 

available tools to help researchers and managers understand or apply local edge influences over 

complex landscapes. A model based on line integrals published in 1994 suggests an approach to 

understanding how local edge influences extrapolate over entire landscapes, but it is intractable 

in its current form because it requires a new solution for every unique shape in a landscape. We 

developed solutions to the model for several simple shapes and show how the model improves 

predictions over simple distance-to-nearest-edge measures for two endangered species in Fort 

Hood, Texas. We then show how we are developing an approximation of the model that will be 

implemented within the Effective Area Model, a GIS-based tool for predicting how edges 

influence habitat quality in real landscapes. 


G-43




L 

A LIFE-HISTORY BASED MULTI-SPECIES FRAMEWORK FOR LANDSCAPE 

CONNECTIVITY CONSERVATION 

R. TODD JOBE 

The University of North Carolina at Chapel Hill 

Saunders Hall 

CB#3220 

Chapel Hill, NC 27599-3220 

(919) 933-8906 

toddjobe@unc.edu 

CO-PERFORMERS: Aaron Moody and Anne Trainor (UNC) 

and managers must consider the dispersal needs of many species when prioritizing 

ecosystem patches for conservation. Part of this consideration is evaluating the 

connectedness of habitats for many species at once. Assessment of habitat connectivity often 

entails the collection of very detailed dispersal behaviors. Such data collection may not be 

possible for many species, however, and other methods of assessing connectivity must be used. 

Here, we present a unified framework assessing habitat connectivity of a species based on 

general life history characteristics. Such characteristics are available for many species, even in 

the absence of detailed dispersal data. Around this general framework we synthesize data from 

species with known dispersal behavior but with varying life histories, including data from a 

group of study species for which we are collecting detailed movement and dispersal data at Fort 

Bragg, NC. Given a suite of species, we can prioritize particular communities and ecosystems 

based on their cumulative value for wildlife movement and persistence in a multi-species, or 

community context. This ecosystem approach has the advantage that ecosystem patches are 

readily delineated from remotely sensed data. We apply this framework to four species on Fort 

Bragg and compare the results of assessing connectivity based on movement data to the lifehistory 

based connectivity assessment. This comparison suggests that the life-history based 

approach may provide a filter from which species may be selected for more detailed connectivity 

assessment. Such species may be considered indicators for connectivity. Using the two 

approaches in concert increases both the accuracy and efficiency of prioritizing habitat patches 

for conservation. 


G-44




CONNECTIVITY OF RED-COCKADED WOODPECKER (PICOIDES BOREALIS) 

HABITAT IN THE SANDHILLS REGION OF NORTH CAROLINA 

ANNE TRAINOR 

University of North Carolina 

Department of Geography 

Campus Box 3220 

Chapel Hill, NC 27705 

(919) 619-4678 

atrainor@email.unc.edu 

CO-PERFORMERS: Dr. Aaron Moody (University of North Carolina); Dr. Jeffrey R. Walters 

(Virginia Polytechnic Institute and State University) 

H 

abitat loss and fragmentation due to human land uses have drastically altered the size and 

configuration of ecosystems and severely reduced many wildlife populations. The 

persistence of these reduced populations depends upon the degree to which landscape features 

facilitate or impede movement between the remaining habitat patches. This ‘habitat connectivity’ 

is usually quantified as the Euclidian distance between habitat fragments. Unfortunately, simple 

distance measurements fail to account for biological factors that determine animal movements 

between these patches. One prominent example in which habitat connectivity plays an important 

role in the persistence of wildlife populations is the federally endangered red-cockaded 

woodpecker (RCW; Picoides borealis), which is endemic to mature longleaf pine woodland. 

These woodlands once covered over 360,000 km 2 in the southeastern United States but now exist 

only as small scattered patches covering only 3% of its former area. Currently, Fort Bragg 

contains some of the largest intact remnants of longleaf pine ecosystems and the largest RCW 

population in North Carolina. To quantify RCW habitat connectivity within longleaf pine forest, 

we have constructed a ‘landscape resistance layer’ by predicting how landscape features affect 

RCW dispersal behavior based on data from 36 radio tagged individuals in 2006 and 2007 on 

Fort Bragg. We then evaluated whether RCWs exhibit a directional bias during forays by 

comparing the observed foray orientations with all possible foray orientations within each 

individual’s maximum observed foray distance. Further, we examined whether the predicted 

resistance layer can be used to explain the directionality in the foray movements. Based on 

conditional logistic regression, RCW movements were positively associated with longleaf 

(B = 0.517, SE = 0.1083, p-value < 0.001) and non-longleaf pine forest (B = 0.489, SE = 0.1466, 

p-value < 0.001) and negatively associated with a high density of large hardwoods (B = -0.056, 

SE = 0.0161, p-value < 0.001). Therefore, pine forests yield the lowest resistance value for RCW 

extraterritorial movements, while dense large hardwoods yield the greatest resistance value 

among forest types. RCW also exhibited significant directional bias during foray movements and 

oriented themselves towards a subset of available territories (X 2 = 64.023, p-value = 0.002, 

df = 35). Increased knowledge of RCW dispersal behavior will help identify areas necessary to 

maintain habitat connectivity and should be useful in establishing and implementing effective 

RCW management strategies. This research is supported by the Strategic Environmental 

Research and Development Program (SERDP Project SI-1471). 

G-45




THE EFFECTS OF HABITAT FRAGMENTATION AND CONNECTIVITY ON THE 

M 

MOVEMENT BEHAVIORS OF A RARE AMPHIBIAN 

DR. NICOLE Y. THURGATE 


Department of Zoology 


Raleigh, NC 27695-5327 

(919) 515-1980 

nythurgate@yahoo.com 

CO-PERFORMERS: Will Fields and Dr. Nick Haddad (North Carolina State University) 

aintaining landscape connectivity for diverse groups of rare species is a significant 

challenge to effective conservation. For rare pond breeding amphibians, adults typically 

remain at the same breeding ponds, whereas it is primarily juveniles that disperse from natal 

ponds. In fragmented landscapes, juveniles must disperse across different habitat types and spend 

time in potentially unsuitable habitat in order to reach other breeding sites. We used two 

complementary approaches to assess connectivity for rare amphibians at Fort Bragg. First, we 

conducted experimental releases of two amphibian species, the rare Carolina gopher frogs (Rana 

capito) and a more widespread species, southern leopard frog (Rana sphenocephala). Juvenile 

frogs were released into enclosures straddling a boundary between pine forest and an open field. 

We compared movements of these frogs within corridors to examine how movement behavior 

may be linked to the conservation status of a species. We found that the two species had distinct 

habitat preferences with Carolina gopher frogs showing an apparent preference for clear-cut open 

fields and southern leopard frogs dispersing into forest habitat. This result highlights the 

complexity of managing habitats for multiple rare species. Other rare species on Fort Bragg such 

as the endangered red-cockaded woodpecker and St. Francis satyr butterfly avoid crossing open 

habitat while gopher frogs prefer them to forest. We also developed a predictive model for 

potential wetland breeding habitat across Fort Bragg using a geographic information system. 

This model was validated with field surveys and produced a map of potential wetland breeding 

sites. Our results from mapping wetland habitat provide a template for future studies to model 

connectivity for amphibians and other rare species. Habitat maps can be combined with 

information on movement behavior to provide a framework for optimizing landscape 

connectivity at Fort Bragg and in the surrounding area. 


G-46




FINAL ASSESSMENT OF DTK9 TEAMS – 2008 FIELD TESTING RESULTS 

MARY E. CABLK, PH.D. 

Desert Research Institute 

2215 Raggio Parkway 

Reno, NV 89512 

(775) 673-7371 

mary.cablk@dri.edu 

CO-PERFORMERS: Cindee Valentin (Applegate School for Dogs); Dr. Kenneth E. Nussear and 

Dr. Todd C. Esque (U.S. Geological Survey); Dr. Susan Clark (Dynamic Competence); 

Dr. Russell S. Harmon (U.S. Army Research Office) 

T 

he objectives of the 2008 field season were to validate the ability of Desert Tortoise-canine 

(DTK9) teams to locate tortoises in the field setting at natural population densities and size 

classes as the final demonstration. The scope of the work included an initial phase of training and 

evaluation of DTK9 teams to find both adult and small desert tortoises less than 180 mm at the 

Desert Tortoise Conservation Center (DTCC), followed by a capability assessment under natural 

field conditions in desert tortoise critical habitat near Las Vegas, NV. The DTK9 team 

capabilities were quantified by the combination of safety, efficacy and reliability as well as time 

and cost. Both new and veteran dog teams were successfully trained, tested and fielded in April 

2008. A series of three tests were designed to demonstrate capability, defining the minimum 

level of proficiency expected of dog teams who would conduct tortoise surveys professionally 

based on quantitative metrics. The first assessment was a basic safety challenge to the dogs. The 

second assessment was a high tortoise density scenario. Safety, reliability, efficacy, the handler’s 

ability to implement a variable-intensity reward system and in-field calibration were evaluated. 

The final assessment was a low tortoise density scenario where teams were evaluated on their 

capability to work after ~ 3 hours without finding a tortoise. Teams were not informed whether 

or not they received a ‘pass’ score for certification based on these three tests. A score of ‘pass’ 

required that all criteria were met for all three assessments. All teams, regardless of whether or 

not they passed the certification criteria were fielded during tortoise survey trials in Piute Valley, 

NV. The purpose of fielding teams that passed and that did not pass was to compare performance 

during the certification assessments with actual field performance. In this manner, we were 

testing the test. Teams found desert tortoises of all size classes including wild hatchling tortoises 

approximately 55 mm in length. Results from the field performance indicated that the assessment 

results carried through to the field. The advantages of using DTK9s for locating desert tortoises 

will include: (i) providing improved desert tortoise population estimates; (ii) the ability to collect 

the data necessary to complete life-tables and improve demographic knowledge; and (iii) having 

an alternative and cost-effective solution for conducting desert tortoise surveys that allocate the 

full range of desert tortoise size classes. 

This work is funded by ESTCP Project SI-0609. 

G-47




FORECASTING THE EFFECTS OF LAND-USE CHANGE ON RED-COCKADED 

WOODPECKERS AT FORT BENNING, GEORGIA USING A SPATIALLY 

EXPLICIT INDIVIDUAL-BASED MODEL (HEXSIM) 

DR. BETSY A. BANCROFT 


College of Forest Resources 

Box 352100 

Seattle, WA 98195-2100 

(206) 543-5772 

betsyba@u.washington.edu 

CO-PERFORMERS: Dr. Joshua J. Lawler (University of Washington); Dr. Nathan Schumaker 

(U.S. Environmental Protection Agency) 

M 

anagers on military installations are often faced with balancing the training needs of the 

military with the protection of threatened and endangered species (TES) on post. In 

particular, the changes associated with the U.S. Army’s Transformation may have large impacts 

on TES at installations around the country. Fort Benning is undergoing development to 

accommodate this Transformation, including the creation of the Maneuver Center of Excellence. 

Fort Benning has approximately 275 active red-cockaded woodpecker (Picoides borealis; RCW) 

clusters, with a goal of 450 active clusters. As part of SERDP Project SI-1541, we are improving 

an existing spatially explicit individual-based model called HexSim (formerly PATCH). We used 

HexSim to explore the potential effects of land-use changes and development associated with 

Transformation on RCW at Fort Benning. We parameterized the model using data from Fort 

Benning and data collected at other locations and successfully reproduced the current 

approximate distribution and abundance of RCW at Fort Benning. We then altered the landscape 

to reflect future development projects relating to Transformation. This new landscape was used 

to forecast the effects of Transformation on RCW at Fort Benning. In anticipation of continuing 

growth of the Army, we created 10 alternate land-use scenarios for Fort Benning extending 

beyond the current Transformation, assuming a 50% increase in training/troop levels over 100 

years. We used the range developments from the various current Transformation projects as a 

framework to guide our scenarios. Our results suggest that future land-use change will likely 

have a negative impact on the RCW population at Fort Benning and that the level of impact will 

depend on the spatial arrangement of future development. 

G-48




ENERGETIC COST OF SIMULATED MILITARY TRAINING ACTIVITIES IN 

SONGBIRDS 

DR. ISABELLE-ANNE BISSON 

Princeton University 

Department Ecology and Evolutionary Biology 

Princeton, NJ 08544 

(609) 258-7925 

ibisson@princeton.edu 

CO-PERFORMERS: Dr. Tim Hayden (Army Corps of Engineers); Dr. Luke Butler and 

Dr. L. Michael Romero (Tufts University); Dr. Martin Wikelski (Max Planck Institute/Princeton 

University) 

U 

nderstanding how species respond and adapt to military-related activities is a crucial step 

towards developing workable and sustainable military practices for species of concern. For 

three consecutive seasons (2006, 2007, and 2008), we used heart rate telemetry to determine both 

acute and chronic effects of simulated military-related stressors on White-eyed Vireos and 

endangered Black-capped Vireos at the Fort Hood military installation in Texas. Heart rate 

telemetry allows direct and continuous monitoring of acute responses to human disturbance and 

chronic energy demands in relation to these stressors. Heart rate was obtained by fitting each 

captured bird (14 White-eyed Vireos and 10 Black-capped Vireos) with 0.5g heart rate 

transmitters (Sparrow Systems, Inc.) and continuously recorded for 60 hours using MP3 

recorders. We calibrated heart rate to energy expenditure for five additional males using an open 

flow, push-through respirometry system showing that heart rate predicted 73.5% of energy 

expenditure. We conducted standardized disturbance trials in the field to experimentally simulate 

a natural stressor, predator presence, and two anthropogenic stressors. Although birds initially 

showed behavioral and heart rate reactions to some disturbances, we could not detect an overall 

increase in energy expenditure during one- or four-hour disturbances. Similarly, overall activity 

rates were unaltered between control and experimental periods and birds continued to perform 

parental duties despite the experimental disturbances. We suggest that vireos quickly determined 

that disturbances were non-threatening and thus show no (costly) physiological response. We 

hypothesize that the lack of a significant increase in energy expenditure in response to 

disturbance in vireos is exemplary for animals with fast life histories. Fast-living animals will 

need to quickly adapt to environmental disturbances so as to maximize energy allocation to 

reproduction. We expect slow-living animals to be much more prone to disturbances. Data 

specific to Black-capped Vireos will be presented at the meeting. 


G-49




INTEGRATION AND VALIDATION OF AVAIN RADARS (IVAR) 

MARISSA BRAND 


53475 Strothe Road 


(619) 553-5334 

marissa@spawar.navy.mil 

CO-PERFORMERS: Gerry Key (Computer Sciences Corporation); Dr. Tim Nohara (Accipiter 

Radar Technologies, Inc.); Dr. Sid Gauthreaux (Clemson University) 

S 

cientists and engineers from the federal government, industry, and academia are evaluating 

data from digital radar systems to identify and track biological targets, and then validating 

these systems under realistic operational conditions. The eBirdRad radar unit utilizes off-theshelf 

X-band marine radar coupled with advanced digital signal processing and tracking 

algorithms to process target information. Overall project objectives include: (1) the use of 

independent visual, thermal and other observations to validate automatic detection, tracking, and 

display of targets in real-time; (2) demonstrate the statistical validity of sampling protocols for 

bird activity; (3) validate protocols and algorithms for streaming real-time bird track data from 

multiple sites for immediate display and subsequent analyses; (4) demonstrate algorithms for 

fusing data from multiple radars; (5) capture baseline data on bird activity at the demonstration 

sites; (6) develop objective criteria for functional, performance, and interoperability requirements 

of these radars, and (7) to guide research to extend avian radar technology. The dissemination of 

information through the peer review process is essential before the natural resources 

management community can effectively use radar to assist in the decision making process. This 

project will demonstrate that avian radar systems can provide natural resource managers and air 

safety personnel with improved tools for automatically monitoring the abundance and behavior 

of resident and migratory birds. 

This work is funded by ESTCP Project SI-0723. 

G-50




CONSERVATION OF THREATENED, ENDANGERED AND SENSITIVE PLANT 

SPECIES ON FEDERAL LANDS IN THE SOUTHEASTERN FALL LINE SANDHILLS 

DR. REBECCA R. SHARITZ 

Savannah River Ecology Laboratory 

P.O. Drawer E 


(803) 725-5679 

sharitz@plantbio.uga.edu 

CO-PERFORMERS: Dr. Donald W. Imm and Dr. Tracey D. Tuberville (Savannah River 

Ecology Laboratory); Dr. Harold E. Balbach (U.S. Army Engineer Research and Development 

Center) 

I 

n the southeastern United States, the Department of Defense (DoD) has extensive land 

holdings along the Fall Line, which occurs between the Coastal Plain and the Piedmont 

provinces. Sandhills throughout this region support a unique flora and fauna, including a suite of 

threatened, endangered and sensitive (TES) plant and animal species. As a result of land uses 

such as agriculture, forestry and urban development, these sandhills woodlands have become 

fragmented and reduced in extent. Thus, military installations along the Fall Line have become 

increasingly important preserves for remaining sandhills species. The DoD must address 

simultaneously the habitat sensitivities of TES species along with demands associated with 

military training and other land-use activities. The objectives of this SERDP-funded research 

(SI-1302) include evaluating habitat characteristics and developing habitat models for selected 

TES sandhills plants, and proposing conservation strategies that are compatible with other land 

use requirements. Populations of nine TES plant species occurring on three Federal installations 

(Fort Benning and Fort Gordon, GA and the Department of Energy’s Savannah River Site, SC) 

were surveyed and their habitat conditions determined, including soil characteristics, canopy 

openness and vegetation composition. GIS analysis using Landsat-7 Enhanced Thematic Mapper 

Plus imagery (leaf-on, leaf-off), and soils information from TES plant populations, were used to 

identify potential additional TES plant habitats, with extensive overlap among species. In 

addition, experimental transplant gardens were established to test specific responses of several of 

the TES plant species to habitat disturbances associated with military training and forest 

management, as well as to examine their potential for population restoration through 

transplantation. Finally, comparison of potential habitat locations of TES plants with known 

burrow locations of the gopher tortoise (Gopherus polyphemus, a TES animal species) at one 

installation revealed that 58% of the burrows were within areas identified as probable habitat for 

one to five of the TES plants. Thus, conservation strategies for at-risk sandhills animal species 

may provide some protection for rare sandhills plants. A holistic conservation approach that 

integrates the habitat sensitivities of multiple TES species, both plant and animal, is 

recommended for military installations along the southeastern Fall Line sandhills. 


G-51




A DECISION SUPPORT SYSTEM FOR IDENTIFYING AND RANKING CRITICAL 

HABITAT PARCELS ON AND IN THE VICINITY OF DEPARTMENT OF 

N 

DEFENSE INSTALLATIONS 

JEFFREY R. WALTERS 

Virginia Polytechnic Institute and State University 


Blacksburg, VA 24061 

(540) 231-3847 

jrwalt@vt.edu 

CO-PERFORMERS: Paige Baldassaro and Ken M. Convery (Conservation Management 

Institute) 

atural resource managers at Department of Defense (DoD) installations are faced with the 

enormous challenge of balancing natural resource demands and federal regulations, while 

simultaneously providing superb training lands. This challenge is exacerbated at installations 

where federal endangered species regulations prohibit or constrain management options and 

training opportunities. 

Because of its endangered status and large area requirements, the red-cockaded woodpecker 

(RCW; Picoides borealis) has become the focal point for threatened and endangered species 

(TES) conservation on military installations in the Southeast and affects natural resource 

management and training activities more than any other species in this region. 

We have developed a user-friendly geographic information system (GIS)-based, spatiallyexplicit 

decision support system (DSS) to help land managers at southeastern DoD installations 

explore the potential effects of various management scenarios on red-cockaded woodpecker 

populations. This tool will be useful to managers and researchers alike, and will provide a basis 

for management decisions that support both endangered species and military training goals. 

In this poster, we illustrate the benefits and features of the DSS using the actual landscape and 

RCW populations at Fort Bragg, Fort Benning and Camp Lejuene. To accomplish this, we 

worked with installation managers to identify several realistic management scenarios and used 

the tool to project the future impact of these scenarios on biologically significant parameters such 

as the size and growth rate of RCW populations. For example, we used the tool to evaluate how 

land acquisition (habitat restoration) and range expansion (habitat destruction) options may 

affect future RCW population size, and assessed the likelihood of occupancy of potential 

recruitment clusters among alternative locations. 

The DSS includes an easy to use wizard style interface and integrates with ESRI ArcMAP. It 

requires only limited GIS skills and uses readily available spatial data. It is currently available 

for beta testing and will be officially released in June 2009. 


G-52




AN ENSEMBLE APPROACH TO MODELING BLACK-CAPPED VIREO HABITAT 

FOR USE IN A SPATIALLY EXPLICIT INDIVIDUAL-BASED MODEL 

C 

CHAD B. WILSEY, M.S. 


College of Forest Resources 

Box 352100 

Seattle, WA 98195-2100 

(206) 543-5772 

cbwilsey@u.washington.edu 

CO-PERFORMERS: Dr. Betsy A. Bancroft and Dr. Joshua J. Lawler (University of 

Washington); Dr. Nathan Schumaker (Environmental Protection Agency) 

hanges in natural disturbance regimes associated with fire suppression and a shifting climate 

may negatively affect threatened and endangered species (TES) occupying shrub habitats 

useful for military activities. Therefore, complying with endangered species protection 

regulations while simultaneously implementing the U.S. Army’s Transformation will require 

tools that assess the extent of shrubland habitat critical for TES populations. We used Random 

Forest, an ensemble-modeling approach that averages the predictions of multiple randomly 

generated classification trees, to construct a habitat model for the black-capped vireo (Vireo 

atricapilla, BCVI) population at Fort Hood, TX. In direct comparisons, the Random Forest 

ensemble-modeling approach outperformed any single classification tree model. Using the 

model, a surface of habitat quality was created for the entire installation and used as the 

landscape for a spatially explicit individual-based model (HexSim) of the Fort Hood BCVI 

population. We parameterized the population model using data from Fort Hood and successfully 

approximated current BCVI distribution and abundance on post. As part of SERDP Project 

SI-1541, the HexSim BCVI model will be used to analyze the potential effects of climate change 

and management on BCVI populations into the future. 

G-53




CAUSES OF LOW HATCHING SUCCESS OF GOPHER TORTOISE (GOPHERUS 

POLYPHEMUS) EGGS AT CAMP SHELBY, MISSISSIPPI 

T 

DR. CARL QUALLS 

University of Southern Mississippi 

Biological Sciences 

118 College Drive #5018 

Hattiesburg, MS 39406-0001 

(601) 266-6906 

Carl.Qualls@usm.edu 

CO-PERFORMERS: Thomas Smith (U.S. Army Corps of Engineers, ERDC-CERL); 

Joshua Ennen (University of Southern Mississippi) 

he gopher tortoise, Gopherus polyphemus, inhabits numerous DoD installations in the 

Southeast, including Camp Shelby in Mississippi. The species has ESA Threatened status in 

the western portion of its range (western AL, MS, and LA) and is of conservation concern 

throughout its range. Thus, protection and recovery of this threatened species is an integral part 

of the military’s environmental stewardship obligation, at Camp Shelby and elsewhere. Despite 

ongoing conservation efforts, western populations of gopher tortoises (including those inhabiting 

Camp Shelby) are declining and their age-class distributions are heavily skewed toward adults– 

suggesting unsustainably low recruitment. This lack of recruitment is largely due to 

unexpectedly low hatching success of the tortoises’ eggs, resulting from a combination of 

intrinsic (egg quality) and extrinsic (nest environment) problems. We present a combination of 

field and laboratory-based studies to determine the causes of observed low hatching success of 

gopher tortoise eggs at Camp Shelby. Our research includes population genetic studies to assess 

genetic variation within and among populations, as well as artificial nest experiments to identify 

specific environmental factors that lead to egg mortality. Results to date indicate that the western 

populations studied exhibit substantially lower genetic variation than do similar-sized eastern 

populations, which experience higher egg hatching success. Thus, low genetic variability may 

contribute to low egg fertility and/or high embryo mortality, explaining a portion of the eggs’ 

failure to hatch. Prior research also indicates that many eggs that are intrinsically capable of 

hatching fail to do so, because some aspect of their nest environment is insufficient to support 

their full development. We have identified the particulate composition of nest soils, specifically 

their clay content, as a strong correlate of hatching success in nests, and are experimentally 

evaluating its effects on hatching success. We hypothesize that high-clay soils may detrimentally 

limit gas exchange within nests, by reducing the diffusive exchange of respiratory gases into and 

out of nests through the soil. Eggs were placed into experimental pairs of nests in both high-clay 

and low-clay content soils which were otherwise constructed identically. These nests are being 

monitored to determine the hatching success of the eggs within them, as well as their 

temperatures and other environmental characteristics. We are also monitoring the respiratory 

microenvironment within each nest weekly, by extracting small samples of interstitial air from 

each nest and measuring their oxygen and carbon dioxide content. 

G-54




MODELING POPULATION VIABILITY OF SPECIES OF CONCERN USING 

COUNT DATA 

DR. KATHERINE STRICKLER 


College of Natural Resources 

Department of Fish and Wildlife Resources 

Moscow, ID 83844-1136 

(208) 885-4343 

kstrickler@uidaho.edu 

CO-PERFORMERS: Dr. Oz Garton, Dr. Jon Horne, and Dr. Brian Dennis (University of Idaho); 

Dr. L. Scott Mills and Dr. Cynthia Hartway (University of Montana); 

Dr. J. Michael Scott and Dr. Matthew Kauffman (U.S. Geological Survey) 

N 

atural resource managers are often asked to predict the effects of different management or 

training activities on populations of threatened or endangered species. Estimation of a 

population's viability is thus an important component of endangered species management. 

Although population viability can be estimated from age or stage-specific vital rates, 

demographic data are difficult to measure and often incomplete. The most commonly available 

data for most species are counts or abundance estimates over time, and there is a need to evaluate 

and improve methods for estimating population viability using these data. Several methods have 

been used to model population dynamics and subsequent viability. These methods are based on 

time-series abundance data with differing assumptions of sampling error, environmental 

stochasticity and effects of density dependence. However, assumptions of these models can be 

abstruse, and the models are often numerically intensive to implement without specific, prewritten 

software packages. As a result, managers and applied ecologists have not been able to 

take advantage of these new techniques effectively. We have developed a paired set of software 

packages called TimeSeriesPVA and MetaPVA, which model population and metapopulation 

viability by estimating relevant parameters of stochastic population growth models based on a 

time-series of abundance data. The software includes most of the models that have been 

developed for this type of data including those based on exponential growth, density dependent 

growth, and population growth influenced by environmental covariates. After estimating model 

parameters, these estimates are then used to infer population viability under different 

management scenarios. We report here on an evaluation of the different modeling approaches 

and their application to sage grouse (Centrocercus urophasianus) populations on and around 

Department of Defense installations in the western United States. 


G-55




WHEN DO WE KNOW ENOUGH TO RE-ALLOCATE LISTED SPECIES 

HABITAT 

DOUGLAS BRUGGEMAN 

Michigan State University 

13 Natural Resources 

East Lansing, MI 48824 

(513) 304-2300 

bruggem3@msu.edu 

CO-PERFORMERS: Thorsten Wiegand (UFZ Helmholtz Centre for Environmental Research); 

Michael Jones (Michigan State University) 

R 

e-allocating habitat for listed species provides a critical management tool for achieving 

military readiness and forging conservation partnerships outside of installation boundaries. 

However, re-allocating habitat for small and/or declining populations may affect the long term 

persistence of species. Landscape ecology is just beginning to understand the impacts of 

landscape dynamics on non-equilibrium populations. Individually-based, spatially-explicit 

population models are capable of reproducing population patterns in dynamic landscapes. 

However, these models were initially criticized due uncertainty associated with model 

predictions. Decision Analysis provides a structured approach for evaluating choices in the face 

of uncertainty regarding system dynamics. We devised a spatially-explicit decision analysis to 

evaluate habitat trades by integrating Pattern-Oriented Modeling (POM) with Landscape 

Equivalency Analysis (LEA). Pattern-Oriented Modeling (POM) provides a method for 

minimizing model prediction error by testing the ability of a large number of alternative SEPMs 

to reproduce patterns observed in nature. The result is a suite of models equally capable of 

reproducing patterns in nature. The suite of models remaining after POM were applied to 

multiple habitat trading scenarios on Camp Lejeune. For each of the remaining models LEA was 

used to determine if habitat patches traded make equivalent contributions to rates of recruitment 

within a patch and rates of migration among patches. LEA accomplishes this by evaluating both 

demographic and genetic responses under a variety of landscape structures. We found that 

despite uncertainty regarding dispersal behaviors, all models remaining after POM were in 

agreement regarding which trade is best. However, we found that the demographic and genetic 

criteria used by LEA to evaluate trades did not agree, suggesting that on-base habitats contribute 

more to landscape function. The results are preliminary because the spatial scale of the study was 

limited, but will be expanded in the near future. 


G-56


Natural Resources Management — Maritime Sustainability 


A STUDY ON BEHAVIORAL RESPONSES OF BEAKED AND OTHER WHALES 

TO SONAR AND OTHER SOUNDS 

T 

PETER L. TYACK 

Woods Hole Oceanographic Institution 

MS #50 

Woods Hole, MA 02339 

(508) 289-2818 

ptyack@whoi.edu 

he responses of Blainville’s beaked whales (Mesoplodon densirostris) and pilot whales 

(Globicephala macrorhynchus) to carefully controlled exposures of mid-frequency sonar, 

killer whale and synthetic sounds have been studied using tags that record sound and behavior. 

The research was conducted on the AUTEC underwater range, which can detect and locate the 

sounds of these whales in the Tongue of the Ocean, Bahamas. This research is designed to 

provide new science-based approaches for mitigating the risk of sonar to beaked and other 

whales. During the first playback to a beaked whale, a simulated mid-frequency sonar sound was 

played back to a Blainville’s beaked whale as soon as it started producing echolocation clicks on 

a deep foraging dive. The source level (SL) was increased from a low level to 212 dB re 1 µPa at 

1 m over 9 min and then maintained at that maximum level for 6 min. The playback continued 

for several minutes once cessation of clicking was confirmed. The maximum received level (RL) 

recorded at the whale was ~140-150 dB re 1 µPa. When the whale surfaced, her behavior 

appeared normal to visual observers. After about 2 hours she started another deep foraging dive. 

Once she started clicking at depth, a playback of killer whale sounds was started. The SL was 

then increased slowly, reaching a maximum SL of 190-203 dB after 10 minutes. The whale 

stopped clicking about 5 minutes into the killer whale playback, a shorter clicking period than 

usual. The RL of the killer whale sounds recorded on the tagged whale just before she ceased 

vocalizing was ~107-117 dB. The sound exposure at the whale continued for several minutes 

once the cessation of clicking was confirmed. The maximum RL recorded at the whale was 

~123-134 dB. The beaked whale showed a clear reaction to these playbacks. Statistical models 

showed that, after accounting for the effects of differences between individuals and sex of the 6 

whales sampled, foraging and ascent behaviors were significantly affected by the playback. Both 

playbacks resulted in a significant reduction in attempts to capture prey (judged by the number of 

buzzes), significantly shorter foraging durations (judged by the production of clicks), 

significantly reduced ascent rate, and significantly increased ascent duration compared to the 

control foraging dives recorded from this species off Andros Island without playback. After the 

killer whale playback, the beaked whale moved away for at least 10 hours. 


G-57




OCEAN SONIC BOOM MODELS FOR ENVIRONMENTAL IMPACT OF SPACE 

C 

LAUNCH VEHICLE, SPACE REENTRY AND SUPERSONIC OVERFLIGHT 

DR. ADAM FINCHAM 

University of Southern California 

Aerospace and Mechanical Engineering 

854 W. 36th Place 

Los Angeles, CA 90089 

(213) 740-5356 

afincham@usc.edu 

CO-PERFORMERS: Mr. John Edwards and Mr. Adel Hashad (Space and Missile Systems 

Center); Dr. Charles Griffice and Dr. Johnson Wang (The Aerospace Corporation) 

onservation and protection of the marine environment in accordance with U.S. laws has 

been the goal of an on-going ocean sonic boom (OSB) study by the Space and Missile 

Systems Center’s (SMC) Acquisition Environmental Office and its technical support contractor, 

The Aerospace Corporation, a federally funded research and development center. Aircraft, rocket 

launch and space reentry vehicle sonic boom models have been studied theoretically and have 

been shown experimentally correct in many cases. However, in collaboration with the University 

of Southern California, SMC has been seeking to better understand and develop ocean wavy 

surface models that predict the biological effects of the sonic boom disturbances that occur over 

a wavy ocean surface. Failure to address OSB impacts on marine mammals is one of the primary 

risks to armed forces launch operations, just as space debris is to supersonic and hypersonic 

reentry operations. The current OSB models have theoretical and experimental implications that 

are unknown and controversial. Like the Navy’s use of sonar, military weapon systems 

operations may be at risk unless technical uncertainties and controversies are minimized by 

ensuring OSB model accuracy. 

G-58




APPLICATION OF VARIABLE FLUORESCENCE TECHNIQUE FOR ASSESSING 

T 

NATURAL AND ANTHROPOGENIC STRESSORS AT DOD CORAL REEFS 

DR. MAXIM GORBUNOV 


Institute of Marine and Coastal Sciences 

71 Dudley Road 

New Brunswick, NJ 08816 

(732) 763-8327 

gorbunov@marine.rutgers.edu 

CO-PERFORMERS: Dan Tchernov, Liti Haramaty, Sophia Johnson, and Paul Falkowski 

(Rutgers University) 

he development of advanced technologies for environmental monitoring of coral reef 

ecosystems requires an understanding of how different environmental factors affect the key 

elements of the ecosystems and the selection of specific monitoring protocols that are most 

appropriate for the identification and quantification of particular stressors. Bio-optical methods 

are particularly useful for rapid and non-destructive assessment of the viability of coral reef 

organisms. Here we present a methodology and instrumentation called Fluorescence Induction 

and Relaxation (FIRe) System for assessment of the photosynthetic and physiological status of 

corals and other benthic photosynthetic organisms. Within the framework of SERDP Project 

SI-1334, we have designed and developed bench-top, diver-operated and moorable instruments. 

The variable fluorescence technique relies on the relationship between chlorophyll fluorescence 

yield and the efficiency of photosynthetic processes and provides a comprehensive suite of 

photosynthetic and physiological parameters, including: the quantum yields of photochemistry 

in Photosystem II (PSII); the functional absorption cross section of PSII; the rates of 

photosynthetic electron transport on the acceptor side of PSII and between PSII and PSI; as well 

as the coefficients of photochemical and non-photochemical quenching. In combination with 

conventional biochemical and molecular biological methods, the FIRe technique was employed 

to study the impact of common natural stresses (episodes of elevated temperature and excess 

irradiance), as well as selected anthropogenic factors (heavy metal contamination) on coral. The 

analysis revealed that different stressors lead to specific modifications to the coral symbioses and 

are characterized by unique FIRe fluorescence signatures that can be used for quantitative 

assessment of coral health and selective identification of the stressors. 


G-59




HIGH RESOLUTION LANDSCAPE MOSAICS FOR CORAL REEF MONITORING 

C 

DR. R. PAMELA REID 

University of Miami 

Rosenstiel School of Marine Atmospheric Science 

4600 Rickenbacker Causeway 

Miami, FL 33149 

(305) 421-4606 

preid@rsmas.miami.edu 

CO-PERFORMERS: Dr. Nuno Gracias, Dr. Diego Lirman, Art Gleason, and Brooke Gintert 

(University of Miami); Dr. Philip Kramer (The Nature Conservancy) 

omprehensive assessment of reef condition is fundamental to Department of Defense (DoD) 

marine operations in tropical areas. Successful and legally defensible assessments of reef 

damage or documentation of declines in reef vitality associated with DoD operations require reef 

monitoring techniques that are simple, accurate, repeatable, and appropriate to the scale of the 

damage. 

The aim of SERDP Project SI-1333 is to develop and evaluate an innovative technology, 

landscape mosaics created from underwater video, to provide DoD with improved reef 

monitoring capability. These mosaics create large scale (up to 400m 2 ), spatially accurate, high 

resolution images of the reef benthos without extensive survey time or a need for scientific 

divers. Based on diver-acquired video of the reef benthos and novel mosaicing algorithms, 

landscape mosaics have been used in the laboratory to extract indices of benthic cover, coral 

colony size, and colony health; lab-based measurements compare favorably with diver surveys. 

The spatially referenced images allow users to make accurate measurements (including colony 

area and diameter, and distance relationships for spatial analysis) directly from mosaics. 

Repeated surveys of the same area are easily referenced for change detection analysis and 

provide an image-based monitoring capability that can survey hundreds of coral colonies over 

time without the use of in situ tagging and underwater relocation. Landscape mosaics also 

provide a large-scale visual permanent record of the state-of-the-reef at the time of collection, 

which is accessible to both the scientific community and general public. To date the mosaicing 

technology has been used to detect and monitor changes in reefs responding to hurricanes, ship 

groundings, and mass bleaching events. 

Recent work within SI-1333 has focused on developing new software tools that extend the 

performance of the basic mosaicing package. The first tool addresses a common problem in 

shallow water video surveys: sun flickering. A new algorithm was created that significantly 

reduces sunlight flickering without affecting image quality. The second tool (blending) addresses 

the merging of multiple registered images into a single large mosaic. Over areas of high 

topography the standard algorithms for image merging result in excessive seams or blurriness 

due to small errors in the image registration. To address this issue, a new method was developed 

to place the seams in areas where those seams are least visible. These enhanced capabilities lead 

to significant improvements in the final mosaic product. 

G-60




PREDICTIVE MODELING OF MARINE MAMMALS AND SPATIAL DECISION 

M 

SUPPORT FOR NAVAL ENVIRONMENTAL COMPLIANCE 

DR. PATRICK HALPIN 


A324 LSRC Building 

Durham, NC 27708-0328 

(919) 613-8062 

phalpin@duke.edu 

CO-PERFORMERS: Dr. Andrew Read, Benjamin D. Best, Ei Fujioka, Lucie J. Hazen, 

Robert S. Schick, and Benjamin Donnelly (Duke University) 

anagement of areas used by marine mammal species require readily accessible estimates 

of the expected distribution and abundance of these species. In order to better meet this 

challenge, we have developed a data management, statistical modeling and decision support 

system to provide this information to planners and decision makers. This system incorporates 

dedicated surveys from the OBIS-SEAMAP marine data archive (http://seamap.env.duke.edu) to 

develop predictive habitat models and deliver the results with a flexible spatial decision support 

system (SDSS). The SDSS, a browser-based interactive map server, enables viewing of original 

survey effort, marine mammal observations, oceanographic imagery, and model results. A suite 

of multivariate statistical models (CART, GLM, GAM and Bayesian approaches) have been 

fitted to observations from at-sea surveys with remotely-sensed environmental data (bathymetry, 

sea-surface temperature, chlorophyll) as well as derived variables such as slope, temperature 

fronts and chlorophyll aggregations. Environmental data from the JPL physical oceanographic 

data archive (PO.DAAC) of past remotely-sensed satellite imagery is used to fit the model, while 

the oceanographic forecast data can be used to make current forecasts for appropriate time 

periods. Model results yield predictive maps for the likelihood of encounter as well as the 

associated standard error. Regions of interest can further be delineated within the SDSS for 

extracting summary statistical outputs, such as histograms and model statistics. The SDSS 

system allows users to view and query observation data and model results from this project as 

well as related SERDP projects and baseline geographic data. 

G-61




PREDICTIVE MODELING OF MARINE MAMMAL DENSITY FROM EXISTING 

T 

SURVEY DATA AND MODEL VALIDATION USING UPCOMING SURVEYS 

DR. JAY BARLOW 

NOAA - Southwest Fisheries Science Center 

8604 La Jolla Shores Drive 

La Jolla, CA 92037 

(858) 546-7178 

jay.barlow@noaa.gov 

CO-PERFORMERS: Elizabeth Becker; Megan Ferguson; Jessica Redfern; Karin Forney; 

Lisa Balance; Paul Fiedler; Nacho Vilchis 

he Navy and other users of the marine environment need to estimate cetacean density within 

their operational areas in order to comply with the requirements of the Marine Mammal 

Protection Act, the Endangered Species Act, and the National Environmental Policy Act. The 

goal of our SERDP-funded research is to develop methods to predict cetacean densities within 

any user-defined region in the eastern Pacific Ocean using habitat variables. This poster 

highlights cetacean-habitat models that we have developed for the California Current Ecosystem 

(CCE) and in the Eastern Tropical Pacific. Densities for individual species or groups of related 

species (termed guilds) were modeled as functions of oceanographic variables and other 

environmental characteristics. Generalized additive and generalized linear modeling approaches 

were used, and the resulting models were similar in most cases. Data from NOAA research 

surveys from 1986-2003 were used to parameterize the models, and models were validated using 

data from surveys in 2005-2006. 

We developed density models for 12 species or guilds in the CCE: striped dolphin (Stenella 

coeruleoalba), short-beaked common dolphin (Delphinus delphis), Risso’s dolphin (Grampus 

griseus), Pacific white-sided dolphin (Lagenorhynchus obliquidens), northern right whale 

dolphin (Lissodelphis borealis), Dall’s porpoise (Phocoenoides dalli), sperm whale (Physeter 

macrocephalus), fin whale (Balaenoptera physalus), blue whale (Balaenoptera musculus), 

humpback whale (Megaptera novaeangliae), small beaked whale species (Ziphius and 

Mesoplodon), and Baird’s beaked whale (Berardius bairdii). We developed density models for 

16 species, subspecies or guilds in the ETP: offshore spotted dolphin (Stenella attenuata), striped 

dolphin, rough-toothed dolphins (Steno bredanensis), short-beaked common dolphin , bottlenose 

dolphin (Turisops truncatus), Risso’s dolphin, eastern spinner dolphins (Stenella longirostris 

orientalis), whitebelly spinner dolphin (Stenella longirostris longirostris), sperm whale , Bryde’s 

whales (Balaenoptera edeni), blue whale, dwarf sperm whale (Kogia sima), Cuvier’s beaked 

whale (Ziphius cavirostris), pilot whales (Globicephala spp.), Mesoplodon beaked whales 

(Mesoplodon spp.), and small beaked whale (Ziphius and Mesoplodon). The density models were 

unique for each species, indicating that none shared exactly the same niche. Models developed 

for specific ecosystems (the CCE or the ETP) had greater predictive power than models that 

were developed from the pooled data. 

G-62


Engine Noise and Emissions 


A COMPREHENSIVE PROGRAM FOR CHARACTERIZATION OF EMISSIONS 

FROM MILITARY AIRCRAFT 

A 

DR. MENG-DAWN CHENG 


1 Bethel Valley Road 

Oak Ridge, TN 37831-6038 

(865) 241-5918 

chengmd@ornl.gov 

CO-PERFORMERS: Edwin Corporan (WP AFRL); Matthew J. DeWitt and 

Christopher Klingshirn (UDRI); Shannon M. Mahurin (ORNL); Robert Kagann and 

Ram Hashmonay (ARCADIS); Richard C. Shores and D. Bruce Harris (EPA) 

comprehensive emission-characterization program has been developed for military aircraft 

on the ground in ambient conditions. Emissions were measured in relation to several factors 

such as engine power setting, sampling configuration, as well as measurement technique. For a 

given pollutant, the emission index was calculated with respect to the engine power level. 

Sampling and measurement technologies utilized in this program are classified in two platforms. 

One class of the measurements perform on the plume sample physically extracted from jet 

engine exhaust, transfer of the exhaust material to time-integrated samplers and continuous 

measurement instruments, and analyzing the collected particulate matter and gases in-line on site 

or off-line in a laboratory after the campaign. The other class of the measurements do not extract 

or transfer sample material from the exhaust plume, instead they rely on optical remote sensing 

techniques for continuous plume measurement on-site. Thus, in principle it could prevent 

potential problems caused by sample extraction. This poster presentation will summarize our 

team’s research accomplishments over the life of SERDP Project WP-1401 program, and present 

the array of instruments and samplers used on both platforms. We will detail and address the 

assumptions needed for deriving emission factors also discuss the pros and cons of both 

measurement platforms in the context of aircraft exhaust characterization. Scientific problems 

unique to each platform and measurement techniques will be discussed. Recommendations for 

further research will be made in this poster presentation. 

G-63


General Interest 


A 

TOXIC INDUSTRIAL CHEMICAL DATABASE FOR THE INTELLIGENCE 

PREPARATION IN THE BATTLEFIELD PROCESS 

DR. K. JAMES HAY 


2902 Newmark Drive 

Champaign, IL 61822-1076 

(217) 373-3485 

kent.j.hay@usace.army.mil 

CO-PERFORMERS: Dr. Victor Medina (U.S. Army ERDC-EL) 

ssessment of evident Toxic Industrial Chemicals (TICs) and Toxic Industrial Materials 

(TIMs) is currently part of the Intelligence Preparation of the Battlefield (IPB) Process, but 

troops may be still at risk to exposure and/or terrorist TIC/TIM usage as weapons. TIC/TIM 

exposures may result during urban operations involving industrial or manufacturing facilities. 

Even if soldiers are adequately protected, TIC/TIM releases can affect neutral or friendly 

populations in the environs of an urban operation. A better understanding of the types of 

TIC/TIMs that may be present in a battlefield from industrial sources is needed as an important 

part of an assessment tool that could be incorporated into the IPB Process 

As part of the project funded by the Army Environmental Quality/Installations Program, titled 

“Rapid Environmental Assessment during the IPB Process”, a database of toxic industrial 

chemicals is being developed. This activity will develop a database containing common 

industrial processes, particularly those expected to be located at potential battlefields based on 

satellite imagery reconnaissance. Each industrial type will have associated TICs and TIMs that 

can be expected to be present. These will be entered into the database along with the expected 

hazard based on toxicity, quantity, and availability. The database will be tied to a GIS mapping 

system that will provide physical layout information to the soldier. Warfighters then may use this 

information to decide if and how to approach particular battlefield settings and operational 

situations. The information gathered for this database will be acquired through the investigation 

of government and industrial informational sources. Upon completion, the database will be in 

Oracle Spatial format and will be the basis made for inclusion into continuation of a more 

comprehensive effort to assess potential battlefields for TIC/TIM hazards. 

The current test database, which for now contains data for sixty-three of the highest priority 

chemicals, incorporates technical data organized into four information areas: identification, GIS, 

hazard assessment, and references. As part of the database, the calculated probability of 

encountering a hazard risk is presented to the user. One of the future goals will be to evaluate the 

effectiveness of GIS tools in locating chemical storage facilities. We envision a demonstration in 

which the system is applied to a known chemical facility. 

G-64


Waste Reduction and Treatment 


T 

VAPOR RECOVERY BY ELECTROTHERMAL SWING ADSORPTION 

DR. K. JAMES HAY 


2902 Newmark Drive 

Champaign, IL 61822-1076 

(217) 373-3485 

kent.j.hay@usace.army.mil 

CO-PERFORMERS: Dr. Patrick D. Sullivan (Air Force Research Laboratory); 

Dr. Mark J. Rood (University of Illinois) 

he development of new vapor recovery technologies can allow for the continued use of 

higher-performance chemicals, re-use of those chemicals, and lower overall emissions of 

Hazardous Air Pollutants/Volatile Organic Compounds (HAPs/VOCs). They may also alleviate 

concerns of greenhouse gas emissions from oxidative technologies. The most energy efficient 

method is adsorption, which is often economically or practically unfeasible with current 

technologies, such as granular activated carbon (GAC) with steam regeneration. VaPRRS was 

developed cooperatively by the University of Illinois, ERDC-CERL, and Air Force Research 

Laboratory (AFRL) as an economical adsorption technology to control emissions from 

Department of Defense (DoD) HAP/VOC emissions sources such as painting operations. 

VaPRRS is a new type of regenerative filter system, which uses a high-performance activated 

carbon fabric cloth (ACFC) contained within a vessel. Applying an electrical current regenerates 

the fabric by rapidly heating the fabric, which efficiently desorbs the contaminant with minimal 

heating of the vessel. The adsorbate is released and condensed onto the inner surface of the 

vessel and is collected as a liquid. The filter is ready for reuse after it cools. A major advantage 

of this technology over conventional systems is that the entire adsorption, desorption, and 

recovery process occurs in the same vessel. This ultimately reduces the size, complexity, and 

cost of the system. 

During a pilot field study at a paint booth at Fort Hood TX, the system achieved greater than 

99% control efficiency. Through ESTCP Project WP-0521, VaPRRS is being demonstrated at 

Hill Air Force Base on a portable system for painting the wheel wells of the C-130 aircraft. The 

portable paint booth encloses the painting operation so that evacuation of the hangar is not 

necessary during painting. However, control efficiency is important because the booth vents back 

into the hangar. A bed of GAC is currently used to adsorb the HAPs/VOCs in the paint booth 

exhaust. When the bed has become saturated, it is sent offsite for disposal or regeneration and a 

new bed is installed. This demonstration replaces that GAC bed with a VaPRRS unit. The 

VaPRRS unit has been scaled from an 80 cubic feet per minute (cfm) flow rate pilot system to 

a 2,000 cfm system. A newly designed and built regenerable ACFC filter array is being 

integrated into a portable paint booth treatment cart in preparation for an early 2009 field test. 

G-65




T 

BIOLOGICAL TREATMENT OF SOLVENT BASED PAINT 

MR. TOM TORRES 

Naval Facilities Engineering Service Center 

1100 23rd Avenue 


(805) 982-1658 

tom.torres@navy.mil 

he objective of this project is to demonstrate and validate that the on-site biological 

treatment of expired shelf life paint is an economically and technically practical solution to 

the problem of waste paint disposal. To accomplish this, a full-scale biological treatment system 

will be assembled using commercially available components and operated at the demonstration 

site (PWC Pearl Harbor, HI). Over the course of the project; design, cost, and performance data 

will be collected and used to validate treatment effectiveness and facilitate technology transfer. 

Pilot studies used conventional biological batch reactors and biofilters populated by mixed 

bacterial cultures to demonstrate the biodegradation of non-volatile and volatile components in 

expired shelf life, solvent-based paints to innocuous and non-hazardous end products. Paint is 

diluted with water and a centrifugal pump is used to recirculate the reactor contents and emulsify 

water insoluble components. Rapid degradation of the insoluble components occurs when 

bacteria colonize the surface of the emulsified components. To promote bacterial growth and 

enhance biodegradation, the emulsified paint is amended with vitamins, amino acids, and 

nitrogen and phosphorous, a pH controller is used to maintain a neutral pH, and a high-pressure 

blower provides air and mixing. Exhaust air is vented through a biofilter charged with compost 

where volatilized compounds are captured and degraded. Process water from the reactor is 

passed through a filter press unit and discharged to the sewer. Solids in the ultrafilter 

concentrate are captured in a filter press and disposed of as non-hazardous solid waste. 

Off-site disposal of expired shelf life paint costs $1.70 and $2.20 per pound for bulk waste and 

one gallon cans respectively, which results in a recurring charge to major facilities (Pearl Harbor, 

San Diego, and Newport) of more than $500K each per year. Based on the pilot studies and 

similar biological treatment systems that are used to treat industrial waste, the estimated cost 

(capital and operation and maintenance) to treat expired shelf life paint will be $0.30 to $0.60 per 

pound or ~ $230K/year, which represents a savings of $270K /year. Since the cost of a full-scale 

biological treatment system is ~ $600K, the return on investment for biological treatment is less 

than 3 years. 

This work is funded by ESTCP Project WP-0520. 

G-66




PROGRESS REPORT: QUALIFICATION, DEMONSTRATION, & VALIDATION 

OF COMPLIANT REMOVERS FOR AIRCRAFT SEALANTS 

AND SPECIALTY COATINGS 

MR. JIM TANKERSLEY 

Battelle 

5100 Springfield Pike, Suite 110 

Dayton, OH 45432-1261 

(937) 258-6724 

tankersleyj@battelle.org 

CO-PERFORMERS: Jeff Kingsley [AFRL/RXSA (PI)]; Diane Kleinschmidt (NAVAIR); Susan 

Saliba (UDRI); John Stropki (Battelle) 

T 

he Air Force, Navy, and commercial airline industry have funded numerous studies to 

identify and evaluate non-chemical, environmentally friendly technologies or processes for 

safely and efficiently removing degraded sealants and specialty coatings from the internal and 

external surfaces of aircraft structures. Technologies have included mechanical, light energy, as 

well as various combinations of these processes. The conclusion from these studies is that there 

is no one technology, method, or procedure that efficiently removes the various types of sealant 

or specialty coating materials without the risk of damaging the underlying substrates or surface 

coatings. 

This ESTCP funded project (WP-0621) has focused on identifying, qualifying, demonstrating, 

and validating an environmentally friendly substitute material or product for removing sealants 

and specialty coatings from aircraft structures. Candidate materials examined are COTS, and are 

assessed on how effectively each material removes different sealants used by Air Force, Navy, 

and commercial aircraft MRO facilities. Structural aerospace materials included 2024-T3 

aluminum alloy and two types of composites (graphite/bismaleimide and graphite epoxy). 

The first phase of the project has been successfully completed. Accomplishments have included 

a material/process baselining assessment, a downselection of sealant remover vendors/materials, 

a controlled set of laboratory testing of COTS materials for polysulfide sealant removal on 

various substrates, followed with successful process demonstration/validation testing performed 

at OO-ALC and FRC-SE. In 2008, the Project Team expanded the study to include newer, nonchromate 

containing polysulfide formulations, polythioether and polyurethane sealants, and an 

expanded array of specialty coatings applied to the external and internal surfaces of military 

aircraft structures. This second phase of the project will also seek to perform compatibility 

testing on a wider variety of composite substrates. The poster presented at this session will detail 

the results achieved thus far. 

AFRL is the lead for the project, and NAVAIR is a partnering agency. Battelle and UDRI are 

responsible for identifying vendors of compliant removers, down-selecting candidate materials, 

and coordinating laboratory and field demonstrations. Project-related technical information 

exchanges include stakeholders from specific Air Force Air Logistic Centers, Navy Fleet 

Readiness Centers, the Army, and commercial MRO organizations. 

G-67


Surface Engineering and Structural Materials 


O 

ROBOTIC LASER COATING REMOVAL SYSTEM 

RANDEL BOWMAN 

Oklahoma City Air Logistics Center 

3001 Staff Drive 

STE 2Y-31 

Tinker Air Force Base, OK 73145-3025 

(405) 417-2888 

randel.bowman@tinker.af.mil 

CO-PERFORMERS: Randall Straw (AFRL); James Arthur (CTC) 

klahoma City Air Logistics Center (OC-ALC), Headquarters Air Force Material Command 

(HQ AFMC/LGPE), and the Air Force Research Laboratory (AFRL) are currently leading 

the Robotic Laser Coating Removal System (RLCRS) program to demonstrate and validate a 

RLCRS as an alternative technology to the current chemical and mechanical methods that are 

used to remove coatings from large off-equipment aircraft components at Tinker Air Force Base, 

OK. This project will demonstrate the ability of this technology to meet the requirements for 

coatings removal in a production environment as well as the pollution reduction that can be 

achieved through its use across the Department of Defense (DoD). The RLCRS system will be 

designed to accommodate processing of large parts that are currently subjected to coatings 

removal operations once they are removed from the airframe. This project is funded by the 

Environmental Security Technology Certification Program (ESTCP) and HQ AFMC. 

This technology has the potential to reduce the environmental burden associated with coatings 

removal operations while reducing the labor and chemical costs and positively impacting the 

production schedule. The implementation of the RLCRS will also provide the maintenance 

facility with the flexibility to remove coatings from components of various sizes and geometries 

using a single system. 

The ultimate goal of the project was to design a system of commercially available off the shelf 

(COTS) components that can be easily integrated onto different robotic platforms. This will 

allow individual depots to adapt the technology to meet their specific configuration and space 

needs. 

The RLCRS system has been completed and implemented at OC-ALC. Demonstration of this 

system in accordance with the ESTCP Demonstration Plan has been completed and OC-ALC is 

currently moving forward with obtaining approvals to use the system on production KC-135 

parts. 


G-68




ULTRAVIOLET (UV)–CURABLE COATINGS FOR AEROSPACE APPLICATIONS 

O 

GLEN BAKER 

309 AMXG/EN 

5875 Southgate Avenue 

Building 225 

Hill Air Force Base, UT 84056-5231 

(801) 775-5596 

glen.baker2@hill.af.mil 

gden Air Logistics Center (OO-ALC), the United States Coast Guard (USCG) Aircraft 

Repair & Supply Center (ARSC) in Elizabeth City, North Carolina, and the Air Force 

Research Laboratory (AFRL) are currently leading the Ultraviolet (UV)-Curable Coatings for 

Aerospace Applications project to demonstrate, validate, and implement commercial off-theshelf 

(COTS) UV-curable coatings as an alternative to currently used hazardous and long cure 

time coatings used on aerospace equipment. The project will demonstrate the ability of this 

technology to replace current solvent-borne coatings in a production environment for topcoat 

applications such as simple geometry off-aircraft components, exterior/interior panels, markings, 

and touch-up and repair. If successful, UV-curable coatings will exhibit the same or better 

performance, reduce the overall environmental burden, and reduce the overall process flow-time 

compared to currently used and approved coatings. Upon successful completion of the efforts 

under this project, UV-curable coatings will be validated, implemented at OO-ALC and the 

USCG ARSC, and ready for implementation at other maintenance and repair facilities 

throughout the Department of Defense (DoD). 

UV-curable coatings are volatile organic compound (VOC)-, hazardous air pollutant (HAP)-, and 

isocyanate-free single component high-solids (nearly 100%) cross-linked coatings cured by brief 

exposure to intense UV light. The chemical reaction, or polymerization, that occurs in UVcurable 

coatings involves two major constituents, oligomers and monomers, and is set in motion 

by the photoinitiators blended into the coating. UV-curable coatings can be applied through 

traditional coating techniques (i.e., brush, roll or spray) and are rapidly cured with exposure to a 

UV light source of the proper intensity and frequency. Implementing UV-curable coatings at 

DoD facilities will lead to significant environmental, occupational, safety, and health benefits, 

and productivity increases throughout the DoD. 


G-69




CORN-HYBRID POLYMER (CHP) BLASTING BENEFITS 

AVIATION WEAPON SYSTEMS 

MS. DONNA PROVANCE 

NDCEE/CTC 

2624 Sweetgum Drive 

Apex, NC 27539 

(919) 303-4323 

Provance@ctc.com 

CO-PERFORMERS: Dr. Scott Sirchio (Naval Surface Warfare Center–Carderock Division); 

Thomas Guinivan (U.S. Army Environmental Command) 

O 

n behalf of the Naval Surface Warfare Center-Carderock Division and U.S. Army 

Environmental Command, the National Center for Energy and Environment (NDCEE) 

evaluated the corn-hybrid polymer (CHP) technology for use on aviation weapon systems. As 

part of this evaluation, the NDCEE conducted five demonstrations to determine if the CHP 

technology satisfies Navy, Army, and Air Force requirements for removing coatings from 

selected components in an efficient, cost-effective manner without damaging delicate substrate 

materials. As a result of demonstration findings, the Services have or intend to implement CHP. 

The NDCEE demonstrated that the CHP process satisfies the following Service requirements. 

• Is environmentally friendly. CHP blasting is a dry abrasive blasting process that uses a 

crystallized cornstarch that is organic, nontoxic, and biodegradable. CHP medium meets 

military specification MIL-P-85891 for Type VII plastic media. 

• Is user friendly. More than 100 personnel witnessed NDCEE CHP demonstrations that 

were held over a 2-year period. Based on participant comments and CHP’s potential to 

reduce or eliminate worker risks, it can be concluded that the CHP technology is more 

user friendly than hand sanding or chemical wiping. 

• Does not damage the substrate. The CHP process was demonstrated on more than 50 

military-supplied components of various substrates, including fiberglass, aluminum, 

Kevlar ® , titanium, graphite composite, magnesium, and steel. The CHP process did not 

damage any of the materials. 

• Meets current removal rates. The CHP blasting technology is usually faster than current 

coatings removal processes for the tested components. 

• Meets or reduces current process costs. NDCEE cost-benefit analyses on nine Navy and 

Army components showed cost avoidance savings ranging from $20,000 to more than 

$1.5 million. 

This poster will showcase findings from NDCEE CHP demonstrations. 

G-70




T 

INFRARED REFLECTANCE IMAGING FOR ENVIRONMENTALLY FRIENDLY 

CORROSION INSPECTION THROUGH ORGANIC COATINGS 

JACK BENFER 

NAVAIR 

NAS Jacksonville 

Building 793 

Jacksonville, FL 32212 

(904) 542-4516 

john.benfer@navy.mil 

CO-PERFORMER: Mr. John Weir (Northrop-Grumman) 

his ESTCP Weapon Systems & Platforms (WP-0407) project addresses the reduction of 

hazardous chemical/waste by employing non-destructive techniques to inspect aircraft 

interior and exterior structures through coatings thus reducing the amount of stripping and 

repainting that occurs at military rework facilities. Hazardous pollutants will be significantly 

reduced by eliminating scheduled organic coating removal and moving to a process where 

infrared (IR) inspection results will be used to determine when and if coating removal is 

required. 

The technology exploits an optically transparent spectral window in military paint systems 

within the Mid-IR spectrum and also the difference in IR reflection properties between corroded 

and non-corroded metallic surfaces. The IR energy passes directly through the coating and then 

reflects off the metallic substrate back through the coating and into an IR camera. Since the 

corroded areas do not reflect the IR energy as well as the non-corroded areas, a picture or image 

is generated by the IR camera much the same as observing the corrosion under standard visual 

techniques. 

The demonstration and validation measurements at NAVAIR Jacksonville and Oklahoma City 

Air Logistics Center on P-3, B-52 and KC-135 aircraft illustrated clearly that the IR imaging is 

an improved method of corrosion inspection compared to the visual inspection method. IR 

imaging will give engineering and corrosion control personnel the capability to make sound 

decisions regarding coating removal based upon improved detection of corrosion through 

coatings. A level of 70-80% accuracy was achieved with this technique as compared to the 5- 

25% accuracy of the visual inspection method. 

The cost and environmental benefit criteria for pollution prevention was projected and applied 

based on actual usage data of materials plus projected waste savings scenarios from the 

demonstration and validation measurements at NAVAIR Jacksonville and Oklahoma City Air 

Logistics Center. The study, based upon a medium sized aircraft (6500 square feet surface area), 

confirms a potential environmental savings of 300,000 pounds of Volatile Organic Compounds, 

2,500 pounds of Chromates, and 1,100,00 pounds of Hazardous Materials can be saved for a 

fleet of 100 aircraft over a 4 year period. Additionally, labor and material savings of $135,000 

per aircraft can be realized. Technology deployment across DOD platforms and weapon systems 

can result in an estimated 15 year savings of 2M lbs VOC, 7M lbs Hazmat, 20K lbs Chromate 

and a $115M cost avoidance. 

G-71




B 

HOW DOES SILANE ENHANCE THE PROTECTIVE PROPERTIES 

OF EPOXY FILMS 

PENG WANG 


2600 Clifton Avenue 

Cincinnati, OH 45221 

(513) 307-0713 

z.p.wang@gmail.com 

CO-PERFORMER: Dale W. Schaefer (University of Cincinnati) 

is-silanes with the general formula of (RO) 3 Si(CH 2 ) 3 -R'-(CH 2 ) 3 Si(OR) 3 , where OR 

represents an alkoxy group and R is an organic functionality, show excellent performance as 

coupling agents in anti-corrosion films; Epoxy resin also has superior chemical and corrosion 

resistance as well as outstanding mechanical toughness. By adding bis-type silane to novolac 

epoxy resins at proper ratio enhanced corrosion performance is achieved compared to neat epoxy 

resin or neat silane, especially on aluminum alloys. Moreover, this epoxy-silane coating system 

is also a direct-to-metal, one-step coating system, which eliminates the need for a priming step. 

In this study, the underlying mechanisms of how silane improves the protective properties of 

epoxy coating were investigated in depth. Morphology, chemical composition, water barrier 

properties, salt exclusion as well as hydrothermal degradation were investigated using x-ray and 

neutron reflectivity. This research is supported by SERDP as Project WP-1341. 

G-72




V 

CAN VANADATES REPLACE CHROMATES 

DALE SCHAEFER 


2600 Clifton Avenue 

Cincinnati, OH 45221 

(513) 377-2166 

dale.schaefer@uc.edu 

CO-PERFORMER: Peng Wang (University of Cincinnati) 

anadates have proven to be a promising candidate to replace the chromates in metalprotective 

applications. Lack of fundamental knowledge regarding vanadate films, 

however, has thwarted optimization and insertion into the metal finishing industry. Although 

sodium metavanadate (NaVO 3 ) is nearly insoluble in water (10%), they still provide good corrosion protection, presumably due to 

enhanced leaching of NaVO 3 . NaVO 3 is also effective when the films are mechanically 

compromised such as by scratching, which indicates that the vanadate inhibitors provide active 

protective. 

In this study, the protection mechanisms of both vanadate conversion coating and vanadate 

inhibitors in water-born primers were investigated by neutron and x-ray reflectivity. Following 

issues were addressed in detail: What are the kinetics of film formation and evolution How fast 

will an effective protective film form What are the speciation profile, the hydration profile and 

density profile normal to the metal surface Is the film uniform or graded How does the film 

change in a deprotection scenario What is the stability of the inhibitor layer in an aggressive 

environment This research is supported by SERDP as Project WP-1619. 

G-73




NANOCRYSTALLINE COBALT-ALLOY COATINGS FOR 

CHROME REPLACEMENT APPLICATIONS 

DIANA FACCHINI 

Integran Technologies, Inc. 

1 Meridian Road 

Toronto, ON M9W 4Z6 CANADA 

(416) 675-6266, Ext. 236 

facchini@integran.com 

CO-PERFORMERS: Dr. Jon McCrea, Dr. Francisco Gonzalez, and Dr. Gino Palumbo (Integran 

Technologies, Inc.); Ruben Prado [Naval Air Systems Command (FRC-SE)]; Dr. Keith Legg 

(Rowan Technology Group) 

T 

he replacement of hard chromium (Cr) plating in aircraft manufacturing activities and 

maintenance depots is a high priority for the U.S. Department of Defense. Hard Cr plating is 

a technique that has been in commercial production for over 50 years and is a critical process 

that is used both for applying hard coatings to a variety of aircraft components in manufacturing 

operations and for general re-build of worn or corroded components that have been removed 

from aircraft during overhaul. In particular, Cr plating is used extensively on hydraulic and 

pneumatic actuator wear surfaces. Chromium plating baths contain chromium in the hexavalent 

state, a known carcinogen. Wastes generated from plating operations must be disposed of as 

hazardous waste and plating operations must abide by EPA emissions standards and OSHA 

permissible exposure limits (PEL). OSHA recently reduced the PEL for Cr6+ and all Cr6+ 

compounds from 52µg/m3 to 5µg/m3. The rule also includes provisions for employee protection 

such as: preferred methods for controlling exposure, respiratory protection, protective work 

clothing and equipment, hygiene areas and practices, medical surveillance, hazard 

communication, and record-keeping. Due to the expected increase in operational costs associated 

with compliance to the revised rules and the expected increased turnaround times for processing 

of components there is tremendous pressure to find an environmentally benign alternative to hard 

Cr. 

Electrodeposited nanocrystalline cobalt-phosphorus (nCoP) coatings have been developed as an 

environmentally benign alternative to hard Cr coatings for non-line-of-sight (NLOS) applications 

under the Strategic Environmental Research and Development Program (WP-1152). 

Demonstration and validation testing was initiated in a project under the Environmental Security 

Technology Certification Program (WP-0411) and is currently ongoing. Nanocrystalline CoP 

coatings show great potential as an alternative to hard chrome for NLOS and LOS applications 

due to: higher cathode efficiency, higher deposition rates, high hardness and good sliding wear 

and corrosion resistance. Originally developed on the laboratory scale, the nCoP deposition 

process has been scaled up to the industrial/production scale. Outlined here are the process and 

properties of the nCoP coating in comparison to hard Cr, and the broad areas of application for 

the coating. A general overview of nanocrystalline materials will be presented with particular 

emphasis on reviewing the process and properties of nCoP coatings as they pertain to a hard Cr 

alternative. A review of the ongoing demonstration and validation program for nCoP currently 

being carried out at Fleet Readiness Center South East (FRC-SE) will also be presented. 

G-74




DEVELOPMENT OF NI-CU-RU CONSUMABLES FOR WELDING OF 

AUSTENITIC STAINLESS STEELS 

PROFESSOR GERALD S. FRANKEL 


2041 College Road 

Columbus, OH 43210 

(614) 688-4128 

frankel.10@osu.edu 

CO-PERFORMERS: Prof. John C. Lippold, Dr. Boian Alexandrov, Jeffrey W. Sowards, and 

Dong Liang (The Ohio State University) 

W 

elding of stainless steel can produce fumes that contain carcinogenic hexavalent 

chromium [Cr(VI)] species. In 2006, OSHA reduced the Permissible Exposure Limit for 

hexavalent chromium, which may severely restrict the use of conventional weld consumables 

containing 12-25% Cr. The motivation of this SERDP-funded study (WP-1415) is to develop a 

Cr-free filler metal based on the Ni-Cu alloy system that is compatible with common austenitic 

stainless steels, including Types 304 and 316. We have successfully shown that using such a 

consumable results in a drastic reduction in Cr(VI) generation during shielded metal arc (SMA) 

welding of austenitic stainless steel. We previously presented results from SMW welds made 

with a Ni-209 (Ni-4Ti-0.7Al-0.4Si-0.3Mn) core wire with Cu and Pd additions in the wire 

coating. It was difficult to achieve the desired weld deposit composition with those consumables. 

Ru was also found to be a cheaper and more effective addition than Pd for corrosion purposes. 

Gas tungsten arc (GTA) and SMA wire was made with the composition Ni-7.5Cu-1Ru-0.5Ti- 

0.5Al-0.02C. SMA weld deposits made with this consumable contained considerable porosity 

though it was found that the GTA welds were porosity free. Therefore an additional consumable 

was made by Electrode Engineering with the composition Ni-7.5Cu-1Ru-4Ti-0.5Al-0.02C. 

Welds were made with the fabricated Ni-Cu-Ru electrodes and weldability and corrosion testing 

is being performed on those welds. Initial weld deposits show that the target composition of Cu 

and Ru was achieved in the weld deposits, and porosity free welds have been successfully made. 

Weldability testing was performed to evaluate susceptibility to solidification cracking. It was 

found that the Ni-Cu-Ru weld metal has only a moderate susceptibility to solidification cracking 

similar to other Ni-based weld metals and the cracking susceptibility increases with increasing 

dilution of 304 base metal. Gleeble-based hot ductility and Strain-to-fracture testing was 

performed on GTA weld deposits made with the Ni-Cu-Ru wire. The solid-state cracking 

phenomenon known as ductility dip cracking (DDC) was found in the samples but no actual 

cracking has been observed in weld deposits. The susceptibility to DDC is similar to other Nibased 

weld metals with a moderate to high susceptibility. Corrosion experiments were performed 

on button samples prepared by GTA melting of Ni-Cu-Ru core wire. The corrosion properties of 

Ni-Cu-Ru core wire button samples were in line with NiCuRu button samples and bead-on-plate 

welds. Corrosion resistance of real welds made with the new Ni-Cu-Ru consumables was also 

assessed. The breakdown and repassivation potentials of the samples with Ni-Cu-Ru welds are 

comparable to welds made with 308L filler metal, which is different than for the Ni-Cu-Pd 

welds. This is associated with the location of crevice attack, which is on the base metal and not 

in the Ni-Cu-Ru welds. 

G-75




SCIENTIFIC UNDERSTANDING OF NON-CHROMATED 

CORROSION INHIBITORS FUNCTION 

PROFESSOR GERALD S. FRANKEL 


2041 College Road 

Columbus, OH 43210 

(614) 688-4128 

frankel.10@osu.edu 

CO-PERFORMERS: Prof. Rudolph G. Buchheit (The Ohio State University); Prof. Greg M. 

Swain (Michigan State University); Dr. Mark R. Jaworowski (United Technologies Research 

Center) 

O 

ver the past 10 years, scientific studies on the mechanism of chromate inhibition has led to 

a new understanding and resulted in the development of new techniques and approaches to 

study corrosion inhibition. The ultimate goal of that work, to assist in the development of nonchromate 

inhibitors has not been realized, partly because the same type of activity has not been 

focused on the non-chromate inhibitors. Non-chromate conversion coatings and inhibiting 

pigments have been developed with some success by Edisonian approaches, but the fundamental 

understanding of their functionality is still lacking, thereby inhibiting further advances and 

creating risk associated with their use. This SERDP-funded project (WP-1620) is addressing the 

mechanisms of leading chromate-free candidates and the cross-cutting, underlying fundamental 

issues. Advances in the scientific understanding of these issues are relevant to many if not all of 

the non-chromate technologies. The project is divided into the following individual topics: 

(1) Studies of the Trivalent Chrome Process (TCP). TCP is a leading non-chromate conversion 

coating, but there is no understanding of if and how it provides active corrosion inhibition. 

(2) Mechanisms of selected inhibitors. Experience has shown that application of the techniques 

used to study chromates can advance the understanding of the inhibition mechanism of nonchromate 

inhibitors. (3) Active inhibition, barrier properties and adhesion. The design of coating 

systems relies on some combination of these three coating functionalities, and the tradeoffs must 

be understood. (4) Paint adhesion strength and mechanism. One major function of surface 

treatments is the improved adhesion of the primer layer, but there is little understanding of the 

adhesion and de-adhesion mechanisms. (5) Inhibitor activation and transport in the primer layer. 

Inhibitive pigments in a polymeric paint matrix must be activated and transported to corroding 

sites, but again little fundamental understanding exists. (6) Interactions between polymer matrix, 

pigment, surface treatment, and alloy. Coating components largely have been developed 

independently but function as a system. The interactions and synergies are critical. 

(7) Characterization of local environments in coating systems. It is the coating/metal interfacial 

environment that controls the behavior of inhibiting species. The pH, oxidizing power, chemical 

aggressiveness (Cl-content) and temperature are the critical local environmental parameters that 

must be understood. 

G-76




CHROMIUM REPLACEMENT AND EROSION MITIGATION TECHNOLOGY 

FOR MEDIUM CALIBER GUN BARRELS 

M 

MARK MILLER 

Benet Labs 

1 Buffington Street 

Watervliet, NY 12189 

(518) 266-4177 

mark.miller9@us.army.mil 

CO-PERFORMER: Frank Campo (Benet Labs) 

edium Caliber Guns use electrodeposited chrome to protect the bore surface from the 

harsh environment of propellant gases. The electrodeposition process uses Chrome IV, a 

known carcinogen. Various laws and statutes exist to eliminate Chrome IV. In addition, 

advanced propellants used in higher lethality medium caliber ammunition increases cannon wear 

and erosion, and shortens barrel service life for current and future gun barrels. The solution is to 

develop environmentally- friendly, erosion resistant, gun bore coatings that meet or exceed 

current performance requirements. The technical objective of this program is to eliminate 

chromium plating in the production of medium caliber guns by developing an environmentally 

acceptable method for depositing wear and erosion resistant materials onto the gun bore surface 

through the exploitation of explosive cladding technology. 

Benet Labs, in conjunction with High Energy Metals Inc. (HEMI) in Sequim, WA and Ares Inc. 

in Port Clinton, OH has successfully cladded and rifled environmentally-friendly tantalum (Ta)- 

10W onto both 12” and 36” truncated sections of a medium caliber 25mm Bushmaster gun barrel 

using explosive cladding technology. The rifling was to full depth and bore size. The rifling 

success is a major milestone and a culmination of the efforts involving multiple technologies and 

processes to yield advancements in the state of the art in Cannon Technology. After successful 

cladding and rifling of a full-length barrel, firing tests are expected to validate performance 

equivalency. 

This work is funded by SERDP Project WP-1426. 

G-77




LOW TEMPERATURE POWDER COATINGS 

MR. WAYNE PATTERSON 

809 MXSS/CLA Science and Engineering Laboratory 

7278 4th Street 

Hill AFB, UT 84010 

(801) 775-2993 

Wayne.Patterson@hill.af.mil 

CO-PERFORMERS: Mr. David Piatkowski (NAVAIR); Mr. James Byron, Mr. James Davila, 

and Mr. Christopher Geib (SAIC, Inc.) 

T 

he Department of Defense (DoD) currently spends millions of dollars each year to procure 

and use, and dispose of toxic and hazardous materials associated with the use of, solventborne 

organic paint coatings. Powder coatings have the potential to eliminate a significant 

amount of the toxic and hazardous materials involved in application of corrosion protection 

coatings. Powder coatings are a VOC/HAP-Free alternative to solvent based paints and feature 

performance properties equal to or better than specification driven solvent based coatings such as 

MIL-C-22750 (epoxy) and MIL-C-85285 (polyurethane). High temperature cure powder 

coatings meeting DoD performance requirements have been commercially available for many 

years and have been utilized extensively on DoD hardware such as tactical missiles. However, 

although numerous aircraft, weapon systems, and ground support equipment could benefit from 

corrosion resistant powder coatings, they are made from temperature–sensitive materials such as 

low-tempered aluminum or composites and simply cannot withstand traditional high temperature 

cure (300°F - 400°F) powder coatings. Over the last few years, lower temperature curing 

powders having a 280°F cure temperature have become available. One such low temperature 

powder coating was developed under SERDP Project WP-1268 by GE Global Research and 

Crosslink Powder Coatings. The objective of the ESTCP Low Temperature Cure Powder 

Coatings (LTCPC) project (WP-0614) has been to build on the work already accomplished under 

the SERDP Project and demonstrate, validate and successfully implement low temperature 

powder coatings on DoD hardware in a depot production environment. The current 

demonstration is verifying the environmental and economic advantages of the proposed 

technology relative to the currently utilized technologies and is validating that the new 

technology is better in terms of cost, schedule, and performance when compared to the baseline 

solvent based coatings. Laboratory testing of coating performance is complete and some target 

hardware has been coated with the LTCPC. Coated Navy ground support equipment is currently 

in use on two deployed aircraft carriers, and a coated C-130 forward landing gear door has been 

installed on an aircraft which will soon depart Ogden Air Logistics Center. The Field Service 

Evaluations will evaluate how well the LTCPC performs on operational equipment in the field. 

The expected benefits of this project to the DoD are: Greener – no VOC’s or HAP’s, Safer – 

minimized worker exposure to hazardous materials, Less Expensive – powder coatings eliminate 

the disposal of solvents and hazardous wastes. 

G-78




P 

ULTRAVIOLET CURABLE POWDER COATINGS 

MR. COREY Q. BLISS 

Air Force Research Laboratory/RXSSO 

2700 D Street 

Building 1661 

Wright-Patterson AFB, OH 45433 

(937) 255-0943 

corey.bliss@wpafb.af.mil 

CO-PERFORMER: Christopher W. Geib (SAIC, Inc.) 

owder Coatings produce a superior durable coating, while reducing/eliminating hazardous 

waste and hazardous air pollutants (HAPs), and do so at a lower cost than conventional 

solvent painting. Powder coatings are generally classified as non-hazardous waste, and have little 

if any disposal or compliance costs. Powder coatings also eliminate the costly environmental 

recordkeeping burden associated with solvent painting hazardous waste. As a bonus, powder 

coatings eliminate volatile organic compound (VOC) paint emissions. VOCs are precursors to 

ground level ozone, a major EPA criteria pollutant that is problematic for many regions. 

Temperature sensitive substrates such as aluminum and magnesium are used in the manufacture 

and sustainment of weapon systems and ground support equipment. This project will 

demonstrate, validate and successfully implement a VOC/HAP-free, ultraviolet (UV)-cure 

powder coating (UVCPC) on DoD depot production hardware to replace solvent-borne organic 

coatings. UVCPC significantly reduces energy use by not requiring ovens and it also cuts 

turnaround times from days to hours. Because no oven is required, large, bulky and oversized 

objects can be powder coated and cured. Only the powder needs to be heated to melting, 

therefore the substrate is exposed to less heat for shorter periods of time. Lower temperature, 

shorter heating/curing times reduce both the energy costs and return to service times associated 

with this process. Combining reduced process times with the improved transfer efficiency of 

powder coatings (up to 95% vs. 60% for wet coatings) results in less expense, on a square foot 

basis, to apply powder coatings. This project will utilize both existing and new UV-curable 

powders in a side-by-side demonstration with the current existing wet paint system (MIL-PRF- 

23377J & MIL-PRF-85285D). The use of state-of-the-art-robotics will also be demonstrated. 

Robot integration with both Infrared and Ultraviolet light sources is underway. The beginning of 

coating validation testing has also begun and will continue through the summer of 2009. We will 

report some of the initial testing results and the current state of the robotic integration. 


G-79




I 

DEMONSTRATION/VALIDATION OF TERTIARY BUTYL ACETATE 

FOR DOD SOLVENT APPLICATIONS 

MR. WAYNE ZIEGLER 

U.S. Army Research Lab 

ATTN: AMSRD-ARL-WM-MC 

APG, MD 21005-5069 

(410) 306-0746 

wziegler@arl.army.mil 

CO-PERFORMER: Mr. Tom Torres (NFESC) 

n recent years, concerns over the ozone layer, photochemical smog and worker health have 

made traditional solvent cleaning products and processes increasingly regulated and 

expensive. This effort is funded by ESTCP Project WP-0616. The objective of this effort is to 

demonstrate the efficacy and validate the economic and process impact of TBAc in DoD solvent 

applications as a replacement for Hazardous Air Pollutant(s) (HAP) and VOC solvents. 

Traditionally, vehicle, equipment, aircraft, and ship maintenance operations utilize organic 

solvents containing HAP, such as MIL-PRF-680 and xylene, to remove dirt, grease, soot, and 

burned-on carbon from various parts. The DoD Services Clean Air Steering Committee and its 

workgroups have established a bottom line goal for DoD to stop using HAP solvents. The 

implementation of HAP free environmentally friendly solvents for cleaning will reduce HAP and 

VOC emissions, improve worker health and safety and significantly reduce the record keeping 

burden associated with demonstrating compliance with the NESHAP regulations. Tertiary-Butyl 

acetate (CH 3 COOC(CH 3 ) 3 ) is the common name for acetic acid, 1,1-dimethylethyl ester. Other 

names include t-butyl acetate, tert-butyl acetate, and, informally, TBAC or TBAc solvent. It is 

a colorless, flammable liquid with a camphor-like odor and an effective viscosity reducer with an 

intermediate flash point and vapor pressure. Industrially, it can be used in a variety of coatings 

and cleaners. This project evaluated TBAC as a replacement for various solvents used in coating 

operations for surface preparation, thinning, clean up and paint equipment cleaning. 

This project addressed each of the services environmental quality requirements: Navy: 2.1.01.g 

Control/Reduce Emissions from Coatings, Stripping, and Cleaning Operations (high priority), 

2.1.01.q Control of VOC and HAP Emissions (high priority) and 3.11.03.a Non-VOC/ODS 

Solvents and Cleaning Systems for Aircraft/Weapon and Shipboard/Shore Applications (high 

priority); Air Force: Need 1232 Avoid requirement for additional facility upgrades to meet the 

VOC/HAP standard; Army A (3.1.a): Alternative Products in Cleaning and Degreasing 

Processes, and Sustainable Painting Operations for the Total Army (SPOTA). 

G-80




P 

ENVIRONMENTALLY BENIGN REPAIR OF COMPOSITES USING HIGH 

TEMPERATURE CYANATE ESTER NANOCOMPOSITES: 

NANOFLUID PROCESSING AND CHARACTERIZATION 

PROFESSOR MICHAEL R. KESSLER 

Iowa State University and Ames Laboratory 

2220 Hoover Hall 

Ames, IA 50011 

(515) 294-3101 

mkessler@iastate.edu 

CO-PERFORMERS: Dr. Mufit Akinc; Xia Sheng; Wilber Lio; Katherine Lawler 

olymer matrix composites (PMCs) are subjected to events and environments throughout their 

lifetime that introduce microcracks and delamination that can greatly compromise their 

strength. Low temperature PMCs are typically repaired via a scarf-type method or a resin 

injection/infusion process. The repair of high temperature PMCs, however, is a long-standing 

problem since most repair resins have a low glass transition temperature (Tg) which limits their 

high temperature use, and resins with high Tg’s are typically not processable. 

Through SERDP-funded project WP-1580, we are currently developing a bisphenol E cyanate 

ester (BECy)/alumina nanocomposite adhesive whose primary phase (BECy) has not only a high 

cured Tg, but is also easily processable (has a low prepolymer viscosity at room temperature) 

and has excellent adhesive and mechanical properties. Alumina nanoparticles are used as the 

reinforcement phase to enhance adhesive strength, tailor viscosity, and further optimize the resin 

for injection repair applications. We have focused on the characterization of three materials: 1) 

neat BECy, 2) BECy/bare-alumina nanocomposites (BECy/Al), and 3) BECy/functionalized 

alumina nanocomposites (BECy/Al-GPS), which are functionalized with (3- 

Glycidyloxypropyl)trimethoxysilane (GPS). DMA tests show that the addition of alumina 

nanoparticles, bare or functionalized, increases the storage modulus and decreases the Tg of the 

nanocomposites. The reduction in Tg for composites containing Al-GPS was lower. 

The long-term creep behavior is predicted based on the time-temperature-superposition (TTS) 

principle. Tensile creep tests at high temperatures (200°C and above) show that both neat BECy 

and BECy/Al-GPS maintain a constant modulus without a significant reduction for a long period 

of time. Data from frequency sweep tests were transformed into time-domain creep compliance 

data using an inverse Fourier transform. The transformed creep data show similar results as 

experimental creep data but predict a longer useful lifespan. Such testing methods eliminate the 

effect of possible physical/chemical “aging” under aggressive test conditions. 

Rheology of BECy/bare-alumina nanocomposites (ranging from 0 to 20 volume percent 

alumina) shows that the viscosity of the monomer/nanoparticle suspension increases with 

increasing particle loading as expected. TEM images show that the particles are well dispersed in 

the cured composite. Lap shear tests of the BECy/alumina nanocomposites are used to 

determine the relation between adhesive strength and particle loading employing 

Bismaelimide/carbon fiber composites as substrates. 

G-81




CHARACTERIZATION OF SPECIES AND COATING MORPHOLOGY 

INVOLVED IN THE CORROSION PROTECTION OF 

RARE EARTH BASED COATINGS 

WILLIAM FAHRENHOLTZ 

Missouri University of Science and Technology 

101 Straumanis Hall, 401 W. 16th Street 

Rolla, MO 65409 

(573) 341-6343 

billf@mst.edu 

CO-PERFORMERS: Matt O’Keefe, Will Pinc, and Becky Treu (Missouri University of Science 

and Technology); Eric Morris (Deft, Inc.) 

C 

orrosion resistant cerium based conversion coatings have been developed to replace 

carcinogenic chromate based coating systems, which are the subject of increasingly 

stringent government regulations. While rare-earth based coatings can meet military 

specifications for salt spray corrosion resistance on high strength aluminum alloys, rare earth 

compounds are not inherently protective. Hence the fundamental processes that lead to 

protection must be investigated, if the performance is to be improved or extended protection to 

other substrates. Factors influencing the corrosion inhibition performance of cerium based 

conversion coatings include process parameters such as surface preparation prior to coating, 

coating solution additives, post treatment, and coating thickness. Characterization of cerium 

based conversion coatings was carried out with scanning electron microscopy and energy 

dispersive spectroscopy along with electrochemical tests to identify migrating species, surface 

morphology, and relationships between coating process parameters and corrosion performance. 

In addition, a focused ion beam system was used to selectively prepare cross sections of the 

conversion coatings to study the influence of features such as coating defects, oxides layers, and 

intermetallic particles in the substrate on coating performance. 


G-82




C 

TERNARY CADMIUM REPLACEMENT COATINGS FOR 

HIGH STRENGTH FASTENERS 

ADAM GOFF 

Luna Innovations Incorporated 

706 Forest Street, Suite A 

Charlottesville, VA 22903 

(434) 220-2513 

goffa@lunainnovations.com 

CO-PERFORMER: Dr. Derek Hass (Directed Vapor Technologies International) 

orrosion protection of high strength fasteners is of utmost importance due to the critical 

nature of structural loads transferred through them and their potential for galvanic corrosion. 

Therefore, adequate corrosion protection is a necessity to sustain both the structural integrity of 

fastener connections and to prevent preferential corrosion of connected members at the expense 

of galvanically-coupled fasteners. Traditionally, electroplated cadmium layers and hexavalent 

chromium rinses have been employed for these applications due to their excellent corrosion 

performance and lubricity for threaded applications; however, cadmium and chromate are 

hazardous substances, known human carcinogens and subsequently have high handling and 

disposal costs. These factors have increased the need to develop new coating technologies and 

corrosion protection systems for cadmium plating and chromate conversion coating replacement. 

Luna Innovations, in partnership with Directed Vapor Technologies International, are 

investigating the potential of Zn-Ni-X ternary alloy coatings as cadmium replacement options for 

high strength steels. Directed vapor deposition (DVD) is the primary deposition method being 

investigated; however other techniques are being evaluated as needed. The DVD process serves 

to eliminate hazardous cadmium and chromium waste streams while at the same time reducing 

the risk of component hydrogen embrittlment, thus extending component service life. In 

addition, a major goal of the program is to adapt the DVD process for coating high strength steel 

fastener components and ultimately offer competitive production throughput as compared to 

traditional fastener cadmium plating production lines. A combinatorial DVD approach is being 

used to rapidly evaluate a multitude of Zn-Ni-X alloy stoichiometries to determine the 

compositions with the overall best corrosion and performance properties. 

This work is funded by SERDP as Project WP-1615. 

G-83




A 

DEMONSTRATION OF A LEAD-FREE SURVEILLANCE AND DETECTION 

PROGRAM TO ADDRESS ROHS REGULATION LEAD-FREE RISKS IN 

WEAPON SYSTEMS AND PLATFORMS 

CHUCK TOMLJANOVIC 

National Defense Center for Energy and Environment 

100 CTC Drive 

Johnstown, PA 15904 

(814) 269-6834 

chuck-t@ctc.com 

CO-PERFORMERS: Ms. Heather Brent, Ms. Jess Grembi, Mr. Gino Spinos, and 

Mr. Paul Mack (NDCEE) 

s a result of the restriction of the use of certain hazardous substances in electrical and 

electronic equipment (RoHS Directive) within the European Union (EU) market, the U.S. 

Department of Defense (DoD) is faced with new and uncertain potential failure modes in certain 

mission critical electronics. The RoHS Directive (effective July 1, 2006) bans new electrical 

equipment containing established levels of cadmium, mercury, hexavalent chromium, 

polybrominated biphenyls (PBB) and Polybrominated Diphenyl Ether (PBDE) flame retardants, 

and lead (Pb). Because DoD electronic acquisition programs depend heavily on commercial “off 

the shelf” (COTS) electronic parts and assemblies, the absence of lead in critical, high reliability 

systems can lead to Pb-free impacts including, but not limited to, solder issues, tin whisker 

impacts/failures, material availability issues, configuration control challenges, and repair/rework 

issues. Short term commercial Pb-free solution strategies in response to the RoHS Directive may 

not necessarily meet the unique and high-performance requirements of mission critical DoD 

weapon systems. The National Defense Center for Energy and Environment (NDCEE), through 

the Mission Critical Environment, Safety, and Occupational Health (MC ESOH) Technology 

Transfer and Support Program is conducting a demonstration/validation (dem/val) of a Pb-free 

surveillance and detection program for weapon systems at the Depot shop floor level. 

Specifically, the objectives of the dem/val include standing-up and evaluating X-ray 

Fluorescence (XRF) technology in a production environment to identify the presence of Pb-free 

COTS within the supply chain, as well as develop and transition a database to collect Pb-free 

data and assess the prevalence of Pb-free materials in acquisition. 

This poster provides an overview of the MC ESOH Program mission, why the global transition 

to Pb-free electronics adversely affects the DoD supply chain and mission readiness, specific 

details regarding the dem/val of XRF spectrometers at the shop-floor level, as well as 

information regarding the transition of a Pb-free surveillance database. Highlights will include 

lessons learned from field verifying XRF units regarding performance, accuracy, reliability, and 

practicality of use in major weapon systems and critical Depot level parts management supply 

chains. Also reviewed will be those items found to be fundamental to continued lateral transition 

and additional implementation elsewhere in response to the mission critical Pb-free challenge. 

Other Depots and installations can use this dem/val as a benchmark approach as they analyze 

their effectiveness regarding Pb-free inspection and mitigation measures in parts management 

where mission critical risks may exist. 

G-84




I 

OPTIMIZING CARC IMPROVEMENTS FOR ARMY WEAPON SYSTEMS 

MR. ROBERT FISHER 

NDCEE/CTC 

100 CTC Drive 

Johnstown, PA 15904 

(814) 269-2702 

fisherr@ctc.com 

CO-PERFORMERS: Donna Provance (NDCEE/CTC); 

Thomas Guinivan (U.S. Army Environmental Command) 

n conjunction with the U.S. Army Environmental Command (USAEC), the National Defense 

Center for Energy and Environment (NDCEE) is helping Army installations to implement new 

chemical agent resistant coating (CARC) formulations: MIL-DTL-64159, Type II, a waterdispersible 

CARC (WD-CARC), and MIL-DTL-53039B, Type II-Polymeric, a solvent-based, 

single-component CARC. As a result of this assistance, Army installations have improved their 

coating operations by reducing air emissions up to 65%, reducing material usage by 30-40%, and 

lowering application times by 25-35%. The Environmental Security Technology Certification 

Program (ESTCP) estimated that a facility could achieve a cost avoidance savings of up to 

$730,000 by implementing WD-CARC, depending on the type of equipment being painted. 

The Defense Land Systems and Miscellaneous Equipment National Emission Standard for 

Hazardous Air Pollutants being proposed by the U.S. Environmental Protection Agency will 

regulate the coating processes for the majority of U.S. Army materiel, including tactical vehicles, 

ground combat vehicles, tactical shelters, munitions, and others. The two new CARCs contain 

lower volatile organic compounds than the original CARC and zero hazardous air pollutants. 

Under its current task, the NDCEE and USAEC are helping installations to overcome challenges, 

real or perceived, to implementing the new CARCs. This assistance includes hosting technology 

demonstrations, conducting coating application training, and obtaining technologies that improve 

the mixing and application process. To date, Fort Stewart and Fort Benning operations have 

switched to WD-CARC because of the NDCEE/USAEC assistance. Two more technology 

demonstrations will be conducted in summer 2008. 

This poster will showcase findings from NDCEE CARC demonstrations. 

G-85




SUPERSONIC PARTICLE DEPOSITION TECHNOLOGY FOR REPAIR OF 

MAGNESIUM AIRCRAFT COMPONENTS 

VICTOR K. CHAMPAGNE 


Aberdeen Proving Ground 

Aberdeen, MD 21005-5069 

(508) 461-9508 

vchampag@arl.army.mil 

CO-PERFORMERS: Phillip F. Leyman (Army Research Laboratory); Robert Kestler, (NADEP- 

CP, Cherry Point, NC); Robert Guillemette (Sikorsky Aircraft, Stratford, CT); Timothy J. Eden 

(The Pennsylvania State University, State College, PA); Keith Legg (Rowan Technology Group, 

Libertyville, IL); Mark Valazquez (CCAD, Corpus Christi, TX) 

M 

agnesium alloys are widely used for fabrication of many components on DoD aircraft 

because of their high strength-to-weight characteristics, especially for complex 

components such as transmission and gearbox housings on helicopters and gearbox housings on 

fixed-wing aircraft. However, magnesium alloys are highly susceptible to corrosion in-service 

and to surface damage due to impact such as during handling, assembly, or repair. Several 

million dollars are expended by DoD each year to either repair or replace Mg alloy components 

that are corroded or damaged in service. 

As part of an overall solution to the problem, Supersonic Particle Deposition (SPD) of pure 

aluminum in addition to aluminum alloys is being evaluated as one of the most viable methods of 

imparting surface protection to Mg alloys. SPD has yielded nearly fully dense coatings with less 

than 1% porosity with bond strengths of 10,000 psi on magnesium substrates. Test results for 

both commercially pure aluminum and high purity aluminum in addition to aluminum alloys 

have yielded enhanced corrosion resistance on magnesium substrates with no deleterious effects 

on the fatigue strength of the magnesium. A materials joint test protocol has been developed 

which will be executed on ZE41A, AZ91C and EV-31 magnesium alloy specimens that have 

been coated with high purity aluminum and aluminum alloy 6061 SPD coatings to evaluate their 

mechanical strength and corrosion resistance. 

The work includes establishment of a demonstration and validation of a SPD facility at NADEP 

Cherry Point (NADEP-CP), and a transition plan to implement SPD as a cost effective, 

environmentally acceptable method to restore dimensional tolerances on actual magnesium alloy 

components on DoD helicopters and fixed-wing aircraft. 

This work is funded by ESTCP as Project WP-0620. 

G-86




PERFORMANCE EVALUATION AND QUALIFICATION OF MAGNESIUM RICH 

H 

PRIMER FOR CHROME FREE AEROSPACE COATING SYSTEMS 

MR. CHRISTOPHER JOSEPH 

Air Force Research Lab–Coatings Technology Integration Office (CTIO) 

AFRL/RXSSO 

2700 D Street, Building 1661 

Wright Patterson AFB, OH 45433 

(937) 656-9260 

christopher.joseph@wpafb.af.mil 

CO-PERFORMERS: Joel Johnson and Mike Spicer (Air Force); 

Craig Matzdorf (NAVAIR) 

exavalent chromium compounds are one of the top hazardous waste materials generated by 

the DoD, and environmental/ESOH regulations continue to restrict their use. However, 

chromate-based corrosion inhibitor pigments are still widely used in coating systems to protect 

high strength aluminum alloys, such as those used in aerospace applications, because to date, 

non-Cr alternatives have not shown superior performance. A “Magnesium Rich” primer has 

recently been developed as a potential alternative to chromated primers that utilizes sacrificial 

magnesium metal pigment to cathodically protect aerospace aluminum alloy substrates. 

Preliminary evaluations had shown this material to be extremely effective as part of a completely 

chromate-free coating system in which a non film forming surface treatment and an Advanced 

Performance Coating (APC) grade topcoat are utilized. An ESTCP test plan was generated to 

perform detailed accelerated laboratory and outdoor performance evaluations to understand the 

robustness of the technology. Furthermore, transition of the technology was planned via 

qualification of the primer as part of a Cr-free coating system on Air Force and NAVAIR 

aircraft. Samples of the Cr-free coating system have been exposed outdoors on AA2024-T3 and 

AA7075-T6 alloys at Daytona Beach and flown on small sections of various aircraft for over one 

year with no corrosion evident. However, accelerated testing of more recent samples in ASTM 

B117 salt fog has shown early failure. The discrepancy between previous laboratory testing, 

recent laboratory testing, and outdoor exposure results presents a challenge to quantify the 

robustness of the technology and to validate the correlation between laboratory versus field 

results. Since this new technology does not function in a manner similar to historic chromatebased 

primers, a new accelerated laboratory test method that accurately predicts field results may 

need to be developed. 


G-87




C 

INVESTIGATION OF CHEMICAL VAPOR DEPOSITION OF 

ALUMINUM AS A REPLACEMENT COATING FOR CADMIUM 

DR. ELIZABETH BERMAN 

Air Force Research Lab/MLSC 


Building 652, Room 122 

Wright-Patterson AFB, OH 45433 

(937) 656-5700 

Elizabeth.Berman@WPAFB.AF.MIL 

CO-PERFORMER: Dr. Eric Brooman 

admium is widely accepted as the coating of choice on high strength steels due to its 

excellent corrosion resistance, adhesion, and lubricity characteristics. However, cadmium is 

a carcinogen, a teratogen, and a toxic metal that can be leached easily causing potential 

contamination of the ground water supply and food chain. 

One approach to cadmium replacement is to use an aluminum coating, which is environmentally 

clean, non-toxic, and safe to handle and use by workers. In addition, aluminum coatings can be 

subjected to temperatures as high as 496°C, while cadmium is limited to 232°C. They may be 

exposed to fuels with no adverse effects, and can be used in space applications because of their 

low vapor pressure. Corrosion tests have demonstrated that ion vapor deposited (IVD) aluminum 

coatings with appropriate post-treatments provide equivalent or superior corrosion protection to 

cadmium-plated steel parts. However, post-treatments result in additional processing steps that 

often use toxic chemicals such as chromates or dichromates. Thus, an alternative deposition 

process is needed. 

The objective of this SERDP project (WP-1405) is to evaluate the use of atmospheric pressure 

chemical vapor deposition techniques to produce uniform and conformal aluminum coatings on 

high strength steel substrates. This approach offers an environmentally benign alternative to 

cadmium plating, as well as promises to provide high production throughput, low cost, and 

coatings with desirable properties and performance. Recent efforts have focused on using triisobutyl 

aluminum and other precursors to deposit coatings 10-25 mm thick at temperatures in 

the range from 250°C to 300°C. Emphasis has been placed on the lower temperature to 

minimize any adverse effects on mechanical properties, such as tensile strength and fatigue 

resistance. These aluminum coatings have been characterized in terms of their composition, 

structure and morphology. Additionally, performance tests are being used to determine their 

properties compared to those of cadmium and IVD aluminum. Results indicate that the coatings 

consist essentially of pure aluminum with traces of oxygen, carbon and hydrogen. The presence 

of hydrogen in the coatings necessitates a post deposition, hydrogen relief bake, as is necessary 

for cadmium coatings) to avoid causing hydrogen embrittlement. The performance tests include 

chemical resistance, paint adhesion, corrosion resistance, electrochemical characterization, 

hardness and tensile strength debit, hydrogen embrittlement susceptibility, as well as fatigue 

debit. Further work is needed to optimize these aluminum coatings deposited at lower 

temperatures for use on high strength steel substrates used for landing gear components. 

G-88




A 

CADMIUM ALTERNATIVES FOR DOD AND NASA APPLICATIONS – 

PHASE II TESTING RESULTS 

MR. STEVEN BROWN 

NAWC Aircraft Division 

48066 Shaw Road, Bldg. 2188 

Patuxent River, MD 20670 

(301) 342-8101 

steven.a.brown1@navy.mil 

Joint Test Protocol (JTP) for evaluation of cadmium alternatives for high-strength steel 

structural components was developed through the Joint Cadmium Alternatives Team 

(JCAT). The test protocol combines the joint requirements of the aviation and ground platform 

community for defense and commercial users. Phase I testing completed in 2006 focused on 

embrittlement/re-embrittlement and adhesion testing of alternative coatings and repair methods. 

Coatings selected for Phase II testing were: LHE Zinc-Nickel, Sputtered Aluminum, 

Electroplated Aluminum, Brush Zinc-Nickel, Brush Tin-Zinc and SermeTel® 249/273. Control 

coatings included both LHE cadmium and IVD aluminum. Phase II testing was fairly extensive, 

however, the portion completed in FY08 included the following: various types of bare and 

painted salt spray corrosion (ASTM B 117, ASTM G 85, GM 9540P), fluid compatibility, 

electrochemical behavior, and lubricity (run-on breakaway torque, torque-tension). Tests were 

conducted by Army Research Labs, Concurrent Technologies Corporation, and Westmoreland 

Mechanical Testing and Research. Portions of the Phase II effort were funded by ESTCP WP- 

0022, the Air Force Pollution Prevention Program and the Naval Environmental Sustainability 

Development to Integration (NESDI) program. Test results and implementation efforts for 

cadmium alternative coatings will be summarized as they apply to various DoD components. 

G-89




(4 

NEW REACTIVE DILUENTS FOR AN ENVIRONMENTALLY EFFICIENT 

APPROACH TO COMPOSITE REPAIR 

DR. ANDREW GUENTHNER 

NAVAIR 

1900 N. Knox Road, Stop 6303 

China Lake, CA 93555 

(760) 939-1626 

andrew.guenthner@navy.mil 

-phenoxyphenyl) methacrylate (1b) and {(4-phenoxyphenyl)methyl} methacrylate (1a) were 

prepared in high yield by the reaction of methacryloyl chloride with the corresponding 

alcohol in the presence of triethylamine. In addition, 4-{4-(4-tributylsilylphenyl) 

phenoxy}styrene (3) was prepared in two steps from 4,4’-dibromodiphenyl ether. All three of the 

diphenyl ether reactive diluents dissolved the polyester resin (Mn ~4000) using ~50-60 wt-% of 

the phenylether diluent to afford repair resin mixtures with reasonable viscosities for use in 

fabricating cloth lay-ups. In the case of 3, we found that in making repairs of engineered defects 

that the polyester resin cured much faster and that led to phase separation. In the case of both 1a 

and 1b we observed complete cure and the system remains homogeneous throughout the repair 

process. Mechanical data will be presented for repaired materials. 


G-90




R 

SHELF-STABLE ADHESIVE FOR REDUCTION OF 

COMPOSITE REPAIR HAZARDOUS WASTE 

JOHN PLAYER 

Infoscitex Corporation 

303 Bear Hill Road 

Waltham, MA 02451 

(781) 890-1338, Ext. 237 

jplayer@infoscitex.com 

CO-PERFORMER: Heather Kauth and Lebzylisbeth Gonzalez (Infoscitex Corporation) 

epairs for military and commercial composite structures found in aircraft, ships, amphibious 

and tactical vehicles are currently achieved, in a large part, using one part epoxy based 

material systems.. These epoxy systems are efficient, reliable, and takes the form of epoxy film, 

liquid shim adhesive and composite prepreg. However, two issues arise from using a one part 

epoxies; (1) The shelf life of a typical aerospace structural film adhesive used for composite 

repair is about 1 year at 0º F but it accumulates a “thermal history” each time it is removed from 

storage, leading to large amounts of expired unused product and (2) Most composite repair 

materials are engineered to cure at 250ºF or greater. When repair temperatures exceed 212ºF, the 

boiling point of water, composite parts subjected to repair can delaminate as the 

absorbed/inherent water turns to vapor. These damaged parts, in turn, add to the overall waste 

disposal burden. The cost of regulatory compliant disposal of expired/uncured repair 

adhesive/resin wastes exceeds millions of dollars per year for large aircraft repair facilities. 

The goal of the SERDP SEED program (WP-1579) was to mitigate the cost by increasing the 

shelf life of the one part epoxy adhesive. Our concept was to achieve this goal via 

microencapsulation of the catalyst accelerator components, reducing room temperature reactivity 

and extending the shelf life of the product. We successfully prepared proprietary complex 

coacervate microcapsules, which showed a significant increase in residual activity at high 

temperature storage with no loss of mechanical properties. The microencapsulation allows a 

more reactive accelerator to be used; our team explored multiple accelerators that enable 200ºF 

cure so that structural repairs performed in the presence of absorbed moisture can be 

accomplished without causing voids and delamination. We found that one of our proprietary 

accelerators enabled reduced onset of cure for epoxy/DCDA/catalyst accelerator resin from 

291ºF to 202ºF. We also found during our lap shear mechanical testing validation that our 

encapsulated catalyst based resin system was statistically equivalent to the control, thus assuring 

no basic property losses with our new material. 

Our technology is a real-world solution which will reap a dividend for both the environment and 

the bottom line. By optimizing our proprietary encapsulation process, and expanding both 

mechanical properties and shelf stability testing, we will lay the groundwork for transitioning 

this technology to large scale manufacturing to supply the needs of military and commercial 

composite repair customers. 

G-91




VALIDATION OF NOVEL ELECTROACTIVE POLYMERS AS 

ENVIRONMENTALLY COMPLIANT COATINGS FOR REPLACEMENT OF 

HEXAVALENT CHROMIUM PRETREATMENTS 

DR. PETER ZARRAS 

NAWCWD 

1900 N. Knox Road (Stop 6303) 

China Lake, CA 93555-6106 

(760) 939-1396 

peter.zarras@navy.mil 

CO-PERFORMERS: Ms. Nicole Anderson, Ms. Cindy Webber, Ms. Amy L. Hilgeman, 

Mr. Andy Schwartz, and Mr. Christopher S. Mahendra (NAWCAD); Ms. Diane Buhrmaster 

(WPAFB/University of Dayton Research Institute); Mr. Michael Spicer (WPAFB); Dr. Mark R. 

Kolody (Kennedy Space Center); Mr. Christopher E. Miller (U.S. Army Research Laboratory) 

T 

he ESTCP Project WP-0527 is currently demonstrating an effective, environmentally 

benign, repairable coating system using electroactive polymers (EAPs) as the replacements 

for chromate conversion coating (CCC) pretreatments on aluminum and steel alloys. The 

NAWCWD, China Lake, California is leading this effort in collaboration with Wright Patterson 

Air Force Base (WPAFB), Naval Air Warfare Center Aircraft Division (NAWCAD), Patuxent 

River, Maryland/Lakehurst, New Jersey, Kennedy Space Center (KSC) and the Army Research 

Laboratory (ARL), Aberdeen Proving Grounds, Maryland. 

The EAP polymers that are being evaluated for this ESTCP project are poly (2, 5-bis (N-methyl- 

N-hexylamino) phenylene vinylene), (BAM-PPV) and poly ((2-(2-ethylhexyl) oxy-5-methoxy)- 

p-phenylene) vinylene), (MEH-PPV). Both of these polymers have demonstrated acceptable 

performance as military alternatives to CCC on aluminum alloys. Each service (Air Force (AF), 

Navy and Army) have completed all laboratory testing prior to field testing these two polymers. 

Both BAM-PPV and MEH-PPV were processed from a VOC-exempt solvent, 4- 

chlorobenzotrifluoride, Oxsol-100. The BAM-PPV coating has proven to be a more robust 

system and will be field tested in FY08. MEH-PPV showed poor shelf-life and processability 

from Oxsol-100 solvent. Current testing includes marine outdoor exposure testing of BAM-PPV 

at KSC and toxicology testing. The field testing by each service will include non-critical 

hardware. The AF C-5 cargo airplane’s rear hatch door, the Army’s door hatch and flagpole 

holder on the Bradley vehicle and the Navy’s EA-6B prowler aircraft jammer pods, landing gear 

doors and loading platform were selected as the non-critical hardware to test the BAM-PPV 

coating for a 12 month study. 

G-92




M 

ENVIRONMENTALLY BENIGN MULTILAYER POLYMER COATINGS 

WITH CONTROLLED SURFACE PROPERTIES FOR 

MARINE ANTIFOULING APPLICATIONS 

PROFESSOR CHRISTOPHER K. OBER 


Materials Science and Engineering 

310 Bard Hall 

Ithaca, NY 14853 

(607) 255-8417 

cko3@cornell.edu 

CO-PERFORMERS: Craig J. Weinman, Daewon Park, Harihara S. Subramanian, and 

Marvin Y. Paik (Cornell University); Daniel A. Fischer (NIST); Dale L. Handlin and 

Carl. L. Willis (Kraton Polymers); Karen E. Sohn, Michael Dimitriou, and 

Edward J. Kramer (UCSB) 

arine biofouling is the unwanted accumulation of microorganisms, plants and animals on 

artificial surfaces submerged in seawater. Biofouling causes undesirable drag, which in 

turn leads to significantly higher fuel consumption by marine interests. Environmentally friendly 

multilayer antifouling coatings based on the control of surface energy and coating modulus are 

being developed to replace traditional toxic copper and tributyl-tin containing ablative coatings. 

These multilayer coatings consist of a thin surface-active block copolymer (SABC) layer 

supported by a thick elastomeric layer. This work seeks to develop new coatings that help 

resolve both the energy consumption issues caused by biofouling and the environmental 

concerns of the previous generation of marine antifouling coatings. 

Polystyrene-block-polyethylene/butylene-block-polystyrene (SEBS) produced by KRATON 

Polymers was selected as the bottom rubbery layer. This triblock copolymer provides the 

necessary low modulus, corrosion protection, adhesion, and durability needed for a multilayer 

coating system. Several approaches to the synthesis of side-chain functionalized SABC have 

been developed. Hydrophobic semifluorinated alkyl groups, hydrophilic poly(ethylene glycol) 

groups, and Zonyl ® amphiphilic nonionic fluorosurfactant groups are all being explored as 

grafted surface-active side-chains. Additionally, amphiphilic, “mixed” surfaces containing a 

variety of ratios of distinct poly(ethylene glycol) groups in conjunction with distinct 

semifluorinated alkyl groups are being explored. Spray coating provides a realistic approach to 

apply these coating systems onto a ship’s hull, and surface analysis using X-ray photo electron 

spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS), and scanning force 

microscopy (SFM) has demonstrated that the elastomeric layer is fully covered by SABC. 

Biofouling tests are being performed in several marine labs, and samples have exhibited 

encouraging antifouling performance with regards to both soft and hard marine fouling. 

Additionally, coating systems are now being tested at several oceanic exposure sites. Promising 

coating compositions have been identified and further development is on-going. 

This work is supported by SERDP WP-1454 with additional support for analytical research 

provided by the Office of Naval Research. 

G-93




EVALUATION OF MULTIFUNCTIONAL UV (MUV) CURABLE CORROSION 

M 

COATINGS ON HIGH STRENGTH ALUMINUM ALLOY SUBSTRATES 

PROFESSOR MATT O’KEEFE 

Missouri University of Science and Technology 

101 Straumanis Hall 

401 W. 16th Street 

Rolla, MO 65409-1170 

(573) 341-6764 

mjokeefe@mst.edu 

CO-PERFORMERS: B. Fahrenholtz (Missouri University of Science and Technology); 

J. DeAntoni (Boeing); B. Curatolo (Light Curable Coatings) 

ultifunctional UV (MUV) curable coatings containing environmentally benign corrosion 

inhibiting compounds are being developed. The coatings are free of volatile organic 

compounds (VOCs) and chemicals on the toxic release inventory (TRI) list. They are being 

developed to replace existing corrosion coatings used on military weapon systems that contain 

hexavalent chromium as the corrosion inhibitor as well as VOCs and TRI chemicals. Initial trials 

demonstrated that a MUV coating on high strength aluminum alloy substrates could pass 3000 

hours of ASTM B117 neutral salt spray testing. The initial trials were done using a high 

concentration of corrosion inhibitor in the MUV coating and were applied to test panels using a 

drawbar. Follow-on work has shown that a reduced level of corrosion inhibitor in the MUV can 

also pass ASTM B117 salt spray testing. The reduced concentration of the inhibitor in the MUV 

was used in the development of a coating applied by a spray deposition process commonly used 

by original equipment manufacturers and military depots. Evaluation of the MUV coating with 

the lower corrosion inhibitor concentration on chromate, cerium and trivalent chrome conversion 

coatings, along with comparison to existing chromate and non-chromate epoxy primer/topcoat 

systems, has been conducted. Results indicate that the MUV coating is capable of good salt spray 

performance, low temperature flexibility and adequate wet tape adhesion on chromate 

conversion coatings. Other MUV properties, such as room temperature flexibility, fluid 

resistance, and performance on non-chromate conversion coatings, are being optimized to meet 

military aerospace requirements. 


G-94




UV CURABLE NON-CHROME PRIMER AND ADVANCED TOPCOAT SYSTEM 

F 

DR. NESE ORBEY 

Foster-Miller 

195 Bear Hill Road 

Waltham, MA 02451 

(781) 684-4170 

norbey@foster-miller.com 

CO-PERFORMERS: Dr. Eric Morris (Deft, Inc.); Mr. Stan Bean (NGC) 

oster-Miller (FMI), Deft, Inc. and Northrop Grumman (NGC) are working to develop an 

environmentally benign surface pretreatment, primer and topcoat system for aircraft 

applications. FMI has a patented chemistry for single-component coating formulations that 

contain no VOC, HAP or TRI constituents and cures rapidly by chemical reaction on exposure to 

UV irradiation. FMI is using this coating chemistry in conjunction with Deft’s proprietary 

corrosion inhibiting pigments to develop high-performance materials that will ultimately 

comprise a corrosion inhibiting coating system that doesn’t contain VOC’s, HAP, or SARA 313- 

reportable chemicals. Specifically, we are developing sprayable, UV-curable corrosion-inhibiting 

primers and high-performance topcoats that will provide superior protection to aluminum 

substrates even when non-chromated surface pretreatments are employed. Further, a one-coat 

formulation will be developed in an attempt to combine the corrosion inhibiting properties of the 

primer and superior durability of the topcoat into a single, high-performance coating. Work done 

to date and results obtained will be presented. 


G-95




DEMONSTRATION/VALIDATION OF HIGH PERFORMANCE CORROSION 

PREVENTIVE COMPOUND (CPC) FOR INTERIOR AIRCRAFT APPLICATIONS 

T 

EL SAYED ARAFAT 

NAVAIR 

48066 Shaw Road, Bldg. 2188 

Patuxent River, MD 20670 

(301) 342-8054 

elsayed.arafat@navy.mil 

he main goal of this demonstration is to validate the effectiveness and the performance of a 

newly developed corrosion preventive compound known as Navguard. This project seeks to 

reduce hazardous waste, VOCs, and HAPs, while improving the performance of this type of 

internally applied corrosion preventive compounds (CPCs). As aircraft age, corrosion often 

occurs in internal structures which are not easily inspected or treated. Fogging CPCs into internal 

spaces of airframes has been shown to be effective in combating metal degradation. However, 

the CPC must be reapplied several times annually, using time-consuming procedures. As an 

alternative, NAVAIR has developed a high performance, long lasting CPC for internal airframe 

applications. The key benefits of using Navguard are reducing VOC emission from CPC 

application by 50% or more, eliminating HAPs, and reducing the maintenance intervals for reapplication 

of CPCs. Navguard was tested through a Lead-The-Fleet demonstration on F-18 at 

NAS Oceana, VA, and Expeditionary Fighting Vehicle (EFV) at US Marine Corps, Camp 

Pendleton, CA, and showed no sign of corrosion after twenty-four months of exposure. 

Currently, Navguard has been applied on multiple platforms such as H-46 (4), EA-6B (5), EFV 

(8), H-60 (1), and F-18 (17) at several DoD testing sites (Army, Navy, and Marine Corps). Oneyear 

maintenance inspection for platforms used in the field test has shown no sign of corrosion in 

the area it was applied. This demonstration will continue for additional inspection intervals to 

evaluate how long the Navguard will perform without needing to be reapplied. The goal is a twoyear 

maintenance interval; four times the current one. For successful demonstration of the new 

technology, the demonstration period has been planned for two years or two-deployments for any 

carrier-based assets. Successful completion of this project will result in the implementation of 

high-performance, long lasting CPCs specifically suited for Navy, Air Force, and Army 

Aviations requirements and operating environments. Two vendors have licensed the Navguard 

CPC formulation to manufacture the product for use by DoD and commercial applications. 


G-96




ENVIRONMENTALLY FRIENDLY COATINGS SYSTEMS 

FOR DOD APPLICATIONS 

DR. JOHN LA SCALA 


AMSRD-ARL-WM-MC 


(410) 306-0687 

jlascala@arl.army.mil 

CO-PERFORMERS: Felicia Levine (ARL); Vincent Crisostomo and Steven Suib (University of 

Connecticut); William Nickerson and Amy Hilgeman (NAVAIR); Brian Placzankis, 

Christopher Miller, and John Escarsega (ARL) 

M 

ilitary coating systems for metals typically consist of an inorganic pretreatment, an epoxy 

primer, and a polyurethane topcoat. Traditional coating systems contain hexavalent 

chromium (Cr6+) and produce significant amounts of volatile organic compound (VOC) 

emissions. However, the latest OSHA regulations impose strict environmental standards forcing 

all industrial sectors and the Department of Defense to reduce VOC and Cr6+ exposure limits. 

As a result, we examined the use of the trivalent chromium process (TCP) and chromium-free 

process (CFP) developed by NAVAIR to reduce Cr6+ use. We have developed modifications to 

increase corrosion resistance through the addition of an organic chelating compound and other 

additives to TCP at low concentrations. ISO titration studies on TCP and a hexavalent-based 

pretreatment, Alodine 1200, liquid pretreatments and pretreated panels showed that Cr6+ is not 

produced from TCP, but is produced in significant quantities by Alodine 1200. Various Cr6+ 

free (class N) primers for NAVAIR have been developed with Deft’s 44GN098 having the best 

performance. ARL has developed chrome free, zero VOC primers, which have performed well in 

studies so far. ARL has also developed two potential zero VOC topcoats for aircraft and land 

systems. The first uses alternative Bayer polyols allowing for the elimination of VOC solvents 

(water is the only solvent) while maintaining water dispersibility cured with the standard 

isocyanates dissolved in ZVOC solvents. The other formulation uses these alternative Bayer 

polyols, but is cured with a ZVOC Isopheronediisocyanate (IPDE) solution. This waterdispersible 

formulation has faster cure and dry time. Furthermore, Low solar absorbing 

formulations have completed and passed evaluations (corrosion, accelerated weathering, etc.) 

and 2 years outdoor exposure. Topcoats with small amounts of fluorinated additives only had a 

marginal effect on performance. 


G-97




DEMONSTRATION OF COMPOSITES WITH LOW HAZARDOUS AIR 

POLLUTANT CONTENTS FOR MILITARY APPLICATIONS 

DR. JOHN LA SCALA 


AMSRD-ARL-WM-MC 


(410) 306-0687 

jlascala@arl.army.mil 

CO-PERFORMERS: Steven Boyd, James M. Sands, and Ian McAninch (Army Research 

Laboratory); Xing Geng, Alexander Grous, and Giuseppe R. Palmese (Drexel University); 

David Fudge, Stephen Andersen, and John Gillespie, Jr. (University of Delaware); Frank Bruce, 

Lt. Dane Morgan, Ken Patterson, and Lawrence Coulter (Air Force Research Laboratory); 

Maureen Foley and Roger Crane (Naval Surface Warfare Center Carderock); Michael Starks 

and Jorge Gomez (U.S. Army TACOM) 

L 

iquid resins used for molding composite structures are a significant source of hazardous air 

pollutant (HAP) emissions. One method of reducing styrene emissions from vinyl ester (VE) 

resins is to replace some or all of the styrene with fatty acid-based monomers. Fatty acid 

monomers are ideal candidates because they are inexpensive, have low volatilities, and promote 

global sustainability because they are derived from renewable resources. This patent pending 

technology allows for the formulation of high performance composite resins with no more than 

25 wt% styrene. As a result, these resins are currently being demonstrated/validated under 

ESTCP WP-0617 for DoD use in Marines HMMWV helmet hardtops, Air Force T-38 dorsal 

covers, MCM composite rudders for the Navy, and Army tactical vehicles, including HMMWV 

hoods, HMMWV transmission containers, and M35A3 truck hoods. This work has validated the 

commercially produced low HAP vinyl ester resins from Applied Poleramics, Inc. for use in 

DoD composite structures. Tests have shown that the established resin formulations meet the 

property requirements, including viscosity, glass transition temperature, modulus, strength, short 

beam shear strength, and fracture toughness. Furthermore the low HAP fatty acid composites 

have improved weatherability relative to the baseline vinyl ester composites. The Army has 

demonstrated the HMMWV transmission container, M35A3 hood, and M939 hood. The Air 

Force has demonstrated the production of an F-22 canopy cover. Validation of these structures is 

underway. An economic analysis has shown that these resins will cost an additional $0.1-1.20/lb 

(depending on manufacturing scale) more than baseline resins. However, these resins reduce life 

cycle cost by more than $1.20/lb making them economically feasible. 

G-98




HYDROGEN RE-EMBRITTLEMENT TEST METHOD FOR CADMIUM PLATING 

H 

ALTERNATIVES AND MAINTENANCE CHEMICALS 

MR. SCOTT GRENDAHL 


Deer Creek Loop 


(410) 306-0819 

sgrenda@arl.army.mil 

CO-PERFORMERS: The Boeing Company, Bell Helicopters 


igh strength steel is used on aircraft components, such as landing gear, and the steel is 

typically cadmium plated to improve the corrosion resistance of the steel. Because high 

strength steel is sensitive to hydrogen embrittlement, precautions need to be taken to ensure that 

when maintenance activities occur on the aircraft they do not cause hydrogen embrittlement of 

the steel. Therefore, aircraft maintenance chemicals are tested per ASTM-F-519, Annex A5 to 

verify that they do not cause hydrogen embrittlement of cadmium plated high strength steel. 

Re-embrittlement testing has been in use for many years by the aerospace industry and is carried 

out with at least five different types of ASTM-F-519 test specimens and at least five different test 

conditions. This means that there are at least 25 different hydrogen re-embrittlement test methods 

currently used. The reason for the different re-embrittlement test methods is the fact that at one 

time there were many different aircraft companies and they all developed their own method to 

test for hydrogen re-embrittlement, and ASTM-F-519 Annex A5 became the repository for all of 

these test methods. Consolidation, or at least a means of comparison, has been a road block since 

inception. 

Efforts are underway to replace cadmium with less hazardous materials and this re-embrittlement 

test is increasingly a testing road block and source of controversy in the implementation of 

cadmium alternatives. In order to satisfy all of the DoD and OEM requirements, and to qualify 

just one maintenance chemical to work with zinc-nickel on high strength steel, it could take as 

many as 25 tests. This is far too many tests to carry-out on just one maintenance chemical and 

there are literally hundreds of chemicals currently being used in the aerospace industry. Under 

current conditions, the total amount of testing required to qualify a single cadmium replacement 

has proven cost and time prohibitive. 

The ASTM-F-07 Committee on Aerospace and Aircraft Test Methods has an F07.04 

subcommittee on hydrogen embrittlement testing that is responsible for ASTM-F-519 and the 

Annex A5 in this specification which deals with hydrogen re-embrittlement testing of aircraft 

maintenance chemicals. This subcommittee is very interested in reducing and improving the reembrittlement 

tests specified in Annex A5 and wants to consider other test specimen materials 

besides cadmium plated steel. However, in order to change the test method, it is necessary to 

determine the accuracy and repeatability of the current and proposed test methods. This work is 

funded by SERDP. 

G-99




T 

NEAR-INFRARED RADIATION BASED COMPOSITE REPAIR 

USING THERMOPLASTICS AS ADHESIVES 

MR. SHRIDHAR YARLAGADDA 

University of Delaware 

201 Composites Manufacturing Science Laboratory 

Newark, DE 19716 

(302) 831-4941 

yarlagad@udel.edu 

he The team of University of Delaware Center for Composite Materials and Kubota 

Research, Inc. has developed novel thermoplastic alternatives to thermoset adhesives for 

military platforms with a near-infrared heating system for bonding and repair of composite 

materials. The use of thermoplastics eliminates the generation of VOC’s and HAPs, as well as 

hazardous waste, and the P-Wave welding system provides a low cost, highly portable system for 

providing the required selective heating at the repair interface. Thermoplastic systems were 

developed that demonstrated equivalent or better peel and lap shear strengths compared to 

thermosets for similar bonding or processing conditions. Potential applications being evaluated 

include bonding of support studs for aircraft interior wiring and field repair of composite 

structures. 

This project is funded by SERDP Project WP-1581. 

G-100


Chlorinated Solvents — DNAPL Source Zone Remediation 


A 

MECHANISM OF BASE-ACTIVATION OF PERSULFATE FOR 

IN SITU CHEMICAL OXIDATION (ISCO) 

DR. RICHARD WATTS 


Box 2910 

Pullman, WA 99164-2910 

(509) 335-3761 

rjwatts@wsu.edu 

CO-PERFORMERS: Olha S. Furman, Ana Maria Ocampo, Robert E. Vaughan, and 

Amy L. Teel (Washington State University); Richard A. Brown (ERM); 

Phillip A. Block (FMC Corporation) 

ctivated persulfate is an increasingly popular reagent for the in-situ chemical oxidation 

(ISCO) remediation of contaminated soils and groundwater. Persulfate is significantly more 

stable than hydrogen peroxide, providing the potential for transport from the point of injection to 

contaminants in lower permeability regions of the subsurface. Persulfate must be activated to 

generate the reactive oxygen species necessary to oxidize most contaminants of concern, such as 

trichloroethylene (TCE), perchloroethylene (PCE), 1,1,1-trichloroethane (TCA), etc. Persulfate 

activation is usually accomplished using transition metals or sodium hydroxide with activation 

by sodium hydroxide currently most common. The objective of this research under ER-1489 was 

to investigate a number of routes of persulfate activation to provide more effective application of 

activated persulfate for ISCO. 

The mechanism of base-activated persulfate was studied in laboratory-scale batch reactors using 

probe compounds that react with specific oxygen species (e.g., nitrobenzene was used as a probe 

for hydroxyl radical and 1,3,5-trinitrobenzene was used as a probe for hydroperoxide anion). The 

generation of specific reactive oxygen species was confirmed by the addition of tert-butyl 

alcohol, which scavenges hydroxyl radical, and isopropanol, which scavenges both sulfate and 

hydroxyl radical. 

Based on the results, we proposed the following mechanism for base-activated persulfate 

decomposition: (1) base-catalyzed hydrolysis of some of the persulfate to form hydroperoxide 

and two sulfate anions; (2) subsequent reduction of other persulfate molecules by the 

hydroperoxide generated in the first reaction to yield sulfate radical and sulfate anion, with 

oxidation of the hydroperoxide to superoxide; and (3) oxidation of hydroxide anion by sulfate 

radical to produce hydroxyl radical. 

In a further investigation of this mechanism, electron spin resonance (ESR) spectra confirmed 

the presence of hydroxyl and sulfate radicals, and the addition of hydroperoxide to a basic 

persulfate system increased superoxide generation in proportion to the concentration of 

hydroperoxide added. The proposed mechanism is consistent with the data obtained to date, and 

explains the widespread reactivity characteristic of base-activated persulfate systems. 

G-101




C 

QUANTIFYING ORGANIC CHEMICALS IN SOIL SAMPLES: EFFECTS OF 

SAMPLING METHOD ATTRIBUTES UNDER VARIED CONTAMINANT 

CHARACTERISTICS AND ENVIRONMENTAL CONDITIONS 

DR. ROBERT L. SIEGRIST 


Environmental Science and Engineering 

Coolbaugh Hall 206 

Golden, CO 80401-1887 

(303) 384-2158 

siegrist@mines.edu 

CO-PERFORMERS: Ryan Oesterreich and Leanna Woods (Colorado School of Mines); 

Dr. Michelle Crimi (Clarkson University) 

ontaminated land continues to present a major challenge on a global scale, and particularly 

for sites where volatile organic chemicals (VOCs), including Dense Non-Aqueous Phase 

Liquids (DNAPLs), are present in soil and groundwater. To enable risk assessment and costeffective 

remediation where necessary, soil and groundwater monitoring is routinely required. 

Although widely employed, standard practices do not necessarily yield accurate and unbiased 

estimates of contaminant levels or remediation effectiveness. To enhance the fundamental 

understanding of current practices and to develop improved methods for obtaining and utilizing 

data from direct-push cores and groundwater wells, SERDP Project ER-1490 is ongoing at the 

Colorado School of Mines (CSM). The project has two complementary elements that are focused 

on understanding and mitigating: (1) the organic chemical losses that occur during sample 

acquisition and handling, and (2) the effects of remediation-induced changes in the behavior of 

untreated organic chemicals including DNAPL compounds. This poster presentation highlights 

the methods and results obtained from the first of these two project elements. During this 

research, soil cores were contaminated under laboratory conditions and then used to quantify the 

ability of different sampling methods to yield accurate and unbiased measurements of 

contaminant levels in soil samples obtained from an intact core and how that ability was affected 

by varied contaminant characteristics and environmental conditions. Three chemicals with 

contrasting properties were studied (1,1,1-TCA, TCE, PCE) at three different contaminant levels. 

Five different sampling methods were studied - including standard and improved methods - 

spanning a range of media disaggregation and atmospheric exposure that can occur during soil 

sample acquisition and handling. Environmental conditions were varied to include different soil 

types (different particle size distributions and organic carbon contents), soil water contents 

(vadose zone and groundwater zone water conditions), and soil temperatures (five levels ranging 

from 5ºC to 80ºC representing different ambient and thermal treatment conditions). Research 

results have revealed that standard sampling methods commonly introduce a negative bias in 

measured concentrations of 50% or more, with the magnitude depending on the attributes of the 

sampling method used and the contaminant characteristics and environmental conditions. The 

research findings provide essential insight into the need for and selection of effective, yet 

practical, sampling methods that can generate accurate and unbiased contaminant data. 

Moreover, the research has revealed that under certain environmental conditions, it may be 

virtually impossible to obtain accurate measurements of certain organic chemicals, illustrating 

the need for alternative strategies for site assessment and remediation performance assessment. 

G-102




DEVELOPMENT OF A PROTOCOL AND SCREENING TOOL FOR SELECTION 

OF DNAPL SOURCE AREA REMEDIATION 

CARMEN A. LEBRÓN 

Naval Facilities Engineering Services Center 



(805) 982-1616 

carmen.lebron@navy.mil 

CO-PERFORMERS: Dr. Julie Konzuk, Dr. David Major, Cherilyn Carrara, Dr. Melanie 

Duhamel, and Dr. Gavin Grant (Geosyntec Consultants, Inc.); Dr. Bernard Kueper and Michael 

West (Queen’s University); Dr. Jason Gerhard and Tiwee Pang (University of Edinburgh) 

A 

Dense Non-Aqueous Phase Liquid (DNAPL) remediation screening tool is currently being 

developed under ESTCP Project ER-0424. The tool will provide users with observed 

performance for various technologies applied at statistically similar sites and thus aid users in 

determining the remedial approach that may meet their site-specific remedial goals. This 

screening tool has as its basis a comprehensive database of case studies of DNAPL remediation 

compiled from various sources comprising remedial performance data from site applications, 

laboratory experiments, and numerical simulation studies. Included in this comprehensive data 

set are the results of numerical simulations (being completed by Queen’s University and the 

University of Edinburgh) of template sites representing typical geological settings and conditions 

encountered at Department of Defense (DoD) facilities impacted with DNAPLs. The screening 

tool will allow users to quickly access a large volume of performance data while filtering the 

output to show only the results relevant to the particular site under study. Users can also filter the 

output by study type or other parameters. 

The numerical simulations of the template sites provide the following information that cannot be 

determined from field applications: (1) more detailed information on remedial performance such 

as total mass removed and mass remaining; (2) improved understanding of the critical factors 

impacting technology performance through sensitivity studies; and (3) direct comparison 

between technology performance and specific site characteristics. For example, the numerical 

modeling completed to date has shown that chemical oxidation using permanganate (MnO4-) 

may reduce downgradient mass flux from a DNAPL source zone within weeks to months from 

treatment initiation and is capable of achieving partial removal of the DNAPL phase. However, 

MnO4- consumption is often inefficient (~8 to 10 times more MnO4- reacts with natural organic 

matter than contaminant in simulations with typical levels of organic matter), and the rate of 

DNAPL removal can become diffusion-limited due to the formation of manganese dioxide 

precipitate rind surrounding the DNAPL phase, prolonging necessary treatment time. 

The screening tool protocol was developed using multivariate regression analyses to identify key 

parameters affecting each performance metric for each DNAPL remediation technology. Results 

of the numerical simulations and case study review will be presented. 

G-103




IMPROVING EFFECTIVENESS OF BIOREMEDIATION AT DNAPL SOURCE 

ZONE SITES BY APPLYING PARTITIONING ELECTRON DONORS (PEDS) 





(805) 982-1616 


CO-PERFORMERS: Dr. David Major and Michaye McMaster (Geosyntec Consultants, Inc.); 

Dr. Frank E. Löeffler and Dr. Kurt D. Pennell (Georgia Institute of Technology) 

P 

artitioning electron donors (PEDs) are water soluble substrates that can partition strongly 

into a Dense Non-Aqueous Phase Liquid (DNAPL). The PED is subsequently released from 

the DNAPL back into groundwater, providing reducing equivalents at the DNAPL water 

interface, which promotes the growth of dechlorinating biomass adjacent to the DNAPL, which 

in turn enhances DNAPL dissolution rates. PEDs offer advantages over traditional electron 

donor applications because their physicochemical properties allow for more specific targeting of 

the DNAPL, resulting in lower overall costs due to increased specificity in their consumption. 

The objective of ESTCP Project ER-0716 is to demonstrate/validate (DEM/VAL) the application 

of a partitioning electron donor to improve the biologically enhanced dissolution rate of 

DNAPLs and ultimately reduce the cost of in-situ bioremediation. The project involves both 

laboratory and field components. The laboratory assessment is required in order to screen the 

suitability of the candidate PEDs, and to collect key data that will be used to design the PED 

field application. The field component will involve applying the selected PED to a DNAPL 

source zone by amending recirculated groundwater with the PED. The recirculation system 

provides control of the delivery process, and allows the operator to tailor the PED addition to the 

site. 

Work to date has focused on the laboratory studies, in which two PEDs have been evaluated, n- 

butyl acetate (nBA) and n-hexanol. Batch and column studies have been conducted to evaluate 

the mass transfer of the PEDs into NAPLs, using both pure trichloroethene (TCE) DNAPL and a 

surrogate NAPL consisting of DEM/VAL site contaminants, TCE and 1,1,1-TCA, in 

hexadecane. These experiments suggest that nBA partitions strongly into the NAPL (n-hexanol 

less strongly), which supports the concept that a single PED application will provide electron 

donor to support microbial reductive dechlorination well beyond the time that PED is actively 

amended to the system, thereby reducing the need for frequent or repeated PED injections 

independent of groundwater velocity. Batch testing has demonstrated that KB 1 Plus ® , a 

consortium of microbes capable of reductive dechlorination of chlorinated ethenes and ethanes, 

is able to degrade nBA for use as an electron donor to dechlorinate TCE and 1,1,1-TCA. 

Ongoing column testing is further evaluating nBA as a PED using DEM/VAL site soil and a 

surrogate NAPL that mimics concentrations observed at the site. Findings from these laboratory 

studies will inform the design of the field implementation at the DEM/VAL site. 

G-104




L 

DNAPL REMOVAL FROM FRACTURED ROCK USING THERMAL 

CONDUCTIVE HEATING (TCH)—TREATABILITY STUDY AND TCH 

DEMONSTRATION PILOT PROGRESS 



ESC411 



(805) 982-1616 


CO-PERFORMERS: Dr. Bernard H. Kueper (Queen’s University); Dr. Gorm Heron, John 

LaChance, and Devon Tarmasiewicz (TerraTherm, Inc.); Pierre J. Lacombe (USGS) 

aboratory treatability studies and installation of the field pilot system is underway for the 

four-year ESTCP-funded project to demonstrate chlorinated volatile organic chemicals 

(CVOC) DNAPL removal from fractured rock (silt- and mudstone) using Thermal Conductive 

Heating (TCH). The demonstration site is located at the former Naval Air Warfare Center 

(NAWC) in West Trenton, New Jersey and the treatability studies are being performed at 

Queen’s University in Canada. 

TCH design includes 15 vertical TCH heaters that are 50-ft long, an insulating vapor cover, and 

an off gas vapor treatment system comprised of a heat exchanger, cooling tower, positive 

displacement blower and granular activated carbon. The area and volume of the pilot test is 

approximately 400 ft 2 and 740 cy, respectively. 

Drilling, coring, and characterization efforts performed during installation of the pilot system 

will provide information on the fracture and matrix properties and hydraulic characteristics of the 

rock, and the mass of CVOCs in the rock. Instrumentation installed in the pilot area will provide 

3-D information on the rate of heat up and the distribution/variability of temperature and 

pressure over time. Sampling and analysis of the extracted vapor stream will provide 

information on the flow rates, amount of water extracted as steam, CVOC concentrations in 

vapor, and the rate and total amount of mass removed from the pilot test volume. 

Samples of bedrock material from the pilot area as well as other types of bedrock are being 

conditioned and tested in the laboratory. These studies include: characterization of rock types for 

matrix porosity, pore throat distribution, organic carbon, and bulk density; forward diffusion of 

trichloroethylene (TCE) and tetrachloroethylene (PCE) into rock samples; heating of rock 

samples and quantification of the relationships between heating temperature, heating duration 

and mass removal; construction of a rock crusher to prepare samples for micro-wave assisted 

extraction; and related analytical and numerical modeling. 

The goal of this project is to provide useful guidelines so that when practitioners apply the 

technology they avoid misperceptions regarding what is attainable in terms of mass removal, 

reduction of aqueous phase contaminant flux, reduction of aqueous phase concentrations, and 

reduction in source zone lifespan. 

G-105




DNAPL DISSOLUTION AND DECHLORINATION IN DISCRETE FRACTURES 

T 

MR. CHARLES SCHAEFER 


17 Princess Road 

Lawrenceville, NJ 08648 

(609) 895-5372 

charles.schaefer@shawgrp.com 

CO-PERFORMERS: Charles Condee (Shaw Environmental, Inc.); Peggy Altman, 

Kaneen Christensen, Jared King, and John McCray, Ph.D. (Colorado School of Mines) 

he dissolution of Dense Non-Aqueous Phase Liquids (DNAPLs) in fractured bedrock is not 

well understood, thereby limiting efforts to predict the longevity of DNAPL sources, select 

appropriate remedial technologies, effectively design and implement in-situ technologies, 

evaluate remedial performance, and estimate remediation time. Experiments were performed 

under SERDP Project ER-1554 in discretely fractured sandstone blocks to evaluate DNAPL 

architecture, and to evaluate impacts of the DNAPL architecture on DNAPL dissolution rates. 

DNAPL residual saturations, DNAPL-water interfacial areas, and dissolution mass transfer 

coefficients were measured in four fractured systems. Bedrock fracture bioaugmentation 

experiments using Dehalococcoides sp. (DHC) are currently underway, where dechlorination 

kinetics, microbial transport, and DNAPL dissolution are being evaluated as a function of DHC 

inoculation dosage. 

Results of the DNAPL dissolution experiments showed that DNAPL residual saturations 

(DNAPL volume/fracture volume) ranged between 0.25 and 0.54 for the rocks studied. DNAPLwater 

specific interfacial areas ranged between 24 cm 2 /cm 3 and 57 cm 2 /cm 3 . No measurable 

correlation was observed between DNAPL-water interfacial area and aperture, aperture ratio, or 

residual saturation. DNAPL-water interfacial areas were comparable to DNAPL-water interfacial 

areas reported in sands with grain diameters similar to the rock apertures. However, the DNAPL 

residual saturation in the fractures were two- to four-times greater than in the sands, suggesting 

that PCE dissolution rates in rock fractures may be substantially less than in unconsolidated 

media, as the effective interfacial area per volume of DNAPL in rock fractures was less than in 

sands. Comparison of dissolution mass transfer coefficients in the bedrock fractures to 

corresponding mass transfer coefficients measured in sands indicated that dissolution rates in 

bedrock fractures were substantially less than those measured in sands, even after normalizing to 

DNAPL-water interfacial area. DNAPL-water interfacial area normalized mass transfer 

coefficients for each bedrock fracture showed a similar functionality with respect to the 

Reynolds Number. 

Preliminary results from the bioaugmentation experiments showed that an effective PCE-toethene 

first-order dechlorination rate constant of 4H10 -4 /hr was measured at an aqueous DHC 

concentration of 1H10 6 cell/L. This observed rate correlates well to rates measured in soil 

columns without DNAPL present. Despite the relatively rapid dechlorination rates, an increase in 

aqueous phase DHC concentrations were not observed over a 3-month period, and rebioaugmenting 

did not result in an increase in measured dechlorination rates. No substantial 

biofouling or clogging of the fracture has been observed. 

G-106




I 

COUPLING POLYMER FLOODS WITH BIODEGRADATION AND CHEMICAL 

OXIDATION TREATMENT – TECHNIQUES TO ACHIEVE MORE EFFECTIVE 

GROUNDWATER REMEDIATION IN HETEROGENEOUS AQUIFERS 

MEGAN M. SMITH 


1500 Illinois Street 

Golden, CO 80401 

(303) 384-2095 

megsmith@mines.edu 

CO-PERFORMERS: Jeff A.K. Silva, Junko Munakata-Marr, and John E. McCray 

(Colorado School of Mines) 

n contaminated aquifer systems, small heterogeneities (resulting from differences in 

permeability or contaminant saturation) often influence the distribution of injected remediation 

agents, causing them to travel mainly through preferential higher-permeability flowpaths. 

Combining a viscous polymer flood with the remediation agent may enhance agent delivery into 

layers of differing permeability within the system and increase the effectiveness of remedation 

treatment, if the polymer solution remains stable in the presence of the remediation agent. Our 

research (SERDP Project ER-1486) combines various polymer solutions with the commonly 

utilized remediation techniques of chemical oxidation and stimulated biodegradation, for more 

thorough clean-up of chlorinated solvents at groundwater sites containing subsurface 

heterogeneities. Compatibility testing of polymer/chemical oxidant mixtures shows that certain 

solutions can be optimized for given site conditions in order to maximize viscosity retention and 

minimize oxidant demand. Xanthan polysaccharide and potassium permanganate solutions prove 

particularly compatible over multi-day timescales, and so the possibility of combining similar 

polymer molecules with permanganate is also investigated. Advantages and limitations of these 

compatible polymer/oxidant combinations are discussed, and possible experimental delivery 

strategies (co-injection versus staggered or graded floods) are compared. In addition, the 

coupling of bioremediation techniques with polymer floods is examined using batch tests 

containing anaerobic dechlorinating bacteria and polymer solutions. The continued ability of the 

microbes to completely degrade the test contaminant (tetrachloroethene, or PCE) to ethene is 

considered as a measure of basic compatibility. At present, results do not indicate that PCE 

degradation is inhibited by the presence of hydrolyzed polyacrylamide or xanthan polymers. 

Although our research initially focused on polymer solutions simply as a delivery vehicle for 

bioaugmenting a contaminated site, experimental findings also raise the possibility of the 

polymer molecules serving a dual role as electron donors. Further experiments comparing the 

rates of dechlorination in microcosms fed both with a traditional electron donor (methanol) and 

without such a donor are used to determine if polymer can serve as an adequate electron donor 

during the process of anaerobic dechlorination of PCE. 

G-107




THE ADDITION OF WATER-SOLUBLE POLYMERS TO ENHANCE THE 

DELIVERY OF IN SITU REMEDIATION AGENTS IN HETEROGENEOUS STRATA 

JEFF ALLEN KAI SILVA 


Environmental Science and Engineering Division 



(303) 579-1275 

jsilva@mines.edu 

CO-PERFORMERS: Megan M. Smith and Dr. John E. McCray (Colorado School of Mines) 

A 

key challenge to subsurface remediation effectiveness is achieving an efficient sweep of 

the contaminated zone during treatment. This is true of forced-injection strategies that rely 

on direct contact between the amendment and the target contaminant, as well as for strategies 

that rely on uniform placement of amendments and subsequent dissolution of the amendment. 

Subsurface permeability heterogeneities can often limit the sweep efficiency of injected 

remediation agents due to by-passing of lower permeability media (LPM) during treatment. If 

sufficient contamination exists within this LPM, remediation fluid by-passing during initial 

treatment can lead to rebounding of contaminant concentrations within the treatment zone. 

Methods designed to mitigate the potential for preferential flow and by-passing effects would 

therefore be highly desirable to the Department of Defense to increase remediation efficiencies 

and reduce the costs of environmental restoration efforts. 

The overall focus of this research (SERDP ER-1486) is to explore the utility and efficacy of 

adding water-soluble polymers to remediation fluids to promote heterogeneity control and 

mitigate by-passing of LPM during in situ treatment. This presentation will initially focus on the 

results of 2-D tanks experiments and numerical simulations performed to test and develop 

predictive relationships between permeability heterogeneity structure and sweep efficiency 

improvement resulting from polymer addition. The importance of these relationships are to allow 

site managers a means of readily assessing whether including polymer within remediation 

amendment formulations would be advantageous at a given site. 

Additionally, 2-D experimental results highlighting the potential for Dense Non-Aqueous Phase 

Liquid (DNAPL) mobilization during polymer-amended remediation fluid delivery will be 

presented. Specifically, these results demonstrate that if DNAPL is present within a treatment 

zone in excess of residual saturation the addition of polymers can promote more horizontal 

migration, rather than downward migration, of DNAPL by enhancing the ratio of viscous to 

capillary forces (i.e., the local Capillary Number). The potential benefits and limitations of this 

process, as it relates to implementation design, will be presented. 

G-108




T 

COUPLING SURFACTANTS WITH PERMANGANATE FOR PCE DNAPL 

MASS REMOVAL: COINJECTION OR SEQUENTIAL APPLICATION 

AS DELIVERY METHODS 

PAMELA J. DUGAN, PH.D. 

Carus Corporation 


LaSalle, IL 61301 

(815) 224-6870 

pamela.dugan@caruscorporation.com 

CO-PERFORMERS: Dr. Robert L. Siegrist (Colorado School of Mines); 


wo-dimensional (2-D) flow-through cell experiments were conducted to investigate coupling 

surfactant-enhanced aquifer remediation (SEAR) with in-situ chemical oxidation (ISCO) of 

tetrachloroethene (PCE) dense non-aqueous phase liquid (DNAPL) for PCE mass destruction. 

Previous batch screening tests were performed on surfactants and cosolvents in the presence of 

the oxidant potassium permanganate (KMnO 4 ), to assess compatibility for coupling with 

KMnO 4 . The anionic surfactants sodium dioctyl sulfosuccinate (Aerosol OT), and sodium 

hexadecyl diphenyl oxide disulfonate (Dowfax 8390) were compatible and selected for use. Two 

delivery methods were investigated: (1) coinjection of 0.66 pore volumes (PVs) of 1.0-wt% 

Aerosol-OT, 0.5-wt% Dowfax 8390, 0.35-wt% CaBr 2 , and 0.75-wt% NaBr, (for enhanced PCE 

solubilization) with 0.5-wt% KMnO 4 (for DNAPL mass destruction), and (2) sequential 

application of 0.66 PVs of the same surfactant solution followed by 0.66 PVs of 0.5-wt% 

KMnO 4 flush. The 2-D cell packing configuration consisted of a fine-grained silica sand matrix 

with an embedded medium-grained sand lens, which allowed for the development of a high 

saturation PCE DNAPL source zone (~9-11% v/v) within the lens of each cell. For both 

experiments the flushing solutions were delivered at a linear velocity of 52 cm/day. Water 

quality samples were collected from eight point sampling ports, as well as the cell effluent. 

Samples were analyzed for PCE, chloride, and permanganate. At the conclusion of the 

experiments, the mass of PCE removed was quantified by destructively analyzing the cell. 

Results indicate complete mass removal using sequential application as a delivery method. In the 

coinjection experiment, cores extracted at the conclusion revealed that 99.8% of PCE DNAPL 

mass was removed. However, it was not possible to close a mass balance between the initial PCE 

added and the PCE removed. It is hypothesized this result was due to incomplete oxidation 

whereby destruction of PCE occurs without mineralization. Results indicate that coupling 

surfactants with permanganate holds promise as a viable method for in-situ mass depletion of 

PCE DNAPL using sequential application as a delivery method. Although experimental results 

were encouraging with respect to the coinjection of surfactants and permanganate for DNAPL 

mass removal, further bench-scale research is warranted prior to implementation in the field. 

G-109




P 

DESIGNING EFFICIENT PERMANGANATE INJECTION SYSTEMS IN 

HETEROGENEOUS AQUIFERS 

ROBERT C. BORDEN 



Raleigh, NC 27695 

(919) 515-1625 

rcborden@eos.ncsu.edu 

CO-PERFORMERS: Dr. Robert L. Siegrist (Colorado School of Mines); 


ermanganate (MnO 4 ) is commonly used to oxidize a variety of groundwater contaminants 

including chlorinated ethenes, aromatic hydrocarbons, phenols and explosives. In this 

process, an aqueous solution of NaMnO 4 or KMnO 4 is injected into the treatment zone. The 

MnO 4 is transported away from the injection point by diffusion and groundwater flow. When the 

MnO 4 comes in contact with a contaminant, a chemical reaction occurs consuming both the 

MnO 4 and the contaminant. However at many sites, most of the MnO 4 is consumed during 

reaction with the Natural Oxidant Demand (NOD) of the aquifer material. 

While permanganate injection systems can be very effective in treating a wide variety of 

contaminants, this approach has not always met design objectives. In some cases, the NOD of the 

aquifer material is greater than expected, resulting in rapid MnO 4 depletion and inadequate 

treatment. In other cases, a significant portion of the contaminant mass is present in difficult to 

access lower permeability zones and remains untreated. Once the MnO 4 is depleted, these 

contaminants can diffuse back into mobile zones causing a rebound in observed contaminant 

concentrations. To be effective, MnO 4 must come into direct contact with the contaminant to be 

treated. However, this can be difficult in heterogeneous aquifers where large spatial variations in 

hydraulic conductivity make it difficult to uniformly distribute the treatment reagents. 

The numerical models MODFLOW and RT3D were used to simulate the transport and chemical 

reaction of MnO 4 and TCE in spatially heterogeneous aquifers. The hydraulic conductivity field 

was generated using the Turning Bands Method with three different levels of heterogeneity: low, 

medium and high. Injection approaches included simultaneous and sequential injection of wells 

arranged in grids. Injection performance was evaluated by calculating the volume-weighted 

contact efficiency and the mass of contaminant remaining at the end of the injection process. 

Design curves were then generated illustrating the effect of different variables on performance. 

A spreadsheet based tool has been developed, as part of ESTCP Project ER-0626, to assist 

designers in planning efficient, lower cost injection systems. Information on aquifer parameters 

and costs for labor, reagent and well installation are entered first. Results from the 

MODFLOW/RT3D model simulations are incorporated as a series of curves illustrating the 

effect of different design variables on performance. The designer can then easily evaluate the 

effect of different injection approaches on MnO 4 distribution, initial capital cost and 30-year life 

cycle costs. 

G-110




IN SITU “ADVANCED MIXED OXIDATION AND INCLUSION” 

TECHNOLOGY: INCLUSION BEHAVIOR OF TCE DNAPL AND 

OZONE INTO CLATHRATES 

DR. RAYMOND BALL 

EnChem Engineering, Inc. 

119 Oakdale Road 

Newton, MA 02461 

(617) 795-0058 

rball@en-chem.com 

CO-PERFORMERS: Yun Li and Weilin Huang (Rutgers University); Yongqing Zhang (South 

China University of Technology and Rutgers University); Elizabeth Erin Mack (DuPont 

Corporate Remediation Group) 

I 

n-situ chemical oxidation (ISCO) is commonly used to remediate volatile organic compounds 

(VOCs) (i.e., petroleum hydrocarbons, chlorinated solvents), but has a number of potential 

complications, including difficulty in treating DNAPL compounds (i.e., perchloroethene [PCE], 

trichoroethene [TCE], dichloroethene [DCE]). Several studies have successfully treated DNAPL 

compounds through the generation and use of radical species (i.e., Hong & Zeng, 2002; Liou et. 

al, 2004). We present an oxidation chemistry using a combination of ozone-hydrogen peroxidepersulfate 

for subsurface remediation of VOCs, with a focus on the breakdown of these 

compounds via clathrate inclusion and enhanced radical production. This chemistry generates 

hydroxyl radical, sulfate radical, perhydroxyl radical, and superoxide radical species in situ, with 

concentrations of each species dependent on solution pH and temperature. Clathrates are used to 

stabilize ozone in situ for enhanced transport and to enhance solubilization of the DNAPL. 

The following results based on batch and column tests, are presented with a focus on the 

application of the technology to in-situ remediation of DNAPL: 

• Relationship of TCE solubility and clathrate solubility; 

• Percentage of TCE degradation with ozonation dose and time; 

• Percentage of TCE degradation with clathrate and ozonation; 

• Percentage of clathrate degradation with ozonation dose and time; 

• Percentage of TCE degradation with ozone-hydrogen peroxide dosages and time; 

• Percentage of TCE degradation with clathrate and ozone-hydrogen peroxide; 

• Percentage of TCE degradation with ozone-hydrogen peroxide-persulfate dosages and 

time; 

• Percentage of TCE degradation with clathrate and ozone-hydrogen peroxide-persulfate. 

A thorough discussion of the chemistry will be presented with additional discussion of in-situ 

applications involving DNAPL compounds. 

G-111




PERSULFATE PERSISTENCE UNDER THERMAL ACTIVATION CONDITIONS 

DR. RICK JOHNSON 


20000 NW Walker Road 

Beaverton, OR 97006 

(503) 748-1193 

rjohnson@ebs.ogi.edu 

CO-PERFORMERS: Paul G. Tratnyek and Reid O’Brien Johnson (Oregon Health & Science 

University) 

C 

ontaminant destruction with in-situ chemical oxidation (ISCO) using persulfate 

(peroxydisulfate) can be enhanced by activation, which increases the rate of persulfate 

decomposition to sulfate radicals. This step initiates a chain of radical reactions involving species 

(including sulfate and hydroxyl radicals) that oxidize contaminants more rapidly than persulfate 

does directly. Among current activation methods, thermal activation is the least sensitive to 

geochemical conditions (e.g., pH and carbonate concentration) and its temperature dependence is 

described by the Arrhenius model. Combining new data for environmentally relevant conditions 

with previously published data, we have computed three sets of Arrhenius parameters (ln A and 

Eact) that describe the rate of persulfate decomposition in homogeneous solutions over a wide 

range of temperatures and pH. The addition of soil increases the decomposition rate of persulfate 

due to reactions with organic matter and possibly mineral surfaces, but the kinetics are still 

pseudo-first-order in persulfate and conform to the Arrhenius model. A series of respike 

experiments with soil at 70°C demonstrate that once the oxidant demand is met, reaction rates 

return to values near those observed in the homogeneous solution case. However, even after the 

oxidant demand is met, the relatively short lifetime of the persulfate at elevated temperatures 

(e.g., >50°C) will limit the delivery time over which persulfate can be effective. 

The results presented here have a number of important implications for the application of 

thermally-activated persulfate oxidation. The first is that thermal decomposition of persulfate 

follows well-behaved kinetics, which should allow the behavior of persulfate to be predicted 

based on straightforward laboratory feasibility tests using relevant materials. Second, the 

presence of soil increases the rate at which persulfate decomposes until the soil oxidant demand 

has been met. Third, once the soil oxidant demand has been met, persulfate continues to degrade 

via the first-order thermal decomposition reaction. Finally, and perhaps of greatest importance, 

the lifetime of persulfate (and therefore the availability of sulfate radical) is relatively short at 

elevated temperatures, which limits the distances over which diffusion of persulfate can be 

effective and which imposes design constraints on the in-situ application of thermally-activated 

persulfate. 

This work is funded by SERDP Project ER-1458. 

G-112




M 

CONTAMINANT MASS TRANSFER DURING BOILING IN FRACTURED 

GEOLOGIC MEDIA 

RONALD FALTA 


Brackett Hall, Room 340C 

Clemson University, SC 29634-0919 

(864) 656-0125 

faltar@clemson.edu 

CO-PERFORMER: Larry Murdoch (Clemson University) 

any sites contaminated with chlorinated volatile organic compounds (CVOCs) are 

underlain by fractured rocks or soils with significant matrix porosity. Remediation options 

for treating these sites are limited because low matrix permeability and unknown fracture 

locations make the delivery or recovery of fluids a challenge. Thermal methods hold promise for 

remediation of fractured media because the mechanisms of thermal conduction and electrical 

resistance heating can efficiently transfer heat without any fluid flow. Once a fractured rock or 

soil is heated above the water boiling point, subsequent depressurization of the fracture network 

by vacuum extraction may induce boiling in the matrix, leading to large gas-phase pressure 

gradients and a steam stripping effect that can remove the contaminants from the matrix. These 

contaminant removal mechanisms, however, have not been demonstrated in the laboratory. 

Numerical simulations show that these processes may be very sensitive to the details of the gas 

and liquid phase relative permeabilities, and to the intrinsic permeability and other rock 

properties. Our current focus in project SERDP (ER-1553) is on experimentally demonstrating 

the boiling phenomena using one-dimensional rock cores with a simulated fracture at one end. 

These cores are instrumented with thermistors and electrodes to allow measurement of 

temperature and electrical conductivity, respectively. The electrical conductivity is a strong 

function of water saturation, and once calibration curves are developed for a particular rock type, 

the electrodes can be used to measure changes in liquid saturation in the core. The core is heated 

by thermal conduction from the outside, and is sealed and contained in a pressure vessel to 

simulate a confining pressure. The core is initially saturated with water, and then heated, while 

the simulated fracture at one end of the core is depressurized. Current experiments involve 

uncontaminated water, to focus on the fluid and heat flow aspects of the boiling process. Future 

experiments will use water that is contaminated with CVOCs to focus on the contaminant mass 

transfer itself. The results of the experiments will be evaluated with numerical analyses, which 

will then be used to evaluate field-scale implementation at contaminated sites. 

G-113




DECISION & MANAGEMENT TOOLS FOR DNAPL SITES: OPTIMIZATION 

OF CHLORINATED SOLVENT SOURCE AND PLUME REMEDIATION 

CONSIDERING UNCERTAINTY 

RONALD FALTA 


Brackett Hall, Room 340C 

Clemson University, SC 29634-0919 

(864) 656-0125 

faltar@clemson.edu 

CO-PERFORMERS: Charles Newell and Shala Farhat (Groundwater Services, Inc.); Suresh Rao 

and Nandita Basu (Purdue University); Hailian Liang (Clemson University) 

D 

etermining the best remediation course of action at sites contaminated by DNAPLs is an 

extremely difficult engineering challenge. Uncertainties in the cost and performance of 

source and plume remediation technologies complicate the decision making process. Predicting 

the impact of the source remediation efforts on plume response is hindered by the lack of tools 

that explicitly relate source remediation to the downgradient plume over time and space. Our 

ESTCP project (ER-0704) is leveraging several recent SERDP and ESTCP research efforts to 

develop an integrated modeling tool to help site managers address these issues. 

An analytical model called REMChlor (for Remediation Evaluation Model for Chlorinated 

solvents) is used as the technical foundation for this project. This model, produced as part of 

SERDP ER-1295, is a significant improvement on existing chlorinated solvent transport models 

such as BIOCHLOR, because it can simultaneously account for both source and plume 

remediation. We have expanded the functionality of REMChlor by: 

• Building a probabilistic framework around the REMChlor source/plume remediation 

code, so that uncertainty in hydrogeologic variables, remediation performance, source 

loading, plume response, risk factors, and cost can be accounted for and visualized by 

users of the new software. This was done using the GoldSim probabilistic simulation 

software; 

• Developing a graphical user interface to the coupled GoldSim/REMChlor model that can 

be freely distributed to the public; 

• Compiling and incorporating results of recent research projects regarding cost and 

performance of source remediation (such as the SERDP Project ER-1293) in the form of 

probability density functions as background information for users of the new tool; and 

• Improving the REMChlor source function to simulate source containment, and added a 

vapor transport calculation module to the cancer risk assessment part of the code. 

The new software gives users a single platform where cost, source treatment, plume 

management, monitored natural attenuation, and risk assessment can all be evaluated together, 

and where uncertainty is incorporated into the site decision making process. 

G-114




I 

A PRELIMINARY ASSESSMENT TOOL FOR USE OF IN-SITU THERMAL 

TECHNOLOGIES AT DNAPL-IMPACTED SITES 

JENNIFER L. TRIPLETT KINGSTON 

Haley & Aldrich 

8735 Rosehill Road 

Lenexa, KS 66215 

(913) 217-6905 

jkingston@haleyaldrich.com 

CO-PERFORMERS: Paul C. Johnson and Paul Dahlen (Arizona State University); 

Shane Williams and Eric Foote (Battelle) 

n-situ thermal soil and aquifer remediation technologies (e.g., electrical resistance heating 

(ERH), conductive heating (CH), steam injection (SI), etc.) have undergone rapid development 

and application in recent years. These technologies offer the promise of more rapid and thorough 

treatment of Non-Aqueous Phase Liquid (NAPL) source zones; however, their field-scale 

application has not been well-documented in the technical literature. 

To gain more information on thermal technology performance this study will tie together a 

combination of results from empirical analyses of available field data and project-specific field 

sampling at target sites. Through the empirical analysis of field data and post-treatment field 

sampling at five sites, the objective was to develop a tool that will enable practitioners, 

regulators, and site owners to anticipate the likely performance efficiency of thermal-based 

technologies for a small number generalized geologic site scenarios. 

Available documents from 182 applications were reviewed, which included 87 electrical 

resistance heating, 46 steam-based heating, 26 conductive heating, and 23 other heating 

technology applications conducted between 1988 and 2007. Approximately 90% of the 182 

applications were implemented after 1995 and about half since 2000. More specifically, this 

review identified the geologic settings in which these technologies were applied, chemicals 

treated, design parameters, operating conditions, and performance metrics. The results of this 

study are summarized in a table linking this information to five generalized geologic scenarios; 

this table was designed to be useful for practitioners considering thermal technologies. The user 

selects one of five geologic settings that most closely resembles their site, and then can quickly 

review which technologies have been applied in that setting, the designs employed, operating 

conditions, and the performance achieved. 

Groundwater impacts, as quantified by dissolved concentrations and mass flux (discharge) into 

the aquifer, were determined by high spatial density sampling and analysis at five thermal 

treatment sites. The range of concentration and mass flux reductions ranged from about




E 

COMBINING LOW-ENERGY ELECTRICAL RESISTANCE HEATING WITH 

BIOTIC AND ABIOTIC REACTIONS FOR TREATMENT OF CHLORINATED 

SOLVENT DNAPL SOURCE AREAS 

TAMZEN MACBETH PH.D., P.E. 

North Wind, Inc. 

1425 Higham 

Idaho Falls, ID 83404 

(208) 557-7846 

tmacbeth@northwind-inc.com 

CO-PERFORMERS: Mike Truex (PNNL); Dr. Mandy Michaelson (USACE, Seattle, WA); 

Tom Powell (TRS, Inc.); Dr. Kent Sorenson (CDM) 

nhanced in-situ bioremediation (ISB), iron-based reduction using zero-valent iron (ZVI), and 

thermal treatment using electrical resistance heating (ERH) have been demonstrated 

independently for residual source zones. Combining in-situ and thermal technologies may 

provide many of the benefits of the in-situ treatments with the shorter remedial timeframe 

associated with thermal treatment. Environmental Security Technology Certification Program 

(ESTCP) Project ER-0719 is focused on demonstrating the benefits of combining low-energy 

ERH with either ISB or ZVI for chlorinated solvent residual source zones. Project objectives 

include the assessment of: (1) the extent to which contaminant degradation is enhanced at 

elevated compared to ambient temperatures; (2) the relative contribution of biotic and abiotic 

contaminant degradation mechanisms at different temperatures; and (3) the cost-benefit of 

applying low-energy heating with in-situ treatments. Phase 1 of the project consists of initial 

characterization and verification of the suitability of each test cell to meet project objectives. 

Phase 2 consists of a field demonstration of ISB and ZVI without heating to establish 

performance of the individual technologies including the degradation kinetics and mass balance 

factors at ambient temperature. Phase 3 consists of a field demonstration of ISB and ZVI with 

low-energy ERH to evaluate treatment performance at elevated temperatures of approximately 

35°C for the ISB cell and 55°C for the ZVI cell including parameters established in Phase 2. The 

focus of the data presented herein is activities completed as part of Phase 1. 

One of the greatest uncertainties to the success of the demonstration was verifying that sufficient 

residual mass was present within the test cells to evaluate removal at ambient and elevated 

temperatures. Therefore, Phase 1 characterization included a soil gas survey in July 2008 

utilizing GORETM Modules to evaluate a large area in and around the proposed test cells to 

establish high-concentration “hot spots.” Following these results, confirmation soil borings and 

sampling, and installation of groundwater monitoring wells and sampling was also conducted in 

August 2008 to verify the presence and concentration of residual mass within soils and to 

establish groundwater and soil vapor concentrations within the planned test cells. The criteria for 

completion of the test cell installation and execution of the demonstration is TCE concentrations 

of at least 10,000 µg/kg in soils and/or 5 ppm in groundwater. Final well installation will occur 

after the decision to continue the demonstration is made and additional hydraulic, groundwater, 

and soil gas characterization will be completed. 

G-116




I 

HYDRAULICS OF IN-SITU ELECTRICAL RESISTANCE HEATING 

AT SUB-BOILING TEMPERATURES 

DR. RICK JOHNSON 


20000 NW Walker Road 

Beaverton, OR 97006 

(503) 748-1193 

rjohnson@ebs.ogi.edu 

CO-PERFORMERS: Brent Sleep and Magdalena Krol (University of Toronto) 

n-situ electrical resistance heating (ERH) has a broad range of potential applications for 

remediation of contaminated groundwater. To date, heating to boiling temperatures and the 

direct removal of contaminants is the most common form of ERH. This approach can be 

effective at rapidly removing contaminants, however, it requires significant infrastructure both to 

deliver the needed power and to treat liquids and vapors driven from the subsurface by the 

heating process. In addition, heating to boiling temperatures does not necessarily couple well 

with other remediation strategies (e.g., biological and chemical). 

Heating at sub-boiling temperatures, on the other hand, can provide conditions that are wellsuited 

to coupled processes (e.g., enhanced microbial activity, chemical oxidation with 

thermally-activated persulfate). However, even at relatively low temperatures (e.g.,




I 

REACTIVITY OF CHLORINATED ETHENES DURING THERMAL TREATMENT 

DR. KURT PENNELL 

Georgia Institute of Technology 

311 Ferst Drive 

Atlanta, GA 30332 

(404) 894-9365 

kpennell@ce.gatech.edu 

CO-PERFORMERS: Jed Costanza, Frank Löeffler, Kelly Fletcher, Nivedhya Ramaswamy, 

Gretell Otaño, and John Callaghan (Georgia Institute of Technology) 

n-situ thermal treatment technologies, such as electrical resistance heating, are capable of 

removing substantial chlorinated solvent mass from the subsurface. Although thermal 

destruction of tetrachloroethene (PCE) and trichloroethene (TCE) has been shown, considerable 

uncertainty exists when attempting to estimate the fraction of contaminant mass that is degraded 

during thermal treatment. The reactivity of PCE and TCE was measured in sealed ampules 

incubated at temperatures ranging from 22 to 120ºC for periods of up 40 days. No more than 

15% of the initial TCE mass was degraded, resulting in the formation of several non-chlorinated 

products including chloride ions, carbon dioxide, carbon monoxide, glycolate, and formate. 

Rates of TCE degradation were relatively insensitive to oxygen content, but increased 

substantially in the presence of iron bearing minerals, with TCE disappearance half-life at 120ºC 

decreasing from 330 to 40 days upon addition of 1% (wt.) goethite. To further explore the effect 

of solids on PCE and TCE degradation, experiments were conducted under SERDP Project ER- 

1419 using soil and groundwater from four sites undergoing thermal treatment. The measured 

half-life for PCE degradation in ampules containing Camelot soil and groundwater was greater 

than 7,000 days at 95°C and was between 590 and 683 days for TCE in ampules containing Fort 

Lewis samples at 95°C. No degradation of PCE, TCE, or cis-DCE was observed in ampules with 

Great Lakes samples, and no degradation of TCE or cis-DCE was detected in ampules with 

Pemaco samples. These findings suggest that abiotic transformation processes are unlikely to 

contribute significantly to TCE and PCE destruction during electrical resistive heating of soils. 

Enhanced biotic reductive dechlorination has been reported to occur at field sites during and after 

thermal treatment. Using two distinct PCE-to-ethene dechlorinating consortia, OW and BDI, we 

observed ethene formation only in cultures incubated below 30ºC. At incubation temperatures 

above 30ºC, either vinyl chloride was the final dechlorination product (35ºC) or no 

dechlorination of PCE occurred (45ºC). No reductive dechlorination occurred in any of the 

microcosms constructed from Great Lakes soils, while in microcosms constructed with Fort 

Lewis soil, reductive dechlorination to cis-DCE occurred in microcosms incubated at 24ºC. PCEto-cis-DCE 

dechlorination in the microcosms incubated at 35ºC required the addition of electron 

donor (lactate), suggesting that substrate consumption in competing microbial processes limited 

reductive dechlorination at 35ºC. Incubation at temperatures ranging from 45 to 90ºC prevented 

any reductive dechlorination activity, however, PCE and TCE dechlorination was restored upon 

cooling to 24ºC followed by bioaugmentation and electron donor addition. These findings 

indicate that temperatures above 30ºC negatively impact dechlorinating populations, but suggest 

that bioaugmentation and biostimulation are promising down-gradient and post-thermal 

treatment options. 

G-118




REMEDIATION OF DNAPL AND LNAPL USING ELECTRICAL RESISTANCE 

E 

HEATING AT U.S. MILITARY BASES 

MR. DAVID FLEMING 

Thermal Remediation Services, Inc. 

7421 A Warren Avenue 

Snoqualmie, WA 98065 

(425) 396-4266 

dfleming@thermalrs.com 

RH is a remediation technology where soil and groundwater is heated by the passage of 

current through saturated and unsaturated soil between the electrodes, not by the electrodes 

themselves. It is the resistance to the flow of electrical current that results in increased subsurface 

temperatures, and this is typically applied to the boiling point of the contaminant and water. 

Steam is created in situ and contaminants are directly volatilized and/or recovered to the surface 

as free product. 

This poster will provide a series of case studies of a variety of projects that have involved the 

remediation of DNAPL and LNAPL using ERH at U.S. military bases. Site background, data 

collected and economics will be presented. 

G-119




T 

DOMINATING PROCESSES DURING DNAPL REMOVAL FROM THE 

SATURATED ZONE USING THERMAL WELLS 

DR. RALPH S. BAKER 

TerraTherm, Inc. 

10 Stevens Road 

Fitchburg, MA 01420 

(978) 343-0300 

rbaker@terratherm.com 

CO-PERFORMERS: John LaChance and Gorm Heron (TerraTherm, Inc.); Uwe Hiester, 

Oliver Trötschler, and Hans-Peter Koschitzky (VEGAS – Research Facility for Subsurface 

Remediation); Myron Kuhlman (MK Tech Solutions Inc.) 

his SERDP-funded research project (ER-1423) has focused on elucidating the principle 

mechanisms that control the performance of Thermal Conduction Heating (TCH) for 

treatment of DNAPL in saturated aquitards. To improve the understanding of the dominating 

processes of heat transfer and remediation processes, large-scale tank experiments with 

controlled boundary conditions were conducted in different set-ups at VEGAS, the research 

facility for subsurface remediation at the University of Stuttgart, Germany. Both tanks (volume 

75 and 150 m 3 ; height 4.5 m) had been filled with different layered systems. Silt-sized material 

was placed in the middle, lower-permeability saturated layer (K s = 10 -6 to 10 -7 m/s), with a sandy 

underlying aquifer layer, and a sandy overlying vadose layer. The groundwater level was 

maintained at the top of the lower permeability layer, which was contaminated in some 

experiments with PCE. Four Heater Wells were operated in the lower permeability layer to steam 

the groundwater and vaporize the contaminants. Two to four SVE Wells were operated in the 

upper sand layer to extract only the vaporized, gaseous contaminants. The groundwater flux was 

controlled, as were power consumption and SVE-fluxes. Furthermore, hundreds of temperature 

sensors, high temperature and corrosion resistant time domain reflectometry sensors for the 

measurement of water saturation and porous samplers were installed to determine characteristic 

heat transport and multiphase flow parameters in the subsurface of the large tanks. 

The 3-D experiments demonstrated that the porewater between the heater wells could be steamed 

and a thermally induced unsaturated zone in the aquitard could be induced. Furthermore, the 

impact of different groundwater fluxes was quantified, as was the contaminant removal 

efficiency. A further aim of the remediation experiments was to determine whether mobilization 

and spreading of the contaminants occurs or can be prevented using TCH. 

The poster presentation will enable a better understanding of the physical processes by 

comparing the results of the experiments with numerical simulations (refer to companion abstract 

submitted by Myron Kuhlman). The influence of parameters such as soil characteristics, 

permeability, configuration of the experiments and operating conditions (e.g., heat input, 

groundwater flux) will be discussed to show what would lead to improved simulations. The 

significant remediation processes in the saturated zone under different boundary conditions will 

be discussed (e.g., contaminants, location of contamination). The comparison of physical 

experiments and accompanying numerical simulations will be presented. 

G-120




E 

EFFECT OF AGGREGATION, HYDROGEOCHEMISTRY, AND CLAY 

ON NZVI EMPLACEMENT IN THE SUBSURFACE 

GREG LOWRY 


Civil & Environmental Engineering 

5000 Forbes Avenue 

119 Porter Hall 

Pittsburgh, PA 15213-3890 

(412) 268-2948 

glowry@cmu.edu 

CO-PERFORMERS: Tanapon Phenrat and Hye-Jin Kim (Carnegie Melton University); 

Fritjof Fagerlund and Tissa Illangasekare (Colorado School of Mines) 

mplacement of polyelectrolyte-modified nano zero valent iron (NZVI) particles at high 

particle concentration in the contaminant source zone is needed for effective in-situ 

environmental remediation using NZVI. This is challenging because it requires understanding of 

multiple complex phenomena, i.e., coupled aggregation and deposition, originating from several 

complex forces in the system (hydrodynamic shear and drag, magnetic attraction, electrosteric 

repulsion, van der Waals attraction) together with subsurface heterogeneity such as the presence 

of clay minerals. The objective of this research is to develop conceptual and semi-empirical 

models to better understand these processes and subsurface heterogeneity (the presence of clay) 

on the emplacement of NZVI for environmental remediation. Two semi-empirical correlations 

are proposed for estimating the deposition and transport of concentrated polyelectrolyte-modified 

NZVI dispersions in saturated porous media. The first semi-empirical correlation determines the 

apparent stable aggregate size formed during their transport in porous media. The second semiempirical 

correlation estimates the attachment efficiency (sticking coefficient) of those 

aggregates. The influence of the adsorbed polyelectrolyte layer property, seepage velocity, 

collector size, and ionic strength and composition on aggregation and deposition of concentrated 

dispersions of polyelectrolyte-modified NZVI in porous media is captured in these models. The 

semi-empirical correlations proposed here can be used to design emplacement strategies for 

NZVI in porous media. We also propose a conceptual model for the influence of charge 

heterogeneity of aquifer media on NZVI mobility. Charge heterogeneity enhances the 

aggregation kaolinite in the pore space which can mechanically filter NZVI. In addition, the 

positively charged sites on clay edges may promote the attachment of negatively charged anionic 

polyelectrolyte-modified NZVI on them. Depending on the size of aggregates, both mechanical 

filtration and deposition onto positively charged clay edge sites limits transport. Excess polymer 

in the injection solution improves transport by making the surfaces of the aquifer media 

uniformly negatively charged. 


G-121




Z 

FIELD APPLICATIONS OF ZVI-CLAY TECHNOLOGY FOR CHLORINATED 

SOLVENT SOURCE ZONES 

DR. TOM SALE 


Engineering Research Center 

1320 Campus Delivery 

Fort Collins, CO 80523-1320 

(970) 491-8413 

TSale@Engr.ColoState.Edu 

CO-PERFORMER: Mitch Olson (Colorado State University) 

VI-Clay uses conventional soil mixing equipment to admix reactive media (e.g., zero valent 

iron) and stabilizing agents (e.g., clay) with contaminated soil. Through mixing, 

heterogeneous subsurface source zones are transformed into uniform bodies of soils, 

contaminants, reactive media, and stabilizing agents. Within the treated interval, reactive media 

drives contaminant degradation while stabilizing agents reduce the hydraulic conductivity. In 

addition, soil mixing overcomes the challenge of delivering reactive media through complex 

geologic media. The overall benefit is a dramatic reduction in contaminant flux from the treated 

interval. 

Appropriate reactive media can be selected to treat site-specific contaminants of concern. A 

common application uses zero valent iron (ZVI) to treat chlorinated solvents. Corrosion of the 

iron drives degradation of the solvents (Gillham and O’Hannesin, 1994). Reaction rates generally 

follow pseudo first-order kinetics. In soils treated by ZVI-Clay, observed half-lives for many 

chlorinated solvents range from 10 to 1,000 hours (Olson, 2005). With these conditions, 

remaining contaminant mass is reduced by 90 percent every few days to a few months. 

Degradation rates are primarily a function of the contaminant and the amount and type of iron 

used. 

Stabilizing agents (typically clay) provide multiple benefits in the ZVI-Clay process. First, 

admixing clay and soil reduces hydraulic conductivity to values similar to bentonite slurry walls 

(




I 

DECISION GUIDE FOR MANAGING CHLORINATED SOLVENTS RELEASES 

DR. TOM SALE 


Engineering Research Center 

1320 Campus Delivery 

Fort Collins, CO 80523-1320 

(970) 491-8413 

TSale@Engr.ColoState.Edu 

CO-PERFORMERS: Chuck Newell (GSI Environmental, Inc.); Hans Stroo (HydroGeoLogic, 

Inc.); Dr. Rob Hinchee (Integrated Science and Technology); Paul Johnson (Arizona State 

University) 

n July of 2005, ESTCP provided funds to support development of documents to assist parties 

in selecting remedies for chlorinated solvent source zones (ER-0530). The project involves 

two primary deliverables. The first is a short overview of current knowledge in the form of 

responses to frequently asked questions. This document is complete and will be posted on the 

ESTCP website in the near future. The second document is a more comprehensive guide to 

decision-making that will build on recommendations presented in “Contaminants in the 

Subsurface” (NRC 2005). A draft of the document will be completed in the fall of 2008. 

Our poster at the partners meeting will highlight project objectives, the content of the 

deliverables, and the timeline for completion of the project. Through presentation of our poster 

we will gain input for our initiatives. Furthermore, we hope to facilitate awareness of our efforts. 

The overall vision of this project is that better access to available knowledge will lead to better 

management of lingering subsurface environmental legacies at DoD facilities. 

G-123




PREDICTING DNAPL SOURCE ZONE AND PLUME RESPONSE 

USING SITE-MEASURED CHARACTERISTICS 

DR. MICHAEL D. ANNABLE 

University of Florida 

220 Black Hall 

Gainesville, FL 32611 

(352) 392-3294 

annable@ufl.edu 

CO-PERFORMERS: Michael C. Brooks and A. Lynn Wood (EPA, Kerr Research Center); 

Kirk Hatfield and James W. Jawitz (University of Florida); P. Suresh C. Rao (Purdue University) 

T 

he challenge facing managers of DNAPL contaminated sites is the difficulty and expense 

associated with source-zone and plume characterization, and the identification of costeffective 

remedial options that: (1) decrease human health and ecological risks, (2) provide 

regulatory compliance, and (3) minimize the need for long-term stewardship. The ability to 

predict DNAPL source zone behavior and plume response is a critical link between source 

characterization and informed site management decisions especially those related to site remedial 

actions. Thus, it is vital that source-zone and plume characterization be conducted within a 

framework that is consistent with appropriate predictive models. 

The current project will demonstrate effective field-scale approaches that forge linkages between 

characterization, prediction, and decision making at DNAPL sites. The project objectives are to: 

(1) develop source-strength functions for site management purposes using existing historical site 

data supplemented with limited flux- and core-based sampling; (2) extend to the field-scale our 

ability to predict DNAPL source depletion through dissolution, based on a priori characterization 

of the source-zone architecture; (3) characterize the near-source plume response to source-mass 

depletion at selected field sites, and within an isolated section of the aquifer, to provide 

understanding needed to predict long-term plume responses; (4) link the characterization of the 

near-source, short-term responses to likely long-term behavior of the dissolved plume; and 

(5) provide recommended guidance on the level of source-zone characterization needed to 

adequately predict source-strength functions and plume response. 

These objectives will be met through three groups of inter-related activities: (1) analysis of 

existing field data from selected sites; (2) observations of plume response under controlled 

conditions in field studies; and (3) evaluation through modeling, including both simplified 

source-depletion models and comprehensive numerical simulators. 

The current phase of the project is selection of up to 20 DNAPL sites with high quality historical 

data sets that can be used to quantify site mass balances and links between source zone and 

plume. Results will be provided for initial sites selected and we seek input regarding additional 

potential sites. 


G-124




C 

COMPUTATIONAL AND EXPERIMENTAL INVESTIGATION OF 

CONTAMINANT PLUME RESPONSE TO DNAPL SOURCE ZONE 

ARCHITECTURE AND DEPLETION IN POROUS AND FRACTURED MEDIA 

DR. EDWARD SUDICKY 

University of Waterloo 

Department of Earth and Environmental Sciences 

200 University Avenue West 

Waterloo, ON N2L 4V9 CANADA 

(519) 888-4567, Ext. 36271 

sudicky@sciborg.uwaterloo.ca 

CO-PERFORMERS: Dr. Walter Illman and Dr. Shaun Frape (University of Waterloo); 

Dr. T.C. Yeh (University of Arizona) 

hlorinated solvents are the most prevalent contaminants at Department of Defense (DoD) 

sites. These are released as Dense Non-Aqueous Phase Liquids (DNAPLs) and there is 

considerable uncertainty in their fate due to its variable release history and geologic 

heterogeneity. DNAPL source zones can contribute to long-term groundwater contamination for 

decades to centuries. Therefore, their remediation and management are of high importance. 

While progress has been made with respect to process understanding in the context of DNAPL 

fate and migration in heterogeneous unconsolidated deposits, there remains a paucity of 

knowledge on the behavior of DNAPLs spilled in fractured geologic media. 

The main objectives of the proposed research are: (1) to develop computational tools for 

predicting aqueous-phase plume response to DNAPL source zone architecture and depletion for 

both porous and fractured geologic media; (2) to conduct a suite of numerical experiments to 

investigate the relationship between DNAPL source-zone characteristics and dissolve-phase 

plume migration in porous and fractured media; (3) to develop a stochastic information fusion 

(SIF) technology to define the DNAPL source and its characteristics by exploiting available 

hydraulic head and concentration data as well as signatures of stable isotope data of chlorinated 

solvents; (4) to conduct laboratory experiments to validate the proposed computational 

approaches; and (5) to apply the technique at a well-characterized fractured rock site at 

Smithville, Ontario, Canada. A data analysis environment will be developed through 

modification of an existing numerical model CompFlow to account for discrete fractures, stable 

isotope fractionation, and capability for stochastic information fusion. This environment will 

allow integration of various existing and newly collected information to provide the best 

unbiased estimates of DNAPLs and their aqueous phase distributions, source locations, and input 

history. The information to be integrated will include well hydrographs, concentration data, and 

isotopic signatures of the contaminants as well as geologic information and measurements of 

hydraulic properties, which have not been utilized effectively at various DoD sites. Fusion of 

these types of information will be accomplished by adopting a novel stable isotope fingerprinting 

technique and its seamless integration with state-of-the art forward and stochastic inverse 

modeling efforts. Through this integrative approach, contaminant plume response to DNAPL 

source zone architecture and depletion can be understood at the level that is beyond the 

capability of current technologies. Uncertainty can be quantified, which is vital to the selection 

of an aggressive active remediation or passive natural attenuation and bioremediation. 

G-125




ASSESSMENT OF REACTIVE IRON PARTICLE DELIVERY APPROACHES FOR 

TREATMENT OF DNAPL SOURCE ZONES 

LINDA M. ABRIOLA, PH.D. 


105 Anderson Hall, 200 College Avenue 

Medford, MA 02155 

(617) 627-3237 

linda.abriola@tufts.edu 

CO-PERFORMERS: Kurt D. Pennell, Ph.D. (Georgia Institute of Technology and Emory 

University); C. Andrew Ramsburg, Ph.D., Nicole D. Berge, Ph.D., and Yusong Li, Ph.D. (Tufts 

University); Jed Costanza, Ph.D. (Georgia Institute of Technology) 

T 

he application of reactive iron particles is being considered for treatment of Dense Non- 

Aqueous Phase Liquid (DNAPL) source zones. Although the success of iron-based 

technologies depends on both delivery and reactivity in the subsurface, few studies have 

investigated the transport of iron-laden suspensions in DNAPL source zones. In such zones, 

groundwater velocity and chemistry must be controlled to prevent unintended DNAPL 

mobilization or adverse changes in contaminant accessibility. Under SERDP Project ER-1487, 

researchers are developing and evaluating delivery systems for application of iron-based 

technologies within DNAPL source zones. 

Efforts to assess subsurface deliverability of the commercially available product RNIP (Toda 

America, Inc.) have focused on obtaining baseline transport parameters and understanding 

transport mechanisms. Results from one-dimensional (1-D) column experiments indicate 

unmodified RNIP slurries move as a distinct iron bank through medium- to coarse-grained sands. 

The pressure head required to drive this RNIP bank through porous media increases with 

increasing particle concentration. An experiment conducted to evaluate the delivery and 

reactivity of RNIP in regions containing entrapped tetrachloroethene (PCE)-DNAPL suggests 

that RNIP may be introduced to DNAPL source zones with minimal unintended DNAPL 

mobilization. Although a fraction of the DNAPL was transformed to ethene (~4%) in this 

experiment, the majority of contaminant removal was attributed to dissolution (~75%). 

Encapsulation of the reactive particles within an oil-in-water emulsion is a novel approach which 

may permit targeting of DNAPL during iron particle delivery. Iron-containing emulsions were 

developed that have mean droplet diameters around 1 micrometer, remain kinetically-stable for 

greater than 1.5 hours and possess densities (0.996-1.00 g/mL at 22°C) and dynamic viscosities 

of less than 10 cP. Breakthrough curves and post-experiment extractions from column 

experiments conducted with medium- and fine-grained sands suggest emulsion droplets and iron 

particles are readily transported at modest pressure gradients. Numerical simulations were 

conducted to evaluate the DNAPL mobilization potential, reactivity, and transportability of 

different ZVI delivery approaches. A two-dimensional multiphase compositional simulator, the 

Michigan subsurface environmental remediation (MISER) model, was modified to incorporate 

iron-mediated reduction reactions within source zones. Preliminary simulations of several 

hypothetical remediation scenarios indicate that the efficiency of aqueous-based ZVI remediation 

technologies will depend upon interphase mass transfer (i.e., dissolution). 

G-126




ITRC’S TECHNICAL AND REGULATORY GUIDANCE FOR BIOREMEDIATION 

OF CHLORINATED ETHENE DNAPLS 

I 

NAJI AKLADISS 

Maine Department of Environmental Protection 

66 Roberts Hill Road 

Topsham, ME 04086 

(207) 287-7709 

naji.n.akladiss@maine.gov 

CO-PERFORMERS: R. Wymore (CDM); W. Clayton (Aquifer Solutions); M. DeFlaun, 

Eric Hood, and D. Major (Geosyntec); J. Farrell (Florida DEP); P. Hadley (California DTSC); 

E. Hausamann (New York DEC); S. Hill (RegTech, Inc./ITRC); J. Lisiecki (FTC&H); 

T. Macbeth (North Wind, Inc.); M.J. Ondrechen (Northeastern University); F. Payne 

(ARCADIS); J. Sechen (Massachusetts DEP); M. Sieczkowski and D. Smith (JRW 

Bioremediation); M. Smith (Vermont DEC); H. Stroo (HGL); L. Syverson (Virginia DEP) 

n 2004, the Interstate Technology and Regulatory Council (ITRC) established a 

Bioremediation of Dense Non-Aqueous Phase Liquids (DNAPLs) Team. This team produced 

two initial documents and has just released the technical and regulatory guidance (Tech-Reg) In- 

Situ Bioremediation of Chlorinated Ethene: DNAPL Source Zones, with an associated Internetbased 

training. The first document reviewed the status of the technology, culminating in the 2005 

publication of a Technology Overview of In-Situ Bioremediation of Chlorinated Ethene 

DNAPLs in Groundwater. Building on the Technology Overview, a Case Study Forum was held 

in March 2006 to document a thorough and critical review of six cutting edge DNAPL 

bioremediation projects by a panel of invited experts from industry, academia, and the regulatory 

community. A Case Study Document was published in April 2007 that presents all six case 

studies, comments from the expert panel, and conclusions of the panel. The recent guidance, 

available at www.itrcweb.org, presents a systematic description of the technical and regulatory 

considerations for ISB (in-situ bioremediation) of chlorinated ethene: DNAPL source zones. 

The Tech-Reg guidance on bioremediation of chlorinated ethene DNAPL source zones, provides 

state regulators and the environmental community in general with a reliable body of knowledge 

and a resource containing credible evidence that bioremediation can be a safe, cost effective 

remediation strategy for DNAPL source zones. The principle objectives of the technical and 

regulatory guidance are: (1) to affect technology transfer between the states; (2) to save state 

regulators valuable time and money when selecting and approving a remedial technology; and 

(3) to provide regulators with scientifically sound and credible evidence they may need to 

support, defend, and obtain authorization and approval for the use of ISB of DNAPL 

contaminated sites. 

The Tech-Reg provides guidance on setting realistic goals for bioremediation of source zones, 

and summarizes the current state of the technology, as updated from the 2005 technology 

overview document. It also provides recommendations on the data needs and site conceptual 

model elements that are unique to bioremediation of DNAPLs. Elements of concern to regulators 

and health and safety issues are addressed. Finally, the document provides guidance on selection, 

design, implementation, and optimization of bioremediation of chlorinated ethene DNAPLS. 

G-127




CASE STUDY: USE OF REFRIGERATED CONDENSATION FOR SVE OFF-GAS 

R 

TREATMENT REMEDIATION FOR CONTAMINATED SEDIMENTS 

LOWELL KESSEL 

G.E.O., Inc. 

836 Quail Meadows 

Irvine, CA 92603 

(714) 709-3683 

lkessel@geoinc.org 

CO-PERFORMER: Jeremy Squire (Haley & Aldrich, Inc.) 

emediation of recalcitrant compounds at sites with high concentrations of volatile organic 

compounds (VOCs) and or non-aqueous phase liquids (NAPL) can present significant 

technical and financial (long term) risk for stake holders. The authors present two case studies 

for which refrigerated condensation, otherwise known as C3-Technology, was utilized in place 

of thermal oxidation or granular activated carbon for startup of soil vapor extraction (SVE) 

remediation activities at these chlorinated solvent impacted sites. The implementation of the 

remediation approach resulted in reduced cost, more rapid source removal and, what became 

evident later, more sustainable methodology. 

The case studies review the technical merits of the three off-gas treatment approaches (i.e., 

granular activated carbon, thermal oxidation, and C3-Technology) and include evaluation of the 

physicochemical site conditions, the fully loaded costs associated with operating the systems, 

and the environmental impacts of operating the systems, including a carbon footprint estimate for 

each. 

The authors provide some key takeaways for consideration of off-gas treatment technologies 

from the perspective of feasibility, cost and sustainability. 

G-128




PRACTICAL COST-OPTIMIZATION OF CHARACTERIZATION AND 

REMEDIATION DECISIONS 

JACK PARKER 

University of Tennessee 

62 Perkins Hall 

Knoxville, TN 37996-2669 

(865) 974-7718 

jparker@utk.edu 

CO-PERFORMERS: Peter Kitanidis, Xiaoyi Liu, and Michael Cardiff (Stanford University); 

Ungtae Kim (University of Tennessee); Dave Becker (USACOE); Aleisa Bloom (ORNL); 

Kyle Gorder (Hill AFB) 

S 

ERDP Project ER-1611 focuses on the development of methods to optimize management of 

DNAPL-contaminated sites to reduce net cost. Computational tools are being developed to 

enable cost-optimized decision-making regarding remedial actions and associated site 

characterization efforts to meet specified remedial objectives with quantifiable uncertainty. 

Substantial uncertainty always exists in DNAPL source characteristics and other site parameters 

that complicate the selection and design of cleanup strategies. The proposed approach directly 

considers effects of uncertainty in performance projections on the decision-making process and 

identifies cost tradeoffs among remedial options, characterization efforts, and monitoring 

strategies. 

Models for dissolved solvent migration with time-dependent DNAPL sources are employed to 

simulate performance of monitored natural attenuation (MNA) and various strategies for source 

mass reduction and dissolved plume remediation. The simulation model is coupled with (1) a 

module to compute net present value cost to meet defined remediation criteria given unit 

monitoring, operating and capital costs and discount rates, (2) an inverse solution to estimate 

model parameters and their uncertainty from available site data, (3) an error analysis module to 

determine calibration-constrained (conditional) distributions of remediation performance and 

cost predictions, and (4) a management optimization code. The latter will determine the optimum 

remediation design considering prediction uncertainty predicated on currently available data, and 

will allow assessment of the value of additional characterization data in term of the potential 

reduction in expected net present value cost. 

Preliminary results are presented for a hypothetical problem involving remediation of a DNAPL 

site. A solution is described that considers DNAPL source depletion and biodecay within the 

source zone and the aqueous plume controlled by net electron donor availability. Model 

calibration is performed using limited ‘noisy’ synthetic monitoring and characterization data. 

The remediation strategy involves injection of a carbon source with amounts, locations and 

frequencies of carbon injection taken as design variables. In addition to capital, operating and 

monitoring costs, the potential for noncompliance with remediation goals is assumed to incur a 

“penalty cost” for implementation of a containment system. The potential benefits of reduced 

parameter uncertainty on cost uncertainty and expected cost are also investigated. 

G-129




IMPACT OF SOURCE-ZONE ARCHITECTURE AND FLOW-FIELD 

HETEROGENEITY ON REDUCTIONS IN MASS-FLUX 

DR. MARK L. BRUSSEAU 

University of Arizona 

Department of Soil, Water and Environmental Science 

429 Shantz Building 

Tucson, AZ 85721 

(520) 626-4191 

brusseau@ag.arizona.edu 

CO-PERFORMERS: Dr. Erica L. DiFilippo and Dr. Kenneth C. Carroll (University of Arizona) 

A 

series of flow-cell experiments was conducted to investigate the impact of source-zone 

architecture and flow-field heterogeneity on the relationship between source-zone massremoval 

and reductions in contaminant mass-flux. The results showed that minimal reductions in 

mass-flux occurred for systems wherein immiscible liquid was present at residual saturation in 

regions that are hydraulically accessible. Conversely, significant reductions in mass-flux 

occurred for systems wherein immiscible liquid was present as both residual saturation and in 

high saturation pools. The systems with significant reductions in mass-flux exhibited multi-step 

behavior. Analysis of immiscible-liquid saturation data measured via imaging confirmed that the 

initial mass-flux reductions for these systems were associated with the removal of the sourcezone 

mass that was hydraulically accessible (within the matrix). Conversely, later reductions in 

flux were associated with mass-removal from the less hydraulically-accessible pools. The age of 

the source zone (time from initial spill to time of initial characterization) significantly impacted 

the observed mass-flux-reduction/mass-removal behavior. The results of this study illustrate the 

impact of both source-zone architecture and flow-field heterogeneity on mass-removal and massflux 

processes. 


G-130




ASSESSMENT OF THE NATURAL ATTENUATION OF DNAPL SOURCE ZONES 

AND POST-TREATMENT DNAPL SOURCE ZONE RESIDUALS 

RYAN EKRE 

Arizona State University 

1711 S. Rural Road, ECG-252 

P.O. Box 875306 

Tempe, AZ 85287 

(480) 965-0055 

ryan.ekre@asu.edu 

CO-PERFORMERS: Dr. Rosa Krajmalnik-Brown, Dr. Paul Dahlen, Dr. Bruce Rittman, and 

Dr. Paul C. Johnson (Arizona State University) 

T 

he selection of corrective action options at most DNAPL-impacted sites is a non-trivial 

exercise. One end-member of remediation options is source zone natural attenuation 

(SZNA). SZNA is often used as a basis for assessing the performance and relative benefits of 

engineered remediation and to define remediation end-points. SZNA is also an implicit 

component of engineered remediation schemes, providing the reduction of post-treatment 

residuals. While there is accepted guidance for assessing the natural attenuation of dissolved 

groundwater plumes, a well accepted and demonstrated approach for assessing DNAPL SZNA 

does not exist. 

This ESTCP project (ER-0705) will demonstrate the assessment of SZNA at a minimum of two 

sites and will produce illustrated guidance that will incorporate demonstration site results. The 

approach will provide answers to questions typically asked by decision-makers, including: (a) Is 

SZNA occurring, and if so, what natural processes contribute to it; (b) What is the current rate 

of source zone mass reduction associated with SZNA, and how might this change in the future; 

(c) What are the longer-term implications of SZNA for groundwater and vapor migration 

impacts at the site; (d) Are the SZNA processes and rates sustainable; and (e) What is the 

projected longevity of the DNAPL source zone (or post-treatment DNAPL residual) 

The data-driven approach utilized in this project was recently introduced for LNAPL sites and 

has been generalized for DNAPL sites. The approach includes three levels of data collection and 

reduction: Group I measurements provide evidence that SZNA is occurring; Group II 

measurements include information necessary to estimate current overall SZNA rates; and Group 

III measurements focus on evaluating long-term implications of SZNA for temporal changes in 

source zone residual composition, source zone groundwater quality, and vapor migration 

impacts. This data-driven approach is consistent with NRC recommendations for “multiple lines 

of evidence” and “footprint” approaches, and is complementary to existing guidance for 

assessing the natural attenuation of dissolved plumes and the SZNA screening-level modeling 

tool development previously supported by DoD. 

To date, the protocol for the assessment of SZNA as it applies to DNAPL sites has been drafted, 

Site 45, MCRD Parris Island, South Carolina and the Sludge Drying Beds, Operable Unit A, Hill 

AFB, Utah have been identified as demonstration sites, and initial site assessments are underway. 

This presentation will provide details on the protocol for the assessment of SZNA, conceptual 

models for the demonstration sites, and data from the initial site investigations. 

G-131


Chlorinated Solvents — Dissolved Phase Remediation 


TREATABILITY STUDY RESULTS FOR THE PEROXYGEN ISCO 

DEMONSTRATION/VALIDATION AT MCRS CHERRY POINT, SC 

DR. RICHARD WATTS 


Box 2910 

Pullman, WA 99164-2910 

(509) 335-3761 

rjwatts@wsu.edu 

CO-PERFORMERS: Jeremiah Trnka, Robert E. Vaughan, and Amy L. Teel (Washington State 

University); Scott Huling and Ann Keely (EPA); Richard A. Brown (ERM); 

Phillip A. Block (FMC Corporation) 

R 

ecent advances in the use of activated peroxygens (hydrogen peroxide and persulfate) for insitu 

chemical oxidation (ISCO) hold promise for the rapid remediation contaminated soils 

and groundwater. These developments are being demonstrated and validated at MCRS Cherry 

Point under ER-0632. An initial task in this study was to perform a treatability study for 

activated perulfate and catalyzed H 2 O 2 propagations (CHP, i.e., modified Fenton’s reagent). 

The first objective was to evaluate heterogeneity of the samples relative to depth and area. The 

cores were collected down to 16 feet, and the sleeves were cut at intervals that ranged from 

18 – 26 inches. A subsample was collected from each core section and evaluated for peroxygen 

stability by four different methodologies: (1) gas evolution following the addition of H 2 O 2 , 

(2) H 2 O 2 decomposition rates, (3) consumption of permanganate, and (4) visual inspection of the 

samples. After extensive evaluation of the cores, two distinctly different types of subsurface 

materials were found. The upper layer of subsurface solids (gs – 10 feet), which was lighter in 

color, had some clay and organic matter, and decomposed peroxygens relatively slowly. The 

deeper layer (10 – 16 feet bgs) was darker in color, had more clay and organic matter and 

decomposed peroxygens significantly more rapidly. Cores from both regions were composited 

for stability screening and contaminant destruction studies. 

The results obtained during the heterogeneity evaluations suggested that peroxygen longevity 

could be a potential limitation in the deployment of peroxygen ISCO at the site. Therefore, a 

significant effort was put into increasing the stability of hydrogen peroxide and persulfate using 

the stabilizers citrate, malonate, and phytate. Slurries containing 10 g of subsurface solids and 4 

ml of groundwater and peroxygen solution received stabilizers in concentrations ranging from 25 

to 300 mM. The addition of stabilizers had a significant effect on H 2 O 2 and persulfate stability. 

For example, under the optimum condition of 150 mM citrate, the half-life for H 2 O 2 was 16 

hours, a 2100% increase in stability compared to unstabilized H 2 O 2 . 

Samples were also investigated for contaminant degradation during peroxygen treatment. 

Destruction of PCE in citrate-stabilized CHP systems was approximately 80%. Base-activated 

persulfate destruction of PCE was 94% in the dark soil with no pH adjustment and 89% in the 

dark soil with a 2:1 molar ratio of sodium hydroxide to persulfate. Even higher degrees of 

contaminant destruction have been documented in the light soil. More detailed contaminant 

destruction studies are underway. 

G-132




CHALLENGES WITH AN ISCO APPLICATION IN THE UNSATURATED ZONE 

E 

SUSANNE BORCHERT, P.G. 

CH2M HILL, Inc. 

2871 West Forest Road 

Freeport, IL 61032 

(815) 233-1051 

Susanne.Borchert@ch2m.com 

CO-PERFORMERS: Jessica Raphael and Lauren Tatar (CH2M HILL); 

Brian Kanzler (Reichhold Chemicals) 

xcavation and offsite disposal of contaminated soil is an effective technology for treating 

source area soil and has a high certainty of risk-reduction. In-situ remedies, however, can be 

more cost effective in treating soil depending on the site-specific characteristics. An evaluation 

of applicable in-situ technologies for source area soil was performed (including soil vapor 

extraction, electrical resistive heating, enhanced reductive dechlorination, and in-situ chemical 

oxidation [ISCO]), and ISCO was determined to have the highest potential of being a costeffective 

alternative for the chlorinated solvent-impacted soil in the unsaturated zone. Although 

ISCO has been used extensively to treat the saturated zone, treating the unsaturated soil is an 

innovative approach. The main contaminants in the source area are trichloroethene (TCE) and 

cis-1,2-dichloroethene. A pilot study using Na-permanganate was conducted to: (1) evaluate the 

feasibility of unsaturated zone saturation during oxidant delivery into the subsurface; and 

(2) determine the cost-effectiveness of oxidation on the volatile organic compounds (VOCs). 

The pilot study was conducted in Fall 2006 on a 16-ft by 18-ft area to a depth of 9 feet below 

ground surface (bgs). Groundwater was encountered between 9 and 10 feet bgs. The maximum 

concentration of TCE and cis-1,2-DCE were 66,000 µg/kg and 2,400 µg/kg, respectively. The 

sodium persulfate soil oxidant demand was < 0.1 g/kg to 0.9 g/kg, while the sodium 

permanganate demand ranged from about 3 to 17.1 g/kg. 

Permanganate was injected at 9 locations within the pilot study area. Immediately following the 

injection, six visual borings were advanced to 12-ft to assess oxidant distribution and level of 

saturation of the unsaturated zone. Where observed, the radius of influence ranged from 2.5 up to 

10-ft; however, several visual borings had limited evidence of permanganate. Performance 

monitoring was conducted on soil and groundwater 1 month post-injection (adjacent to the 

baseline locations) along with 10 additional visual borings. Permanganate concentrations in 

groundwater were measured post-injection using a spectrophotometer. Although little visual 

evidence of permanganate distribution was obtained, the TCE and cis-1,2-DCE concentrations in 

soil decreased between 44 and 93%, respectively, however, their concentrations in groundwater 

increased up to ten fold. Due to tight soil in the upper portion of the unsaturated source area, soil 

excavation was chosen as the main contaminant removal mechanism. Permanganate was then 

sprayed in the open pit to impact the remaining unsaturated soil and upper saturated zone. 

The presentation will discuss oxidant dosages, the flexible pilot study approach, injectant flow 

rates and pressures for optimizing distribution, challenges encountered during oxidant delivery, 

and performance monitoring results. 

G-133




IN SITU CHEMICAL OXIDATION FOR GROUNDWATER REMEDIATION: 

RESPONSES TO PROJECT MANAGERS—FREQUENTLY ASKED QUESTIONS 

DR. ROBERT SIEGRIST 




(303) 384-2158 

siegrist@mines.edu 

CO-PERFORMERS: Michelle Crimi (Clarkson University); Ben Petri, Fritz Krembs, Junko 

Munakata Marr, and Tissa Illangasekare (Colorado School of Mines); Tom Simpkin, 

Tom Palaia, and Gene Ng (CH2M Hill); Michael Singletary (Naval Facilities Engineering 

Command Southeast Division) 

A 

mong the technologies available to remediate contaminated sites, in-situ chemical oxidation 

(ISCO) is often considered and utilized to clean up organic chemical contamination in 

source zones and/or associated groundwater plumes. A wide variety of organic contaminants in 

soil and groundwater have been addressed with the oxidants permanganate, catalyzed hydrogen 

peroxide propagations (CHP), activated persulfate (S 2 O - 8 ), ozone, peroxone, and percarbonate; 

which have been introduced through an assortment of delivery approaches. Full-scale ISCO 

deployment is accelerating, but care must be taken to achieve performance goals in a costeffective 

manner while avoiding unforeseen adverse effects. 

Toward advancing the standard-of-practice of ISCO to enable more predictable, cost-effective 

application, the development of an ISCO Technology Practices Manual (TPM) is in progress 

under ESTCP Project ER-0623. One element of the TPM is a Frequently Asked Questions 

(FAQs) document. The FAQ document provides a concise overview of current knowledge 

regarding ISCO applicability, design, implementation, and performance for groundwater 

remediation in the form of “FAQs.” The FAQs are those most commonly asked by and most 

useful to remedial project managers. Each question is addressed with a brief, focused response. 

Questions are categorized under the ISCO process headings “ISCO Screening,” “ISCO 

Conceptual Design,” “ISCO Implementation,” and “ISCO Monitoring.” The intended audience 

of the FAQ includes DoD Remedial Project Managers (RPMs); however, the document is also 

well-suited for site owners/managers in general. It is assumed that readers have a general 

understanding of site characterization/assessment and remediation technology selection and 

application (i.e., not intended for users new to the field of contaminated sites and remediation). 

Additional elements of the TPM include: (1) Principles of ISCO for Groundwater Remediation, 

which provides a detailed review of some of the broader issues covered in the FAQ; (2) a 

Database for ISCO, named DISCO, which presents a compilation and analysis of ISCO field site 

case histories that can be queried based on site-specific geology and contaminant features; and 

(3) an ISCO Protocol, which is a decision process with tools for screening, design, and 

implementation of ISCO. These components are directly interrelated. For example, the FAQ 

document refers to case history data and lessons learned through analysis of database 

information. Information is thus cross-linked throughout the individual components of the TPM. 

This poster will focus on responses to a selection of the more commonly asked FAQs. 

G-134




S 

SIMULATION OF LABORATORY IN SITU THERMAL DESORPTION OF 

DNAPLS 

DR. MYRON KUHLMAN 

MK Tech Solutions, Inc. 

12843 Covey Lane 

Houston, TX 77099 

(281) 564-8851 

mikuhlman@sbcglobal.net 

imulations of 2D-flume and large-tank heating and remediation experiments were conducted 

with the thermal simulator STARS. Both the temperature distribution in the containers and 

production rate of vaporized perchloroethylene (PCE) were modeled well. However, migration 

of the PCE from the lenses where it had been placed was not predicted well since flow of 

dissolved DNAPL countercurrent to upwardly flowing water is difficult if not impossible to 

model because the grid blocks in the simulations are just not small or heterogeneous enough. 

Capillary pressure and DNAPL relative permeability were the most important variables 

controlling heating of the containers and migration of the DNAPL in the experiments. The 

capillary pressures used are significantly lower than measured capillary pressures because 

numerical dispersion in simulations affects movement of fluids in the same way as capillary 

pressure does. In the tank experiments the aquifer-influx rate was also very important because 

high aquifer-influx rates force the DNAPL to migrate upward and horizontally both as a separate 

liquid or component dissolved in the water. Low aquifer-influx rates allow the DNAPL to 

migrate downward as both a free liquid and in the vapor phase or the DNAPL could condense 

from the vapor beyond the heated zone. In either case, DNAPL that migrates from the heated 

zone can only be recovered slowly at a low concentration. The predicted and actual ideal aquiferinflux 

rate for these experiments appeared to be 0.55 m/day (2 m 3 /day in a 6H6 meter tank). This 

prevented migration of the DNAPL and allowed ninety percent of the PCE to be recovered in 

two weeks from a large-tank remediation experiment. When higher rates were used the DNAPL 

quickly migrated outside of the heated zone and was recovered slowly. 

Migration of a DNAPL and the difficulty of recovering DNAPL that is flushed or condensed 

outside of the small heated zone in these experiments are artifacts of these experiments that are 

not important in field thermal-conduction-heating projects because the SVE wells are placed 

inside (not outside) the heaters in field projects. Moreover, migration of the DNAPL has 

occurred over years in the field and did not begin when the experiment started. Thus, this study 

shows that simulation is a versatile tool for modeling and explaining the phenomena that are 

important in actual thermal projects and how simulations can be modified to best predict 

movement of liquids and gases in In-Situ Thermal Desorption projects. 


G-135




BIOLOGICAL AND PHYSICAL-CHEMICAL APPROACHES FOR DEGRADATION 

OF 4-CHLOROANILINE AND ANILINE 

PROFESSOR DONNA FENNELL 


Department of Environmental Sciences 

14 College Farm Road 


(732) 932-9800, Ext. 6204 

fennell@envsci.rutgers.edu 

CO-PERFORMERS: Yun Li and Weilin Huang (Rutgers University); Yongqing Zhang (South 

China University of Technology and Rutgers University); Elizabeth Erin Mack (DuPont 

Corporate Remediation Group) 

A 

niline and 4-chloroaniline (p-chloroaniline, PCA) are contaminants at DuPont 

Corporation’s Chambers Works in Deepwater, New Jersey. Although degradation of these 

compounds is well documented under aerobic conditions, their fate in reduced environments is 

less well understood. We are developing treatment methods for PCA and aniline that are 

compatible with treatment of co-mingled pollutants at the site. Biodegradation under different 

redox conditions and oxidation by persulfate were examined as potential methods for 

remediation of sediments contaminated with PCA and aniline. Sediments were obtained from 

contaminated and background (lightly contaminated) locations of a groundwater aquifer and a 

freshwater canal. In addition to aniline and PCA, the co-contaminants such as dyes, PAHs, 

benzene and chlorinated benzenes are present. Microcosms were established under denitrifying, 

Fe (III)-reducing, sulfidogenic and methanogenic conditions. Original microcosms were initially 

amended with 100 µM and then increased to 1 mM aniline or PCA. 

Aquifer microcosms showed loss of aniline under nitrate-reducing, Fe (III)-reducing and 

sulfidogenic conditions, and PCA loss under nitrate-reducing conditions. Microcosms from canal 

sediments showed loss of aniline under nitrate-reducing, Fe (III)-reducing and sulfidogenic 

conditions and slow loss of PCA under nitrate-reducing conditions. Since both aniline and PCA 

loss was observed under nitrate-reducing conditions, nitrate-reducing enrichment cultures were 

initiated by inoculating with 10% (vol/vol) of active sediment microcosms. Enrichments were 

incubated at 25°C and amended with 1 mM aniline or PCA. We also investigated the kinetics of 

heat-assisted persulfate oxidation rates of aniline and PCA at various pH, temperature, oxidant 

concentration and ionic strength levels. Future studies will examine the utility of combining 

these procedures. Additional tests to characterize aniline and PCA degradation pathways and 

rates and the microbial community in the enrichment cultures are ongoing. 

G-136




E 

DECISION FLOWCHART FOR THE USE OF MONITORED NATURAL 

ATTENUATION AND ENHANCED ATTENUATION— 

CHLORINATED ORGANICS 

KIMBERLY A. WILSON 

South Carolina Department of Health and Environmental Control 

2600 Bull Street 

Columbia, SC 29201 

(803) 896-4087 

wilsonka@dhec.sc.gov 

CO-PERFORMERS: Judie Kean (Florida DEP); John Doyon (New Jersey DEP) 

nhanced attenuation (EA) and enhanced bioremediation are terms being used at an 

increasing rate in the environmental field. While these remedial strategies are being used in 

combination with monitored natural attenuation (MNA), and remedial source zone approaches, 

there have been no definitions or guidance for implementation of these strategies at contaminated 

chlorinated sites. The Interstate Technology and Regulatory Council (ITRC) Enhanced 

Attenuation: Chlorinated Organics (EACO) team has developed “second-generation” 

management tools/procedures that include defining EA and evaluating site conditions, through a 

decision process. This new management approach encourages energy efficiency and provides for 

the development of innovative solutions for the environment. 

The ITRC EACO team includes members from six state regulatory agencies, industry, federal 

agencies, including the Department of Energy (DOE) and EPA, academia, and stakeholders. The 

EACO team and the DOE MNA/EA for Chlorinated Solvents project team formed a partnership 

to develop the concept of EA and to provide regulators and the community with new, viable 

decision process for EA implementation. The ITRC team has published a technical guidance 

document to help determine how/when to use EA, developed a flow chart to and a Resource 

Guide that describes MNA and EA processes and provides references for additional technical 

information. The Decision Flowchart provides a clear and concise pathway that includes the 

evaluation of plume stability, decisions on the remedial path, and then the evaluation of 

enhancement options. It is anticipated that the Decision Flowchart will provide regulators and 

others with guidance in regards to the evaluation of the overall site conceptual model, and the 

incorporation of a phased-complete approach for site rehabilitation using new EA strategies. 

G-137




VERIFICATION OF METHODS FOR ASSESSING THE SUSTAINABILITY OF 

MONITORED NATURAL ATTENUATION 

MARK WIDDOWSON 

Virginia Polytechnic Institute and State University 

Department of Civil & Environmental Engineering 

Blacksburg, VA 24061-0105 

(540) 231-7153 

mwiddows@vt.edu 

CO-PERFORMERS: Francis Chapelle (U.S. Geological Survey); Jack Parker (University of 

Tennessee); John Novak (Virginia Tech); Carmen Lebrón (NAVFAC) 

U 

nder SERDP project ER-1349, Chapelle et al. (2007) developed a methodology for 

assessing MNA sustainability at chlorinated solvent sites. The methodology uses the 

comprehensive numerical model SEAM3D version 2.1 to assess sustainability by integrating 

effects of DNAPL source depletion, advection, dilution, dispersion, volatilization, abiotic 

reactions, and microbial transformations. At chloroethene sites, reductive dechlorination is 

typically the critical attenuation process in MNA-based remedial strategies. Sustainable 

reductive dechlorination is controlled by fluxes of electron acceptor and donor species from 

recharge, dispersion from upgradient groundwater, and dissolution of solid phase bioavailable 

organic carbon within the aquifer at sites where only indigenous carbon is present. Long-term 

MNA sustainability is determined by computing the net plume behavior in response to the 

stoichiometric balance between electron donors and acceptors and transport processes using 

SEAM3D. This proposed approach utilizes a simple but novel method to quantify the 

operationally defined BOC (Rectanus et al. 2007) and a field-scale source-zone depletion (SZD) 

function to estimate contaminant fluxes and remediation time-frame (Parker and Park 2004). 

The three main technical objectives of the proposed effort are to: (1) validate a methodology for 

calculating by establishing correlations with field-measured dissolved oxygen and chloroethene 

concentrations, concentrations of natural organic carbon compounds present in aquifer sediment, 

and rate and extent of reductive dechlorination; (2) verify the upscaled SZD function using site 

contaminant concentration data for a range of source zone geometries; and (3) demonstrate longterm 

MNA sustainability assessment using SEAM3D v.2.1. Initial results suggest that while 

BOC correlates positively with total organic carbon (TOC) of aquifer sediment, TOC alone is not 

a clear indicator of the rate and extent of reductive dechlorination. Concentrations of BOC in 

sediments from a variety of chlorinated ethene-contaminated sites correlate positively with 

amino acid concentrations. Because amino acids are known to be relatively bioavailable carbon 

compounds, this suggests that the sequential chemical extraction procedure used to measure 

BOC—a much simpler procedure than measuring concentrations of compounds such as amino 

acids—is a useful indicator of bioavailable carbon in soils and aquifer sediments. 

This work is funded by ESTCP Project ER-0824. 

G-138


Perchlorate 


LABORATORY STUDIES ON APPLICATIONS OF DIFFERENT AMENDMENTS 

FOR PERCHLORATE DEGRADATION 

MARC DESHUSSES 

University of California, Riverside 


Civil and Environmental Engineering 

Box 90287 

Durham, NC 27708 

(919) 660-5200 

marc.deshusses@duke.edu 

CO-PERFORMERS: Yue Wang and Mark R. Matsumoto (University of California, Riverside) 

I 

n the presence of a suitable electron donor, perchlorate can be degraded to non-toxic chloride, 

via either biotic or abiotic mechanisms. In this study, an array of laboratory microcosm 

experiments were conducted to evaluate the most effective amendments for future in-situ 

remediation of perchlorate in the source (vadose and saturated zones) and plume edge 

(biobarriers) at a large contaminated site. All experiments were conducted with actual 

contaminated soil and groundwater spiked with an appropriate concentration of perchlorate. Two 

amendments, emulsified oil substrate (EOS) and EHC, a treatment for surface soils and 

sediments, were selected as electron donor for biobarrier area application, and four amendments, 

EOS, glycerin, high fructose corn syrup (HFCS), sodium acetate, were selected for source area 

application. For the biobarrier area, perchlorate concentration was spiked to about 500 µg/L. 

Both EOS and EHC supported the reduction of perchlorate to below 4 µg/L within a week. 

Addition of nutrients (1 g/L (NH4)2HPO4) shortened the lag time of perchlorate degradation in 

EOS microcosm but had little effect on the reduction rate. For source area, the perchlorate 

concentration was spiked to 68000 µg/L. Two different amendments concentration were tested. 

A faster rate of perchlorate reduction was obtained at a high concentration (5% (v:v)) of EOS 

compared to a low EOS concentration (1% (v:v)). In contrast, the concentration of either glycerin 

or acetate had no impact on perchlorate reduction. Addition of HFCS did not result in a 

successful treatment endpoint. The addition of nutrients accelerated the initiation of perchlorate 

reduction in all source area microcosms. The presence of nitrate in natural groundwater was 

found to compete with perchlorate reduction. The experiments will serve to determine the best 

field remediation strategy. 


G-139


Perchlorate 


E 

SEMI-PASSIVE ELECTRON DONOR ADDITION FOR ENHANCED IN SITU 

BIOREMEDIATION OF PERCHLORATE-IMPACTED GROUNDWATER 

THOMAS A. KRUG 


130 Research Lane 

Guelph, ON N1G 5G3 CANADA 

(519) 822-2230 

tkrug@geosyntec.com 

CO-PERFORMERS: Evan Cox and David Bertrand (Geosyntec Consultants, Inc.) 

nhanced in-situ bioremediation (EISB) is being used at an ever increasing number of sites to 

treat perchlorate-impacted soils and groundwater. SERDP/ESTCP recently undertook to 

prepare a monograph providing information on implementation of EISB for perchlorateimpacted 

groundwater developed during a number of research projects funded by SERDP, 

ESTCP and other agencies. This poster provides a summary of one chapter of the monograph 

which provides information on semi-passive approaches for addition of electron donor for 

treatment of perchlorate-impacted groundwater. 

Semi-passive EISB involves groundwater recirculation and the addition of electron donor on a 

periodic basis to stimulate natural microbiological populations. The approach is similar to active 

recirculation EISB approaches, in that groundwater is recirculated between injection and 

extraction wells. However, with the semi-passive approach, groundwater is recirculated for an 

“active phase” of a limited duration to distribute the electron donor, and then the recirculation 

system is shut off for a “passive phase” of longer duration. The extraction and injection wells 

may be designed to create a biobarrier perpendicular to the direction of groundwater flow, or to 

distribute electron donor throughout source areas or other target treatment zones. This poster 

discusses when to consider this approach, advantages and limitations of the approach, and the 

design, operation and monitoring of systems using the semi-passive approach. 

This poster also includes a case study of a demonstration of semi-passive remediation conducted 

by Geosyntec at the Longhorn Army Ammunitions Plant (LHAAP) in northeast Texas with 

funding from ESTCP (Project ER-0219). In this case, the approach used at the LHAAP site 

involved periodic addition of electron donors over a period of 3 weeks every 6 to 10 months. The 

approach is significantly less expensive than active recirculation systems but avoids the negative 

impacts on water quality resulting from passive systems where very large quantities of electron 

donor are added at one time in order to maintain reducing conditions for several years. The data 

from the demonstration show that significant reductions in perchlorate concentrations can be 

achieved using the semi-passive biobarrier system for EISB of perchlorate without having 

significant impacts on secondary water quality characteristics. 

G-140


Perchlorate 


A TIERED APPROACH FOR EVALUATING PERCHLORATE 

NATURAL ATTENUATION 

MS. SHERI L. KNOX, P.E. 

Solutions-IES, Inc. 

1101 Nowell Road 

Raleigh, NC 27607 

(919) 873-1060 

sknox@solutions-ies.com 

CO-PERFORMERS: M. Tony Lieberman (Solutions-IES, Inc.); Robert C. Borden, P.E., Ph.D. 

(North Carolina State University); Mark B. Yeaton (Naval Facilities Command Indian Head); 

Richard Zambito, P.E. (Alliant Techsystems, Inc.) 

P 

erchlorate can and does naturally attenuate in the subsurface. However, it can be difficult to 

document monitored natural attenuation at many sites. ESTCP has recently released a draft 

protocol for demonstrating monitored natural attenuation (MNA) of perchlorate using a tiered 

approach: Tier 1 - determine the spatial and temporal distribution of perchlorate; Tier 2 - 

characterize the suitability of bio-geochemical conditions for perchlorate biodegradation; and 

Tier 3 - confirm microbiological indicators of perchlorate biodegradation. With funding from 

ESTCP, Solutions-IES has documented the MNA of perchlorate at two sites using this tiered 

approach. 

At the Naval Support Facility in Indian Head, MD, elevated perchlorate concentrations (~24,000 

µg/L) from a former rocket motor hog-out facility gradually decline as the plume migrates 

toward Mattawoman Creek, a tidal stream 400 feet downgradient from the source. Tier 1 and 

Tier 2 activities supported further investigation into using MNA as a remedial alternative. 

Perchlorate declined by 3 orders-of-magnitude during migration through the intertidal zone, 

resulting in residual perchlorate (3.4 to 6 µg/L) in the shallow groundwater beneath the creek and 

no detectable impact to the creek. Some of the decline in perchlorate concentration may be due 

to dilution and intertidal mixing. However, the overall decline is much greater than would be 

expected based on dilution alone indicating that perchlorate is biodegrading. Columns were 

installed in the stream bed to provide a direct measure of in-situ biodegradation (Tier 3). 

Measured first-order biodegradation rates were between 24 to 61 per year due to high levels of 

organic carbon in the intertidal sediments. 

At an Alliant Techsystems (ATK) manufacturing facility, Tier 1 and Tier 2 activities provided 

evidence for MNA of perchlorate. To supplement existing lines of evidence, in-situ columns 

were installed at ATK approximately 70 ft from the stream edge, and were used to measure 

perchlorate biodegradation in shallow sediments just prior to discharge to the stream. Perchlorate 

decreased from 133 µg/L to below detection over a six month monitoring period. First-order 

biodegradation rates were between 7 to 9 per year. The tiered approach offers a systematic 

process to evaluate perchlorate MNA at complex sites. This work is funded by ESTCP Project 

ER-0428. 

G-141


Perchlorate 


CONTINUOUS AND SEQUENCING BATCH OPERATIONS OF A HYDROGEN 

BASED MOVING BED BIOFILM REACTOR TO ACHIEVE VERY LOW 

EFFLUENT PERCHLORATE CONCENTRATIONS 

EBERHARD MORGENROTH 

University of Illinois at Urbana-Champaign 

Department of Civil and Environmental Engineering 

205 North Mathews Avenue 

Urbana, IL 61801 

(217) 333-6965 

emorgenr@uiuc.edu 

CO-PERFORMERS: Jin Woo Lee, Sanghyung Lee, and Lance Schideman 

(University of Illinois); Byung J. Kim (U.S. Army Engineer Research and Development Center, 

Champaign, IL) 

P 

erchlorate (ClO - 4 ) is used as an oxidant in rocket fuels and in explosives and has now 

become a widespread groundwater contaminant. Nine states in the U.S. have recently 

defined state perchlorate advisory levels ranging from 1 to 18 µg/L for drinking water. 

Perchlorate can be reduced biologically using either organic compounds (e.g., acetate) or 

hydrogen as electron donors. We evaluated a hydrogen-fed moving bed biofilm reactor (MBBR) 

to treat concentrated perchlorate streams (10 to 1,000 mg/L) to achieve effluent concentrations 

below the detection limit (4 µg/L). Completely mixed conditions in the MBBR are beneficial to 

avoid problem often observed in fixed bed biofilm reactors such as biomass stratification, 

clogging, and short-circuiting. But completely mixed conditions in the MBBR can provide a 

challenge when the target is to remove perchlorate down to the detection limit. These kinetic 

challenges can be overcome when operating the MBBR as a sequencing batch reactor (SBR) 

taking advantage of higher conversion rates due to higher bulk phase concentrations during most 

of the cycle while, at the end of the cycle, achieving perchlorate concentrations below the 

detection limit. The specific purpose of this study was to evaluate the pros and cons of SBR 

operation and to compare them with continuous MBBR operation. A 10 L bench scale MBBR 

was operated for more than a year as a continuous flow reactor or as an SBR. Hydrogen gas was 

introduced at the bottom of the reactor and recirculated from the head space to provide hydrogen 

transfer and mixing of the reactor. Effluent concentrations below the detection limit could be 

achieved both with continuous and SBR operation. But continuous operation required long 

hydraulic retention times (> 60 hours) for complete perchlorate removal while complete removal 

with SBR operation was achieved with 12-hour hydraulic retention times and loading rates up to 

2 g ClO - 4 /(Ld). Biofilm accumulation and kinetics were monitored throughout the reactor 

operation and removal kinetics were evaluated. Operating the MBBR as a SBR reactor can be 

advantageous for the treatment of concentrated waste streams with requirements for very low 

effluent concentrations. Ongoing work is evaluating the application of the SBR MBBR also for 

lower influent perchlorate concentrations and for combined perchlorate and RDX removal. 

G-142


Perchlorate 


DETERMINING THE ORIGIN OF PERCHLORATE USING STABLE ISOTOPE 

ANALYSIS 

PAUL HATZINGER, PH.D. 




(609) 895-5356 

paul.hatzinger@shawgrp.com 

CO-PERFORMERS: N. Sturchio, Ph.D. and A. Beloso, Jr. (University of Illinois at Chicago); 

J.K. Böhlke, Ph.D. (USGS); B. Gu, Ph.D. (ORNL); W. A. Jackson, Ph.D. (Texas Tech 

University); G. Harvey, (USAF) 

P 

erchlorate (ClO - 4 ) has both natural and synthetic sources. Perchlorate has long been known 

to co-occur with nitrate and other anions in caliche deposits in the Atacama Desert of Chile. 

These deposits were widely imported in the United States during the first half of the 20th century 

as an agricultural fertilizer. In addition to Chilean caliche, natural perchlorate has now been 

detected in mineral deposits and in surface soils throughout arid regions of the western United 

States. The key objective of this ESTCP-funded project (ER-0509) is to distinguish natural from 

man-made perchlorate using isotope-ratio mass spectrometry, as well as to understand the extent 

and origin of variations in the isotopic compositions of synthetic and natural perchlorate. 

Techniques have been developed to collect, purify, and measure the isotopic composition of 

perchlorate (d 37 Cl, d 18 O, and D 17 O) in both source materials and environmental samples. 

Consistent differences have been observed between natural perchlorate derived from Chilean 

caliche (and fertilizers prepared from this material) and all synthetic sources tested to date. The 

d 37 Cl values in the synthetic samples average 12 ‰ higher than the Chilean perchlorate, while 

the d 18 O values average 11‰ lower. The natural perchlorate is also characterized by a distinctive 

17 O excess (D 17 O ≈ 10‰) that readily differentiates it from man-made perchlorate (D 17 O ≈ 0‰), 

and suggests an atmospheric origin with ozone as a reactant. 

Isotopic analyses of perchlorate in groundwater have been performed at locations across the 

U.S., and both synthetic and natural signatures have been observed, as have signatures indicating 

local mixtures of these sources. The data suggest that perchlorate originating from past 

agricultural practices contributes significantly to groundwater contamination in some regions, 

including southern California and Long Island, New York. Interestingly, stable isotope ratios of 

naturally-occurring perchlorate in groundwater at several sites in the western U.S. (including 

Texas, New Mexico, and Oregon) deviate from those of Chilean derived perchlorate, indicating 

that such perchlorate was formed by a different mechanism or that it may have been modified by 

biological, physical, or geochemical processes after deposition. Additional studies are ongoing to 

explain the genesis of isotopic variations in natural perchlorate. 

G-143


Perchlorate 


COMPARISON OF GENES INVOLVED IN PERCHLORATE BIODEGRADATION 

DR. MARTINA M. EDERER 


Environmental Biotechnology Institute 

860 W. Idaho Street 

Moscow, ID 83844 

(208) 885-5979 

mederer@uidaho.edu 

CO-PERFORMERS: Reema Bansal, Jenni Crawford, Dr. Andrzej Paszczynski, Dr. Tom Hess, 

and Dr. Ronald Crawford (University of Idaho) 

P 

erchlorate compounds have been used in the United States for more than 50 years, and 

estimates are that more than 15.9 million kg of perchlorate salts have been discharged into 

the U.S. environment since the 1950s. There are a number of methods to remediate perchlorate 

contamination in the environment; however, most non-biological methods are either not very 

cost effective or produce high volumes of secondary wastes. Bioremediation presents an 

attractive alternative to traditional perchlorate cleanup technologies. A number of 

microorganisms have been isolated that grow by anaerobic reductive dissimilation of chlorate 

and/or perchlorate. The reduction pathway consists of two enzymes: perchlorate reductase and 

chlorite dismutase, encoded by the pcrABCD operon and cld gene, respectively. We have cloned, 

sequenced, and compared the cld genes from four different organisms (Pseudomonas stutzeri, 

Pseudomonas chloritidismutans, Dechloromonas hortensis and Dechlorosoma sp.) as well as the 

complete pcr operon of Dechlorosoma sp. We found that the cld genes from all four organisms 

are more closely related to each other than to previously published cld sequences. Both, the 

sequences for cld and pcr that we determined were most closely related to equivalent loci in the 

Dechloromonas aromatica genome (NC 007298). Further, we subcloned the cld genes from P. 

chloritidismutans and Dechlorosoma sp. into expression vectors and determined activity of the 

enzymes their new hosts by monitoring disappearance of chlorite by mass-spectrometry (MS), 

which proved to be a fast and easy assay method. The enzyme from either organism is actively 

expressed in log phase E. coli cells, but not in Sinorhizobium meliloti strain 1021. As reported 

by others, expression was not sensitive to oxygen. We have also cloned the entire pcr operon and 

linked cld gene from Dechlorosoma sp. in pCR2.1 (Invitrogen). We are in the process of 

subcloning this complete set of genes into an expression vector and characterizing expression of 

the pathway in E. coli by monitoring disappearance of perchlorate using MS. Further studies will 

focus on the cloning and expression of additional perchlorate degradation genes from novel 

enrichment cultures that we have obtained, and expression of all our cloned genes in diverse 

bacterial species and ultimately in naturally-occurring bacterial biofilms to facilitate in-situ 

bioremediation of perchlorate. This work is funded by SERDP Project ER-1562. 

G-144


Perchlorate 


L 

FIELD-SCALE BIOREMEDIATION OF PERCHLORATE IN GROUNDWATER 

UTILIZING AN ACTIVE-PASSIVE TREATMENT APPROACH 

DAVID LIPPINCOTT, P.G. 




(609) 895-5380 

david.lippincott@shawgrp.com 

CO-PERFORMERS: Paul B. Hatzinger, Ph.D. and Charles Schaefer, Ph.D. 

(Shaw Environmental, Inc.); John Cullinane Jr., Ph.D. (U.S. Army Engineer Research and 

Development Center) 

aboratory studies suggest that in-situ treatment of perchlorate in groundwater can be a 

successful remedial option at many sites. Perchlorate-reducing bacteria are naturallyoccurring 

in groundwater and can often be stimulated to biodegrade perchlorate through the 

addition of various electron donors. However, for full-scale treatment to be effective, an electron 

donor must be successfully mixed with the perchlorate-contaminated groundwater, often in a 

very heterogeneous aquifer. The primary approaches to deliver electron donor to the subsurface 

include: (1) groundwater extraction-reinjection systems that actively mix soluble donors into 

groundwater, and (2) passive systems employing slow-release organic substrates that utilize 

natural groundwater flow for distribution. Each of these approaches is generally effective for 

perchlorate treatment. However, active treatment systems often have significant operation and 

maintenance (O&M) issues due to biofouling of injection wells, and passive systems frequently 

produce and/or mobilize significant secondary groundwater contaminants including iron, 

manganese, hydrogen sulfide, and sometimes arsenic. This field project utilized a hybrid “activepassive” 

approach for electron donor addition. This system employs intermittent groundwater 

extraction-reinjection to establish a recirculation zone and mix electron donor within a treatment 

area, then allows natural groundwater flow to further distribute the donor. 

The active-passive system was installed at the former Whittaker-Bermite Facility in Santa 

Clarita, CA, after extensive site investigation and groundwater modeling. A pair of extraction 

wells were installed approximately 20 meters apart and perpendicular to groundwater flow, and a 

single injection well was placed between the two extraction wells. A network of 11 monitoring 

wells was used to assess system performance. Citric acid was added as the electron donor in 5 

active treatment phases. During these phases (1-3 weeks each), the extraction wells were 

operated at 6-10 gpm total flow and citric acid was added in large pulses, generally followed by 

chlorine dioxide to prevent well fouling. The system was shut down between the active events 

(passive mode). Perchlorate concentrations in five of the monitoring wells (of 8 in the treatment 

zone) declined from ~ 300 µg/L to < 2.5 µ/L during the 7-month demonstration, and 

concentrations in 2/3 remaining wells declined to < 50 µg/L. Nitrate levels in each of these wells 

also declined significantly, from > 15 mg/L to < 0.2 mg/L. Iron and manganese levels increased 

in some of the monitoring wells, but mobilization of arsenic was not observed. Significant 

biofouling was not observed during the course of the demonstration. The pilot test shows that an 

active-passive design can be used to effectively mix electron donor into groundwater for 

perchlorate treatment with minimal O&M due to well biofouling. 

G-145


Perchlorate 


USING PERCHLORATE REDUCTASE FROM DECHLOROMONAS AGITATA STR 

CKB TO DETECT PERCHLORATE IN THE PPB RANGE 

R 

JOHN COATES 

University of California, Berkeley 

271 Koshland Hall 

Berkeley, CA 94720 

(510) 643 8455 

jcoates@nature.berkeley.edu 

CO-PERFORMERS: Mark Heinnickel, Stephen Smith, and Jonathon Koo 

(University of California, Berkeley) 

ecognition of perchlorate as a widespread contaminant across the United States posing an 

adverse health threat has influenced its placement on the contaminant candidate list. Current 

methods of detection require use of expensive and time-consuming ion chromatographic 

equipment that requires highly trained personnel. Our studies have focused on the development 

of an alternative mechanism for perchlorate determination. The goal of these studies is to 

develop a simple, highly sensitive, specific bioassay for perchlorate that can be performed on the 

benchtop with basic equipment. Our bioassay takes advantage of the unique biochemistry of the 

perchlorate reductase enzyme (PCR) purified from the perchlorate reducer, Dechloromonas 

agitata strain CKB. Our results indicated that the biochemical electron donor, NADH, combined 

with the dye N-methylphenazinium methosulfate (PMS) provided the optimum mechanism for 

supplying electrons to the PCR to reduce perchlorate. Monitoring NADH concentrations by 

absorbance at 340 nm revealed a strong reproducible correlation between the perchlorate reduced 

and the NADH oxidized by PCR under anaerobic conditions. A similar correlation was observed 

when the assay was conducted aerobically on a benchtop underneath mineral oil. To bring the 

detection limit to below California regulatory limits, a perchlorate concentration step was added 

to the protocol. In our procedure, modified from a protocol published by the U.S. Army Corp of 

Engineers, the perchlorate sample is loaded on styrene-divinyl benzene columns pre-conditioned 

with DTAB and eluted using MOPs buffer. Interfering ions, such as nitrate or chlorate, are 

differentially eluted to avoid false positives. These combined techniques quantitatively detected 

perchlorate in samples that have concentrations less than 1 ppb. More importantly, the developed 

bioassay, detected perchlorate in 6 different groundwater and soil samples and the results were 

verified with excellent accuracy using ion chromatography. From an economical aspect, each 

sample requires only $0.43 worth of chemicals and materials per measurement. This is far less 

than the cost per sample analyzed by ion chromatography. Furthermore, the only equipment 

necessary for this analysis were pippets, quartz cuvettes, and a handheld spectrophotometer. The 

cost of cuvettes and a handheld spectrophotometer can be as low as $500, significantly cheaper 

than an ion chromatography system ($25,000). These studies have resulted in the successful 

development of a highly sensitive and robust colorimetric biossay for the specific determination 

of perchlorate concentrations. This assay has proven to be cheap and accurate and has already 

been reliably applied to the determination of perchlorate contamination in diverse environmental 

groundwater and soil samples. This work is funded by SERDP Project ER-1530. 

G-146


Perchlorate 


NOVEL ELECTROCHEMICAL PROCESS FOR TREATMENT OF 

PERCHLORATE IN WASTE WATER 

YUEHE LIN 

Pacific Northwest National Laboratory 

902 Battelle Boulevard 

P.O. Box 999 

Richland, WA 99352 

(509) 371-6241 

Yuehe.lin@pnl.gov 

CO-PERFORMERS: Dawon Cho, Jagan Bontha, and Jun Wang (Pacific Northwest National 

Laboratory) 

T 

he objective of this project is to develop an innovative and cost-effective technology for the 

treatment of perchlorate from wastewaters generated by treatment processes. The technology 

is based on electroactive ion exchange technique combined with nanostructured electroactive ion 

exchange materials. The technology will be sufficiently safe as to be easily extended for the 

treatment of drinking water because the perchlorate uptake step is essentially an ion exchange at 

open circuit, thus no pretreatment of drinking waters is required. Since the ion 

adsorption/desorption is controlled electrically without generating a secondary waste, this 

electrically active ion exchange process is a green process technology that will greatly reduce the 

operating costs. 

We have developed a direct electrochemical approach to synthesize novel hybrid material 

composed of a conducting polypyrrole (PPY) matrix on the surface of carbon nanotubes (CNTs). 

We found that a porous CNT matrix improves the redox switching stability of PPy films greatly. 

The feasibility and potential applications of PPy/CNT for removing perchlorate from aqueous 

solutions through electrically switched anion exchange have been demonstrated. The high 

surface area of carbon nanotubes and ion exchange properties of PPy provide the composite film 

with a high capacity and stability for anion uptake and elution. The selectivity of PPy films for 

the perchlorate ion is demonstrated through cyclic voltammetric measurements. Furthermore, the 

functionality of PPy can be easily achieved by introducing a new functional group; therefore, the 

selectivity and capacity can be further improved. Such a novel and stable hybrid material 

promises a new route to develop a practical process for removing perchlorate through electrically 

switched ion exchange. Recent progress on technology development will be presented. This 

work is funded by SERDP Project ER-1433. 

G-147


Heavy Metals 


IMPACT OF DISSOLVED SI ON UPTAKE OF AS(III) BY FES-COATED SAND 

UNDER ANOXIC CONDITIONS 

YOUNG-SOO HAN 

The University of Michigan 


1351 Beal Avenue 

Ann Arbor, MI 48105 

(734) 846-5705 

hankr@umich.edu 

CO-PERFORMERS: Dr. Avery H. Demond and Dr. Kim F. Hayes (The University of Michigan) 

A 

s part of SERDP Project ER-1375, FeS-coated sand is being evaluated for removal of 

As(III) from groundwater under anoxic conditions. When FeS-coated sand is contacted by 

water as a permeable reactive barrier (PRB) material, dissolved Si is present. Dissolved Si has 

been noted to reduce the sorption of arsenic using sorbents targeted to remove arsenic under oxic 

conditions, (e.g., iron oxides and activated carbon; Roberts et al. 2004, Gu et al., 2005). 

However, it has yet to be demonstrated whether dissolved Si hinders the removal of As(III) by 

FeS under anoxic conditions. This study reports on the impact of dissolved Si on As(III) uptake 

by FeS. 

The effect of dissolved Si on As(III) sorption was tested in 0.5 g/L FeS suspensions over a range 

of concentrations at pH 5, 7 and 9. The results show that dissolved Si has a negligible impact on 

As(III) at all the tested conditions. At pH 7, in the absence of dissolved Si, 0.5g/L FeS removed 

0.112 mM (84%) and 0.012 mM (90%) of As(III) out of the total added of 0.133 mM and 0.0133 

mM, respectively. When 0.35 mM of sodium meta silicate (Na 2 SiO 3 ) (10 ppm) was added to the 

system at pH 7, the same amounts of As(III) were removed (i.e., 0.110 mM and 0.012 mM 

As(III), respectively). At pH 9, As(III) removal was not affected by the presence of dissolved 

silicate, even though the As(III) removal efficiency was about 10% of the pH 7 results. At pH 5, 

conditions under which the highest As(III) uptake is achieved, dissolved Si also had a negligible 

impact. As(III) removal was 100% for total As(III) concentrations over the range of 0.0133 mM 

to 1.33 mM, and 84% at the highest total As(III) concentration of 2.667 mM. These results 

indicate the removal of As(III) by FeS-coated sands under anoxic conditions is not impacted by 

the inhibitory effects of dissolved Si observed for iron oxide based sorbents used for As removal. 

References: 

Roberts, L.C., Hug, S.J., and Ruettimann, T., et al. (2004) “Arsenic removal with iron(II) and iron(III) waters with 

high silicate and phosphate concentrations.” Environ. Sci. Technol. 38, 307-315. 

Gu, Z.M., Fang, J. and Deng, B.L. (2005) “Preparation and evaluation of GAC-based iron-containing adsorbents for 

arsenic removal.” Environ. Sci. Technol. 39, 3833-3843. 

G-148


Heavy Metals 


P 

INTERACTION OF FES AND ZVI PRBS WITH CALCIUM, CARBONATE, 

AND NITRATE 

ANDREW HENDERSON 

University of Michigan, Department of Civil & Environmental Engineering 

EWRE 

1351 Beal Avenue 

Ann Arbor, MI 48109-2125 

(734) 615-5903 

henderad@umich.edu 

CO-PERFORMER: Dr. Avery H. Demond (University of Michigan) 

ermeable reactive barriers (PRBs) with zero-valent iron (ZVI) have effectively treated 

groundwater at many sites worldwide (ITRC, 2005). Yet performance issues remain; for 

example, the PRB at Monticello, UT, failed due to the buildup of CaCO 3 (s) (Mushovic et al., 

2006). In a statistical review of PRB performance performed as part of this project (SERDP 

Project ER-1375) (Henderson and Demond, 2007), it was found that alkalinity and nitrate were 

both correlated with increased risk of PRB failure. 

Currently, iron sulfide-coated sand is being investigated as an alternative PRB medium for the 

removal of heavy metals. As a source of sulfide, FeS may sequester heavy metals through 

sorption or the formation of highly insoluble metal sulfide phases. Work performed as part of 

this project has shown that, under anaerobic conditions, the removal of As(III) by FeS is greater 

than that reported for ZVI (e.g., Lackovic et al., 2000). 

For the successful application of FeS-coated sand in PRBs, understanding the geochemical 

interactions of FeS with natural groundwaters is crucial, especially in cases where experience 

with ZVI indicates that the dissolved solids may lead to permeability losses. A combination of 

experimental and geochemical modeling approaches is being used to investigate permeability 

loss due to calcium carbonate formation in FeS and ZVI systems in the presence and absence of 

nitrate. Column tests with deoxygenated water, 7 mM calcium and carbonate and 1.6 mM nitrate 

have been conducted. In the absence of nitrate, pH and calcium measurements have indicated 

little precipitation in FeS columns; in contrast, a modest pH increase was observed in the ZVI 

column. With nitrate present, pH increases in both media were greater. The mineralogy of the 

precipitates formed in these columns is being assessed using XRD, XPS, and SEM. 

The formation of solids in anaerobic FeS and ZVI systems, with and without nitrate present has 

also been investigated using geochemical modeling. The modeling has shown that the mass of 

solids formed is greater in the ZVI systems than in the FeS systems, with greater quantities 

formed in both media in the presence of nitrate. Thus, the potential for solids formation in FeS is 

less than that in ZVI, suggesting a smaller loss of permeability over time. 

1. Henderson. A.D., Demond, A.H., Environmental Engineering Science 24, 401-423. 

2. Interstate Technology & Regulatory Council (ITRC). 2005. Report PRB-4. PRB Team, Washington, D.C. 

3. Lackovic, J.A., et al. 2000. Environmental Engineering Science 17: 29-39. 

4. Mushovic, P.T., et al. 2006. Technology News and Trends 23: 1-3. 

G-149


Heavy Metals 


T 

FIELD DEMONSTRATION OF ARSENIC SEQUESTRATION 

DR. MARY F. DeFLAUN 


3131 Princeton Pike 

Building 1B, Suite 205 


(609) 895-1400 

mdeflaun@geosyntec.com 

CO-PERFORMERS: Jackie Lanzon, M.S. and Mike Lodato (Geosyntec Consultants, Inc.); 

T.C. Onstott, Ph.D. and Eric Chan (Princeton University) 

he precipitation of dissolved metals in groundwater under anaerobic conditions has been the 

subject of numerous studies, but there has been very limited research on the mineralogy and 

the stability of these precipitates under variable geochemical conditions. Examining the 

mineralogy and establishing the rate of dissolution of these precipitates under aerobic conditions 

is the subject of this SERDP-supported research (Project ER-1373). A field research site was 

established at Site No. ST-65, a former refueling area at the Avon Park Air Force Range in 

Florida. Sediment and groundwater were collected from the area with the highest concentration 

of arsenic (As) in groundwater (1800 ppb) and were used to construct four flow-through 

columns. In these experiments indigenous sulfate reducing bacteria were stimulated with 

injections of lactate, ethanol, ferrous iron and sulfate over a period of several months under 

strictly anaerobic conditions. Naturally-occurring arsenic in the groundwater as well as spikes of 

arsenic added to the groundwater was removed in the columns. Speciation by XANES 

spectroscopy of column sediments detected primarily As-bearing sulfides, including orpiment, 

arsenopyrite and realgar. Aerobic water was then passed through one of these columns for a 

period of five months. The results of the column studies demonstrated that we can successfully 

sequester As under anaerobic, sulfate-reducing conditions, and that the precipitated As sulfide is 

resistant to dissolution under aerobic conditions. Less than 3% of the precipitated arsenic was 

released over 5 months with the addition of fully-oxygenated water. A small-scale field pilot 

demonstration is currently being conducted at ST-65. The field plot is approximately 30’ H 30’ 

and a recirculation system is being used to distribute amendments throughout the test plot. There 

are six wells: an injection well, a recovery well, and four monitoring wells. Sediment-filled bags 

were hung in all of the monitoring wells and one of these is collected periodically to assess the 

precipitates formed. Geochemical data indicate that sulfate reduction is occurring. Analytical 

data indicate that the amendments are well distributed, and arsenic is being removed from the 

groundwater in the test plot. 

G-150


Heavy Metals 


E 

SOIL METAL BIOAVAILABILITY ADJUSTMENT 

AMY L. HAWKINS 

NAVFAC ESC 



(805) 982-4890 

amy.hawkins@navy.mil 

CO-PERFORMERS: Dr. Mark Barnett (Auburn University); Dr. Nick Basta, Dr. Elizabeth 

Dayton and Dr. Roman Lanno (The Ohio State University); Dr Stan Casteel (University of 

Missouri); Dr. Philip Jardine and Tonia Mehlhorn (Oak Ridge National Laboratory) 

STCP Project ER-0517 is in the process of demonstrating how soil properties can be 

incorporated into a screening tool to predict bioavailability and toxicity of As(V), Cd, Cr, 

and Pb in contaminated DoD soils, and that in vitro methods can be used for risk assessment 

(RA) of toxic metals in soil by cross-correlating in vitro and in vivo studies. 

An initial project workshop was held, resulting in numerous suggestions towards accomplishing 

project goals. The workshop concluded that significantly more complete and coupled data sets 

are needed that link in vivo and in vitro bioavailability with soil characterization and metal 

speciation data. Site selection was drawn from DoD sites including 40+ soil sites previously 

studied under SERDP ER-1166 (Barnett / Jardine) and ER-1210 (Basta / Lanno). 

Twelve soils are being used for ecological bioassays and in vitro studies. In vitro studies will 

also use many of the soils from ER-1166 and ER-1210). The study includes one contaminated 

soil and one control sample from each site. Swine dosing is being done on four of the soils. 

The study encompasses multiple soil types. Use both existing and new data to create more robust 

data sets for cross-correlation and model validation. 

Measures of metal bioavailability can be used to eliminate sites or portions of sites from further 

risk assessment. Two types of approaches could be used: 

1. Where background data on the site such as total metal levels and soil properties are 

available, direct application of the models developed from ER-1166 and ER-1210 would 

provide estimates of the hazard posed by metals at the site; 

2. For sites where little information is available, chemical data such as an in vitro GI 

extraction for human risk or a weak salt extraction for ecological risk would be 

meaningful for making a decision regarding the site. 

These values would be compared to screening criteria to determine whether any further 

assessment is warranted. 

G-151


Heavy Metals 


L 

EFFECTIVENESS OF GRASSES TO STABILIZE METAL TRANSPORT FROM 

SMALL ARM TARGET BERMS 

AFRACHANNA BUTLER 

U.S. Army Engineer Research and Development Center 

3909 Halls Ferry Road 

Vicksburg, MS 39180 

(601) 634-3575 

Afrachanna.D.Butler@usace.army.mil 

CO-PERFORMERS: Dr. Steven L. Larson and Dr. Victor Medina (U.S. Army ERDC); 

Milton Beverly (Environmental Research and Development); David Carter and 

Anthony McCarty (Alcorn State University); Eric Holland (Mississippi State University); 

Scott May (University of Mississippi) 

ive fire testing and training on small arms ranges is essential to the U.S. Armed Forces. 

During range training, bullets are continuously fired into target berms depositing metal into 

the soil. Berms often lack vegetation, and frequently suffer from soil erosion and heavy metal 

(ex. lead-Pb) transport in surface water and, more rarely, into groundwater. 

A large-scale study is being conducted to determine the effectiveness of grasses to reduce the 

migration of heavy metals from a target berm into surface and subsurface water. The study 

consists of a soil from a southeastern United States site. Cynodon dactylon (Bermuda) and 

Eremochloa Buse (Centipede) grasses, which are both native to the Southeast, were planted in 

clean soil. Following grass maturity, M-16 lead rounds were fired weekly for ten weeks into 

unplanted and planted soil berms. Live-fire events were immediately followed by a rain 

simulation procedure to create runoff and leachate. Data obtained from the weekly runoff and 

leachate analyses will determine if Pb and other metals migrating from the impacted berm are 

stabilized and reduced in a planted environment. Plant tissue and soil will be analyzed at the 

termination of the experiment to investigate possible bioaccumulation of metals. These results 

will be presented at the conference. 

G-152


Heavy Metals 


ATTENUATION PROCESSES FOR METALS AND RADIONUCLIDES: A SURVEY 

OF STATE AND FEDERAL REGULATORS AND STAKEHOLDERS 

DIBAKAR GOSWAMI 

Interstate Technology and Regulatory Council 

Attenuation Processes for Metals and Radionuclides Team 

444 North Capitol Street, NW 

Suite 445 


(509) 372-7902 

dgos461@ecy.wa.gov 

CO-PERFORMERS: Carl Spreng (Colorado Department of Public Health and Environment); 

Karen Vangelas (Savannah River National Laboratory); Smita Siddhanti (EnDyna, Inc.); 

Ann Charles (New Jersey Department of Environmental Protection); Natalie Pheasant 

(Tennessee Department of Environment and Conservation); Kenda Neil (NAVFAC Engineering 

Service Center); Anna Butler (U.S. Army Corps of Engineers); 

Peter Strauss (PM Strauss & Associates); Jeff Short (Stakeholder) 

A 

number of Department of Energy (DOE) sites, Nuclear Regulatory Commission (NRC) 

sites, and many Superfund and Department of Defense (DoD) sites are contaminated with 

radionuclides and/or metals. One of the remedial approaches could use attenuation-based 

processes that rely primarily on immobilization of contaminants as stable and/or nontoxic 

species. Until the recent publication of the Environmental Protection Agency’s (EPA) threevolume 

Technical Report Series: Monitored Natural Attenuation of Inorganic Contaminants in 

Groundwater, there were no regulatory compliance guidance documents that specifically 

addressed the use of attenuation-based remedies for metal- and radionuclide-contaminated 

groundwater. This lack of guidance has contributed to inconsistent approaches and application of 

attenuation-based remedies and generally discouraged consideration of such remedies. The net 

result is that many sites face intractable closure problems. The Interstate Technology and 

Regulatory Council (ITRC) Attenuation Processes for Metals and Radionuclides Team is in a 

unique position to develop guidelines that will facilitate the use of this new EPA guidance. An 

initial step in deciding on the specific approach of the ITRC product is determining the existing 

state of regulatory acceptability regarding the concept of the attenuation process and its 

deployment. To assess this, ITRC developed a web-based survey of regulators and stakeholders 

in conjunction with ongoing research at EPA and DOE national laboratories. The findings of the 

survey are presented in three parts, each with specific objectives. Part A gathered information 

that will help assess the extent to which monitored natural attenuation (MNA) and other 

attenuation-based remedies have been implemented at sites contaminated with metals and/or 

radionuclides and factors contributing to that implementation. The data collected in Part B will 

help direct future research and policy development to support the evaluation, implementation, 

and monitoring of attenuation-based remedies. Part C provides additional detail regarding 

specific contaminants. 

G-153


Site Characterization, Monitoring, and Process Optimization 


NANOPARTICLES-BASED IMMUNOSENSORS FOR SENSITIVE DETECTION OF 

EXPLOSIVES, PCB, AND PAHS 

T 

YUEHE LIN 

Pacific Northwest National Laboratory 

902 Battelle Boulevard 

Richland, WA 99352 

(509) 371-6241 

Yuehe.lin@pnl.gov 

CO-PERFORMER: Jun Wang (Pacific Northwest National Laboratory) 

he emergence of nanotechnology is opening new horizons for highly sensitive 

electrochemical assays of environmental pollutants such as explosives, PCB, and PAH. In 

this presentation we will describe the development of novel electrochemical immunosensors for 

detection of TNT, PCB, and PAHs based on the functionalized nanoparticles label. The analogs, 

modified with poly(guanine)–functionalized NPs, are attached on the magnetic beads via 

immnoreaction and then displaced into solution by analytes. The resulting solution was separated 

and transferred to electrode surface for electrochemical measurements. The sensitive assay of 

TNT, PAHs, and PCB is realized by dual signal amplifications: (1) a large amount of guanine 

residues is introduced in the solution through the displacement and poly(guanine)-functionalized 

silica NP label; (2) Ru(bpy) 2+ 3 -induced catalytic oxidation of guanine, which results in great 

enhancement of anodic current. The performance of the electrochemical immunosensor was 

evaluated and some experiment parameters were optimized. The immunosensor based on the 

poly[guanine]-functionalized silica NP label offers great promise for rapid, simple, cost-effective 

detection of explosives, PCB, and PAHs. 

References: 

1. J. Wang, G. Liu, H. Wu, and Y. Lin. “Sensitive electrochemical immunoassay for 2,4,6- 

trinitrotoluene based on functionalized silica nanoparticle labels.” Analytica Chimica 

Acta, 2008, 610, 112-118. 

2. Y.Y. Lin, G. Liu, C.M. Wai, and Y. Lin. “Bioelectrochemical Immunoassay of 

Polychlorinated Biphenyl.” Analytica Chimica Acta, 2008, 612, 23-28. 

3. Y.Y. Lin, G. Liu, C.M. Wai, and Y. Lin. “Magnetic Beads-based Bioelectrochemical 

Immunoassay of Polycyclic Aromatic Hydrocarbons.” Electrochemistry Communications 

2007, 9, 1547-1552. 

G-154




ADAPTIVE LONG-TERM MONITORING AT 

ENVIRONMENTAL RESTORATION SITES 

KARLA HARRE 




(805) 982-1609 

karla.harre@navy.mil 

CO-PERFORMERS: Tanwir Chaudhry (NAVFAC ESC/SBAR, Inc.); Robert Greenwald and 

Weiwei Jian (GeoTrans, Inc.); Charles B. Davis, Ph.D. (EnviroStat); Matthew Zavislak and 

Barbara S. Minsker, Ph.D. (Summit Envirosolutions, Inc.) 

T 

he objective of this project is to demonstrate and validate the recently developed Summit 

monitoring tools by applying the software at three sites. The software is intended to reduce 

costs and improve effectiveness of long-term monitoring, while achieving remediation goals. 

Two major modules comprise the Summit software: Sampling Optimizer and Data Tracker. The 

purpose of Sampling Optimizer is to identify redundant sampling locations and/or frequencies in 

historical data. The purpose of Data Tracker is to assist users in comparing current monitoring 

data with historical data to identify cases where current data deviate from expectations based on 

historical values and patterns. Model Builder, an additional component primarily used by 

Sampling Optimizer, has two sections: one for model fitting, visualization, and analysis, and 

another for visualizing relative uncertainty. The Summit monitoring tools have been applied by 

GeoTrans, representing a typical Department of Defense (DoD) contractor, at three sites: Camp 

Allen Landfill Norfolk Naval Base, (Norfolk, VA); the Former George Air Force Base 

(Victorville, CA); and the Former Nebraska Ordnance Plant (Mead, NE). Results include the 

following: 

• Kriging using quantile transformation qualitatively provided the best representation of the 

measured data, relative to other combinations of interpolation technique (inverse distance 

weighting) and data transformation (log or none) options. 

• Sampling Optimizer provided useful trade-off curves of sampling cost versus the error 

that results from removing samples. These tradeoff curves allow the user to identify 

optimal monitoring plans that represent significant reductions in the number of samples 

with acceptable loss of information. The software allows the user to select a monitoring 

plan along the tradeoff curve and view a map of the plume generated with the full data set 

versus the plume generated with the optimized number of samples. The user determines 

visually if that plan provides an adequate representation of the plume, and if not, the user 

can select other plans along the tradeoff curve. 

• Data Tracker quickly identified many situations in which current data deviate 

significantly from historical values and patterns and provided useful displays of 

concentration versus time for further evaluation and reporting. 

The software was found to be easy to learn and use for a typical DoD analyst/contractor. In 

addition to documenting software functions and capabilities, GeoTrans recorded the time and 

effort required to prepare and import the data and execute the various software functions. 

G-155




SUSTAINABILITY TOOL FOR ENVIRONMENTAL REMEDIATION 

CHARLES J. NEWELL, PH.D., P.E., D.E.E. 

GSI Environmental, Inc. 

2211 Norfolk, Suite 1000 

Houston, TX 77098 

(713) 522-6300 

cjnewell@gsi-net.com 

CO-PERFORMERS: Tiffany N. Swann, Lila M. Beckley, and Dr. Ata U. Rahman (GSI 

Environmental, Inc.); Erica Becvar (Air Force Center for Engineering and the Environment); 

Douglas Ruppel, Gerry Moore, and David Woodward (Earth Tech AECOM) 

W 

ith greater awareness of the size of the “footprint” of environmental remediation, there is 

need to develop a simple tool to compare various remediation technologies holistically so 

that remediation professionals can incorporate sustainability concepts into the decision making 

process. At present, remediation designs are generally based on cost, risk reduction and 

compliance with existing laws and regulations. The sustainability tool incorporates several 

sustainability criteria, such as carbon dioxide emissions, energy consumption and impacts on 

ecosystem service for land and/or groundwater. 

This initiative is sponsored by the Air Force Center for Engineering and the Environment 

(AFCEE) for incorporation of sustainability concepts into U.S. Air Force remediation projects. 

The sustainability tool is intended to be used as a planning tool for implementation of 

remediation technologies at new sites, as well as for evaluation and optimization of existing 

remediation technology systems. Specifically, the tool will allow users to estimate sustainability 

metrics for the following technologies: (1) Soil Vapor Extraction, (2) Excavation, (3) Enhanced 

Bioremediation, and (4) Pump and Treat. Additional technologies will be added at a later date. 

The tool is Microsoft Excel-based and consists of two tiers. Tier 1 calculations are based on 

rules-of-thumb that are widely used in the environmental remediation industry. Tier 2 

calculations are more detailed and allow the user greater control of the input values. The tool 

consists of the following sections: User Input, Design and Materials and Consumables, and 

Sustainability Metrics Output. In the Design and Materials and Consumables sections, users can 

either select default values or can input site-specific values. 

The output section of the tool displays the carbon dioxide emissions, energy use, economic cost, 

safety/accident risk, and change in resource service for land and groundwater for each 

technology. The tool provides several innovative features for evaluation of the output metrics. 

These are: (1) scenario planning (e.g., consideration of different futures for carbon offset costs); 

(2) reporting of metrics in traditional units (e.g., tons of CO 2 emissions) as well as values 

converted into a common unit for easier comparison; and (3) using a consensus-building virtual 

meeting room where stakeholders can weigh the importance of different sustainability metrics. A 

case study will be presented to depict the tool’s functionalities, including these innovative 

features. By combining sustainability metrics with the traditional selection criteria in an easy-touse 

tool, the sustainability tool allows remediation professionals to compare various technologies 

holistically to maximize the overall environmental benefit of cleanup actions. 

G-156




GEOPHYSICAL IMAGING FOR INVESTIGATING THE DELIVERY AND 

DISTRIBUTION OF AMENDMENTS IN THE HETEROGENEOUS SUBSURFACE 

OF THE F.E. WARREN AFB 

A 

ROBERT KELLEY 

Regenesis 

1011 Calle Sombra 

San Clemente, CA 92673 

(815) 230-3516 

bkelley@regenesis.com 

CO-PERFORMERS: Susan Hubbard, Ph.D. and Jonathan Ajo-Franklin, Ph.D. (Lawrence 

Berkley National Laboratory); Belinda Butler-Veytia (URS Corporation) 

common goal in within the in-situ remediation practice is to achieve better delivery of 

amendments to subsurface aquifer systems. Recent projects have explored the combination 

of innovative emplacement techniques, such as hydraulic fracturing, and amendment monitoring 

techniques to better understand delivery methods and long-term amendment distribution. 

Uncertainties associated with the site conceptual model and/or amendment delivery can lead to 

increased project costs due to uncertainty in overall remedial performance (e.g., use of safety 

factors). By reducing uncertainty in amendment delivery, remedial design safety factors have the 

potential to more closely match actual remedial performance, thus reducing overall project costs. 

This ESTCP project (ER-0834) has been designed to focus on the installation of sand fractures 

with Hydrogen Release Compound (HRC ® ) via hydraulic fracturing for biostimulation. Soil 

borings have been used to understand the propagation of sand fractures and distribution of the 

HRC ® within the aquifer. Significant interpretation between data points is required to estimate 

the size of installed fractures and the impact of emplaced HRC ® , resulting in design uncertainty 

and use of safety factors to ensure treatment. 

Geophysical imaging in combination with hydraulic fracturing has the potential to reduce 

uncertainty during the remedial design phase, and following implementation, during performance 

monitoring. If geophysical imaging can be cost effective in comparison to monitoring tools 

currently used and provide data to support a reduction in remedial design uncertainty, it is 

anticipated that its use will result in significant decreases in overall project costs and will be 

widely applicable. 

Multiple geophysical methods (seismic, radar, electrical) will be evaluated to monitor and detect 

the distribution of amendments introduced via hydraulic fracturing. In addition to responding to 

lithologic heterogeneities, three additional classes of geophysical responses are expected to be 

associated with the fracture amendment delivery strategy: those associated with the initial 

hydraulic fracturing, those related to the properties of the amendment, and those associated with 

biogeochemical transformations (such as gas generation or variations in total dissolved solids). 

The first phase of work will be presented including ongoing laboratory experiments, where 

geophysical attributes and/or petrophysical relationships are being evaluated to provide a unique 

signature of the context of fracture installation. 

G-157




ADAPTIVE RISK ASSESSMENT MODELING SYSTEM: 

EVALUATION AND TECH TRANSFER 

DR. SMITA SIDDHANTI 

EnDyna, Inc. 

7925 Jones Branch Drive, Suite 5300 

McLean, VA 22102 

(703) 848-8840 

siddhanti@endyna.com 

CO-PERFORMERS: Brian Espy (Alabama Dept. of Environmental Management); 

Stephen DiZio and Fran Collier (CalEPA, Dept. of Toxic Substances); Ligia Mora-Applegate 

(Florida Dept. of Environmental Protection); Scott Hill (U.S. Army Environmental Center) 

T 

he Interstate Technology and Regulatory Council (ITRC) Risk Assessment Resources Team, 

in its pursuit of exploring methods and tools to assist with risk management of waste sites, 

collaborated with the United States Army Corps of Engineers (USACE), developers of a new 

risk assessment model called the Adaptive Risk Assessment Modeling System (ARAMS). The 

ITRC Team developed a paper that summarizes the ITRC Risk Team’s evaluation of ARAMS 

Version 1.3. In order to validate and improve ARAMS, the team used the modeling system to 

assess risk of real-world sites. These results were compared and contrasted with other accepted 

methods such as SADA (Spatial Analysis and Decision Assistance), EPA’s RAGS (Risk 

Assessment Guidance from EPA Superfund), and select State paradigms. 

ARAMS uses existing databases and models for exposure, intake/uptake, and effects (health 

impacts), incorporating them into a Conceptual Site Model (CSM) framework. ARAMS allows 

the user to visually specify multimedia pathways and risk scenarios with objects. The user is free 

to select the particular model or database of interest for each object. Thus, ARAMS is adaptable 

for assessing different risk scenarios. The core of ARAMS is the object-oriented CSM. It is 

created using RAGS Part D format. Overall, ARAMS is based on a widely accepted risk 

paradigm that integrates exposure and toxicity to characterize risk. 

The objective of this paper is to inform the main target audience (the Army Environmental 

Quality Technology Program (EQT), developers of ARAMS, and the Risk Assessment 

Resources Team) about the ease or difficulty in using ARAMS. A secondary objective is the 

provision of recommendations for improving the ARAMS usability and acceptability among 

consultants, regulators and other stakeholders. The sections detail the following topics: the model 

overview, pros/cons of this modeling system, lessons learned by the team about ARAMS, 

potential regulatory and institutional hurdles, obvious technical gaps, and 

conclusions/recommendations. 

In addition, the ITRC Risk Assessment Resource Team is hosting the ARAMS/SADA 

Technology Transfer Workshop on 6-8 October, 2008 in Kennebunkport, Maine. This Workshop 

is designed to increase awareness of available risk assessment tools. Workshop participants will 

learn to use two of these available tools: ARAMS (Adaptive Risk Assessment Modeling 

System) and SADA (Spatial Analysis and Decision Assistance) including hands-on applications 

of case study scenarios. 

G-158




AN EVALUATION AND IMPLEMENTATION GUIDE FOR GROUNDWATER 

CONTAMINANT MASS FLUX MEASUREMENT METHODS 

PROFESSOR MARK N. GOLTZ 

Air Force Institute of Technology 

2950 Hobson Way, Building 640 

AFIT/ENV 

Wright Patterson AFB, OH 45433-7765 

(937) 255-2998 

mark.goltz@afit.edu 

CO-PERFORMERS: Maj. Jack G. Wheeldon (WPAFB); C1C Anthony E. Hylko (USAFA); 

Dr. Michael Brooks and Dr. A. Lynn Wood (EPA); Dr. Alfred E. Thal Jr. (AFIT); 

Maj. Sonia Leach (HQ AAFES) 

R 

ecent studies have shown that contaminant mass flux is an important parameter to quantify 

in order to assist remediation decision making at sites with contaminated groundwater. Mass 

flux measurements may be used to: (1) prioritize sites for remediation, (2) evaluate the 

effectiveness of source removal technologies or natural attenuation processes, and (3) define a 

source term for groundwater contaminant transport modeling. The purpose of this study is to 

critically review the methods currently available and under development to measure groundwater 

contaminant flux, and provide guidelines for the implementation and use of those methods in the 

field. The study considers various factors that need to be evaluated by a remediation project 

manager in order to decide which flux measurement technology to use, and how best to apply the 

technology. A multi-attribute decision tree was developed to assist in this evaluation. It is 

anticipated that the information in this study, along with the decision tree, will help facilitate 

implementation of the innovative groundwater flux measurement technologies currently in 

development. 

This study looks at the conventional transect method (TM), and the newer passive flux meter 

(PFM), modified integral pumping test (MIPT), and tandem circulating well (TCW) methods of 

measuring contaminant mass flux. In order to facilitate transfer and application of these 

innovative technologies, it is essential that potential technology users have access to credible 

information that addresses technology capabilities, limitations, and costs. This study provides 

such information on each of the methods by reviewing implementation practices and comparing 

the costs of applying the methods at 16 standardized “template” sites. The results of the analysis 

are consolidated into a decision tree that can be used to determine which measurement method 

would be most effective, from cost and performance standpoints, in meeting management 

objectives at a given site. 

The study found that, in general: (1) the point methods (i.e., the TM and PFM) were less 

expensive to use to characterize smaller areas of contamination while the pumping methods (the 

MIPT and TCW) would be more economical for larger areas; (2) the pumping methods are not 

capable of high resolution sampling, which may be required to characterize heterogeneous 

systems or to design remediation technologies; and (3) when high resolution is required, the 

PFM is more economical than the TM. Finally, the study demonstrated that, arguably, the newer 

methods are as accurate as the traditionally used TM. This work is funded by ESTCP Project 

ER-0318. 

G-159




I 

INTEGRATED COMPLIANCE MODEL FOR PREDICTING WATER QUALITY 

STANDARDS FOR COPPER COMPLIANCE IN DOD HARBORS – 

COMPLEMENTING A FATE AND EFFECTS MODEL WITH A 

BIOTIC LIGAND MODEL FOR SEAWATER 

DR. BART CHADWICK 


Environmental Sciences and Applied Systems Branch, Code 71750 


San Diego, CA 92152-6325 

(619) 553-5333 

bart.chadwick@navy.mil 

CO-PERFORMERS: Dr. Ignacio Rivera-Duarte, Gunther Rosen, and Dr. P.F. Wang (SSC- 

Pac); Paul Paquin, Dr. Adam Ryan, Robert Santore, and Dr. Sasha Hafner (HydroQual, Inc.); 

Dr. WooHee Choi (CSC) 

ntegration of a fate & transport model with a toxicity model provides an efficient tool for 

development of site-specific Water Quality Standards (WQS) in DoD harbors. Development 

of WQS in DoD harbors is desirable as the national criterion for regulation of copper in marine 

waters (WQC) proposed by the Environmental Protection Agency (EPA) tends to underestimate 

the natural attenuation of copper toxicity in harbors. Application of overly conservative national 

WQC at DoD facilities has led to difficulties in compliance with discharge permits, and 

disproportionate cost requirements for containment and/or treatment systems. Site-specific WQS 

provide the level of protection intended by the WQC, while allowing realistic regulations to 

DoD. However, development of site-specific WQS involves a long-term and expensive effort in 

order to collect, test and analyze samples. The Environmental Security Technology Certification 

Program is supporting Project ER-0523 for the demonstration of an integrated modeling system 

that provides improved methodology for achieving copper compliance in harbors, which is 

consistent with the current regulatory framework based on the Biotic Ligand Model (BLM) for 

freshwater (EPA, 2007). The integrated model has two components, the seawater-BLM 

(developed as part of this project), and the existing hydrodynamic transport & fate algorithm 

Curvilinear Hydrodynamics in Three Dimensions model (CH3D). The model is applied at a 

harbor-wide scale, and accounts for the natural physical, chemical, biological and toxicological 

characteristics of the harbor to achieve more scientifically based, cost-effective compliance. The 

integrated model is also a management tool for the optimization of efforts on source control, as it 

is robust enough for forecasting effects on copper concentration and toxicity in the harbor as 

results of these controls. The integrated model was demonstrated in San Diego Bay and Pearl 

Harbor. In both harbors the spatial and temporal distributions of copper species, toxic effects and 

Water-Effect Ratio predicted by the integrated model are comparable to previously measured 

data. These results substantiate the support by EPA for future incorporation of the seawater-BLM 

in a full-strength seawater criterion. In San Diego Bay, the integrated model estimates that there 

is a safety factor of two between the actual copper concentrations and the predicted site-specific 

WQS, indicating that application of the predicted site-specific WQS will result in achievable 

discharge limits while still providing the level of protection intended by the Clean Water Act. 

G-160


Energetics 


THE GENES FOR BACTERIAL DEGRADATION OF RDX ARE ON A PLASMID 

S 

DR. STUART STRAND 


167 Wilcox Hall 

Seattle, WA 98195 

(206) 543-5350 

sstrand@u.washington.edu 

CO-PERFORMERS: Peter Andeer and Dr. David Stahl (University of Washington); 

Dr. Neil Bruce and Dr. Elizabeth Rylott (University of York) 

everal degradation pathways for RDX have been hypothesized based on metabolite analysis, 

however only one gene has been directly linked to RDX degradation, xplA. The xplA gene 

was first located in the RDX degrading isolate, isolated from Southern England and subsequently 

in 22 other isolates of the Corynebacteriae. We have since isolated a Microbacterium sp., 

Microbacterium sp. Strain MA1, from RDX contaminated soil from Milan, TN, which can grow 

using RDX as sole source of nitrogen. The xplA gene is located on a plasmid in Microbacterium 

sp. and R. rhodochrous 11Y. Analysis of sequence from the Microbacterium plasmid in the 

vicinity of the xplA gene provides insight to a possible method for lateral transfer of xplA as well 

as identification of other genes relevant to RDX uptake and metabolism. This information may 

prove valuable in remediating RDX contaminated soil by stimulating native xplA harboring 

microbes in situ or promoting the transfer of the gene to and within indigenous populations. 

Stable isotope probing (SIP) of communities from the Milan, TN soil samples using 15N-RDX 

were conducted to identify populations utilizing RDX as a nitrogen source. These studies were 

used to look at if, and under what conditions, xplA bearing isolates would be involved in the 

aerobic degradation of RDX in situ. 

This research is funded by SERDP Project ER-1504. 

G-161


Energetics 


A 

FEASIBILITY OF USING FORAGE GRASSES FOR THE CONTAINMENT OF 

2,4,6-TRINITROTOLUENE AND 1,3,5-TRINITRO-1,3,5- 

TRIAZACYCLOHEXANE AT EGLIN AIR FORCE BASE, FLORIDA 

LAURA B. BRENTNER 

The University of Iowa 

Department of Civil & Environmental Engineering 

4105 Seamans Center 

Iowa City, IA 52242 

(319) 335-6454 

lbrentne@engineering.uiowa.edu 

CO-PERFORMER: Jerald L. Schnoor, Ph.D., P.E. (University of Iowa) 

model, greenhouse-scale study is conducted using two different native soils collected from 

Eglin Air Force Base (EAFB), FL, to assess the environmental and physiological factors 

contributing to the success of phytoremediation of TNT by non-invasive grass species at the 

testing range site. The environmental factors include physical-chemical soil properties, 

contaminant aging in soils, and microbial populations present in native soils. These factors are 

assessed by comparing performance in a potted plant study. Two different native soil types with 

very different physical-chemical characteristics, which have either been aged with or freshly 

contaminated with [U 14 C]-TNT, are compared. Comparisons are also made between unplanted 

pots and pots containing Populus trichocarpa cuttings or a grass mixture of Popsalum notatum 

Pensacola (bahiagrass) and Panicum vigratum Alamo (switchgrass). Concentrations of TNT are 

monitored by extracting TNT from soil and plant tissue samples and analyzing them using a 

liquid scintillation counter and high-performance liquid chromatography to determine 

contaminant removal and detoxification potential. Plant performance is further explored by 

analyzing toxicity and uptake of contaminants using autoradiography methods. The resulting 

data, including soil characteristics and microbial concentration estimates, will be used to test a 

mass-balance mathematical model, adapted from Sung et al. (2004), for predicting TNT 

concentrations in soils in a phytoremediation system. Possible molecular detoxification methods 

are also investigated to provide an additional line of evidence for the treatment capacity of the 

plants. This work is funded by SERDP Project ER-1499. 

G-162


Energetics 


ENGINEERING TRANSGENIC GRASSES FOR IN SITU TREATMENT OF 

RDX AND TNT 

NEIL C. BRUCE 

University of York 

Centre for Novel Agricultural Products 

Heslington, Kent YO10 5YW UNITED KINGDOM 

+44 1904 328777 

ncb5@york.ac.uk 

CO-PERFORMERS: George Zhang, Sharon Doty, and Stuart E. Strand (University of 

Washington); Antonio J. Palazzo (ERDC-CRREL); Elizabeth L. Rylott (University of York) 

D 

ecades of military activity on live fire training ranges has resulted in severe contamination 

of land and groundwater by recalcitrant high explosives. The explosive RDX is a major 

concern, because of its high mobility through soils and subsequent contamination of ground 

water. The objective of this SERDP-funded project (ER-1498) is to engineer plants to contain 

and degrade TNT and RDX in the root zone of explosives contaminated soil. To achieve this 

goal we are investigating the introduction of microbial genes discovered for RDX degradation 

and TNT phytotoxicity resistance into grasses that can be used on training ranges. 

We had previously demonstrated that expression of the rhodococcal gene xplA in the model plant 

system Arabidopsis confers the ability to tolerate and degrade high concentrations of RDX. 

Furthermore, we had also demonstrated that expression of the bacterial nitroreductase nfsI gene 

in Arabidopsis confers resistance to toxic levels of TNT and that the nitroreductase TNT 

transformation products are conjugated to sugars as part of the detoxification process in plants. 

We have now demonstrated that expression of these bacterial genes in creepingbent grass 

enables the transgenic grass lines to tolerate and detoxify high concentrations of RDX and TNT 

respectively. Transgenic creeping bent grass expressing xplA were also observed to efficiently 

remove RDX from liquid media and to utilize RDX-derived nitrogen for growth. As a model 

system for RDX phytoremediation in the field, creeping bent grass expressing xplA and nfsI are 

currently being evaluated in RDX and TNT contaminated soil. 

We have selected three robust species of wheatgrass to engineer and potentially use in the field, 

western (Agropyron smithii), slender (A.trachycaulum) and Siberian (A.fragile), two of which are 

native. The wheatgrasses have broad applicability in a wide geographic range that includes 42 

military facilities in the Intermountain West, they are not invasive, and they have been shown to 

germinate and establish more rapidly. Western wheatgrass is a rhizomatous and relatively low 

growing native plant that is less likely to carry a fire and is also more resilient to training 

activities. 

G-163


Energetics 


OPEN BURN/OPEN DETONATION (OB/OD) MANAGEMENT USING LIME 

FOR EXPLOSIVES TRANSFORMATION 

ANDY MARTIN 

USACE-ERDC 



(601) 634-3710 

andy.martin@usace.army.mil 

CO-PERFORMERS: Dr. Steven Larson, Dr. Jeffery Davis, and Debbie Felt (USACE-ERDC); 

Gene Fabian (Aberdeen Test Center); Gregory O’Connor (ARDEC) 

M 

unitions must be destroyed or demilitarized depending on their lifespan, stability (i.e., 

unexploded ordnance), and/or specific legal requirements (i.e., international treaties). Two 

of the common technologies used are either Open Burn or Open Detonation (OB/OD) operations 

to demilitarize or destroy the munitions. The use of the OB/OD areas can release munitions 

constituents such as residual RDX, TNT, and associated metals used in the munitions casings. 

Once released in the OB/OD area the contaminants can be transported into the environment by 

surface water, ground water, and wind erosion. 

This ESTCP project (ER-0742) will develop a technology that will address the reduction of RDX 

and TNT munitions constituents at an active OD range via the application of lime to induce 

alkaline hydrolysis. The lime addition will also immobilize the metals associated with common 

munitions. Minor erosion control measures will be established to reduce the surface water 

transport of sediments off range through earthen berms. 

Building on the observations from ESTCP Project ER-0216, the proposed technology will reduce 

the RDX/TNT being released into the surface water and ground water in the area of the OD 

range, will immobilize the metals on site, and reduce soil erosion from the range. The potential 

cost savings to an installation includes a reduced or potentially no-cost associated with off-site 

cleanup of surface water and groundwater. In addition, the in-situ degradation of RDX and TNT 

will reduce the overall source zone munitions constituents loading and in the long term reduce 

future on-site clean up costs. This work is funded under ESTCP Project ER-0742. 

G-164


Energetics 


S 

REDUCING TRANSPORT OF ENERGETIC COMPOUNDS 

AT LIVE FIRE RANGES 

DR. MARK E. FULLER 




(609) 895-5348 

mark.fuller@shawgrp.com 

CO-PERFORMERS: Dr. Charles E. Schaefer and Dr. Robert J. Steffan 

(Shaw Environmental, Inc.) 

oil, sediment, and groundwater at many DoD installations have become contaminated with 

various military-related chemicals. Our SERDP and ESTCP research projects (ER-1229, 

ER-0434) have been examining low-cost, readily available materials that can be applied to live 

fire ranges to prevent the migration and/or promote the degradation and immobilization of TNT, 

RDX and HMX. 

A combination of Sphagnum peat moss and crude soybean oil (PMSO) is being examined. 

Laboratory data from batch and column experiments allowed development of a reactive transport 

and fate model which allowed predictions of the flux (loading) of explosives to the subsurface 

and groundwater. The model simulations indicated that the loading would be reduced by the soil 

treatments by a combination of sorption and biodegradation. 

A field evaluation of the technology was performed employing outdoor ex-situ soil plots. The 

study was directed at measuring the reduction in the flux of explosive compounds (i.e., RDX, 

HMX, TNT) from freshly deposited Composition B detonation residues into the underlying soil. 

Over a 1 year period, the PMSO treatment layer reduced the average flux of RDX at 

approximately 30 cm below the soil surface by between 5- and 500-fold compared to control 

plots. The maximum RDX flux at a depth of 30 cm below the soil surface in the control plots 

was 4 H 10 -3 mg/cm 2 /d, compared to


Energetics 


T 

BIOREMEDIATION AND PHYTOREMEDIATION OF RDX AND HMX 

IN TROPICAL SOILS 

DR. ROGER BABCOCK, JR. 

University of Hawaii 

Holmes Hall 383 

2540 Dole Street 

Honolulu, HI 96822 

(808) 956-7298 

rbabcock@hawaii.edu 

CO-PERFORMERS: Stephen Turnbull (Schofield Barracks DPW Environmental); 

Dr. Susan Schenk (Hawaii Agricultural Research Center) 

he Makua Military Reservation (MMR) on Oahu has been in operation since the 1940s and 

currently contains the only combined-arms live fire (CALFAX) training range available in 

the State of Hawaii. The energetic compounds hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), 

and octahydro-1,3,5,7-tetranitro-1,3,5,7 tetrazine (HMX) have been detected in Open 

Burning/Open Detonation area (OB/OD) soils and vadose zone pore water at concentrations 

above EPA Region IX Preliminary Remediation Goals. This ESTCP project (ER-0631) is 

investigating an inexpensive method to lower RDX and HMX concentrations within the 

subsurface, and thereby reduce the potential for off-site migration. 

Two remedial technologies are being deployed in tropical soils for this study: phytoremediation 

and biodegradation. Phytoremediation will be used to evaluate the effectiveness of plants at 

reducing residual energetic contamination within the root zone. Biodegradation will evaluate the 

effectiveness of in-situ enhanced aerobic and anaerobic bioremediation of RDX and HMX 

dissolved in vadose zone pore water beyond the root zone. Neither of these technologies have 

been rigorously tested for their effectiveness in the unique tropical soils of Oahu Hawaii. 

This project has two parts, (1) a greenhouse treatability study, and (2) a phytoremediation and 

bioremediation field demonstration. The treatability study was conducted to determine needs of 

and optimal conditions for the field demonstration. The 12-month phytoremediation field 

demonstration will be conducted to validate the greenhouse degradation rates from plant uptake 

and biodegradation in several test plots at MMR. The concentration of energetic compounds in 

the soil, leachate, plant root and plant shoot will be monitored throughout the duration of the 

field demonstration study. The treatability study was undertaken to measure the degradation of 

the energetic compounds under controlled (greenhouse) conditions. Soil from the MMR was 

excavated, sieved, placed in 54 4-gallon pots with 6 different treatments, inoculated with RDX 

and HMX, and located in a greenhouse with controlled irrigation. Completed between February 

and June 2008, the treatability study found that RDX was degraded within 30 days in treatments 

supplemented with molasses and those with Guinea grass. There was little removal in controls. 

Small amounts of HMX were not degraded. Low concentrations of RDX degradation products 

(DNX, TNX, and MNX) were detected in leachate samples. Several distinct bacteria isolates 

capable of degrading RDX as sole carbon source were isolated from the soils. The treatability 

study included two doses of molasses (1:20 dilution and 1:40 dilution) and found that the lower 

dose was effective and will be used in the field demonstration. 

G-166


Energetics 


USE OF THE JAPANESE QUAIL EMBRYO TO STUDY THE DEVELOPMENTAL 

TOXICITY OF NITROGLYCERIN (NG) 

N 

GHALIB K. BARDAI, MSC. 

McGill University 

Department Pharmacology & Therapeutics 

3655 Prom. Sir-William-Osler 

Montreal, QC H3G 1Y6 CANADA 

(514) 283-6447 

ghalib.bardai@cnrc-nrc.gc.ca; ghalib.bardai@mail.mcgill.ca 

CO-PERFORMERS: Barbara F. Hales (McGill University); 

Geoffrey I. Sunahara (Biotechnology Research Institute) 

itro based compounds are used by the military in the manufacture of explosives and in solid 

propellants. This use has led to widespread environmental release. Human and wildlife 

exposure to nitro compounds occurs through multiple pathways. Transformation of nitro 

compounds in vivo results in the release of nitrite, an important intracellular signalling molecule. 

We have shown previously that exposure to CL-20, a polynitro explosive, resulted in embryo 

developmental malformations. Based on these data, and the current literature of nitrite signalling 

specificity, we hypothesize that nitro-based compounds exert their embyrotoxic effects via nitrite 

formation. We have used nitroglycerin (NG) as a model nitro compound and quail embryos 

(Coturnix coturnix japonica) as a model species to investigate the mechanisms underlying the 

developmental toxicity of nitro compounds. NG (0, 1, 10 or 100 µg/µl, in corn oil) was injected 

in ovo (n=10-11/group) at 0, 33 and 72 hours of embryonic development. There was a dose 

dependent increase in embryolethality, with non-specific malformations. In the survivors, an 

increased incidence of microphthalmia (small eye) was observed which peaked in the 33 hour 

treatment group (1 µg/µl: 20%; 10 µg/µl: 40%), decreasing at 72 h to 22% in the 10 µg/µl group. 

Histological examination of ocular tissue from affected embryos showed a thin and highly 

disorganized retinal pigment epithelium and retina, a thin neural retina and the absence of an 

optic nerve. TUNEL positive apoptotic cells were found in a well-defined region of the 

microphthalmic eye. Alcian blue staining revealed the presence of an abnormal distribution of 

the extracellular matrix. To localize the effects of NG, filter papers soaked with NG were placed 

on the developing eye in ex ovo studies. The control eye developed normally whereas 

development of the NG exposed eye was arrested. 

Thus, NG exposure induced microphthalmia in quail embryos. These studies validate the use of 

NG as a model teratogen in quail embryos to elucidate the developmental cell-signalling 

pathways disrupted by nitro based compounds. This project was supported by FRSQ studentship 

to G.Bardai and SERDP Project ER-1416. 

G-167


Energetics 


TOXICITY OF NITROGLYCERIN AND SELECTED AMINODINITROTOLUENES 

TO TERRESTRIAL PLANTS 

SYLVIE ROCHELEAU 


6100 Royalmount Avenue 

Montreal, QC H4P 2R2 CANADA 

(514) 283-6447 

sylvie.rocheleau@cnrc-nrc.gc.ca 

CO-PERFORMERS: Roman G. Kuperman, Ph.D., Michael Simini, Ph.D., and 

Ronald T. Checkai, Ph.D. (U.S. Army, ECBC); Myrianne Joly, B.Sc., Louise Paquet, B.Sc., 

Jalal Hawari, Ph.D., and Geoffrey I. Sunahara, Ph.D. (BRI); Guy Ampleman, Ph.D. and 

Sonia Thiboutot, Ph.D. (DRDC-Valcartier) 

W 

e assessed individual phytotoxicities of 1,2,3-trinitroglycerin (NG), 2-amino-4,6- 

dinitrotoluene (2-ADNT), and 4-amino-2,6-dinitrotoluene (4-ADNT), using one 

dicotyledonous species (alfalfa Medicago sativa) and two monocotyledonous species (Japanese 

millet Echinochloa crusgalli and perennial ryegrass Lolium perenne). We designed our studies to 

develop toxicity data for deriving Ecological Soil Screening Levels (Eco-SSLs; U.S. EPA, 2005) 

using Sassafras sandy loam (SSL) soil that supports high relative bioavailability of energetic 

materials (EMs). Plants were exposed to individual EMs either freshly amended or 

independently weathered-and-aged in soil for one month (NG) or three months (ADNTs). 

Definitive toxicity tests were performed according to ASTM and U.S. EPA standard protocols. 

Analytical determinations of EMs in soil were done using a modified U.S. EPA Method 8330B. 

Toxicity data were analyzed using nonlinear regression models to determine NG, 2-ADNT or 4- 

ADNT concentrations in soil producing a specified percent effect (ECp and corresponding 95% 

Confidence Intervals; CI) on the plant growth endpoints. 

Preliminary results for NG freshly amended in SSL soil yielded the EC20 and 95% CI values for 

shoot growth (dry mass) of 1 (0-2) mg/kg for ryegrass, and 92 (9-175) mg/kg for alfalfa. 

Weathering-and-aging of NG in SSL soil significantly decreased the toxicity for ryegrass shoot 

growth, with an EC20 value of 26 (12-41) mg/kg but did not affect alfalfa shoot growth, based 

on the EC20 value of 83 (25-141) mg/kg compared to the phytotoxicities of NG in freshly 

amended SSL soil. Preliminary results for 2-ADNT freshly amended in SSL soil yielded EC20 

values for shoot growth (dry mass) of 22 (4-41) mg/kg for ryegrass, 0.002 (0-0.1) mg/kg for 

alfalfa, and 83 (5-160) mg/kg for Japanese millet. Weathering-and-aging of 2-ADNT in SSL soil 

significantly decreased the toxicity to ryegrass and alfalfa, based on the respective EC20 values 

for shoot growth of 64 (42-86) and 36 (0-134) mg/kg. In contrast, weathering-and-aging of 2- 

ADNT in SSL soil significantly increased the toxicity to Japanese millet, based on the EC20 

values for shoot growth of 0.04 (0-0.28) mg/kg. Results of the ongoing investigations with 4- 

ADNT will be presented in the poster. This work was funded by SERDP Project ER-1416. 

G-168


Energetics 


ASSESSING THE BIOACCUMULATION POTENTIAL OF RDX AND HMX IN 

B 

SOIL INVERTEBRATES AND PLANTS 

GEOFFREY I. SUNAHARA, PH.D. 


6100 Royalmount Avenue 

Montreal, QC H4P 2R2 CANADA 

(514) 496-8030 

geoffrey.sunahara@nrc.gc.ca 

CO-PERFORMERS: Sabine G. Dodard, Manon Sarrazin, Kathleen Savard, Myrianne Joly, 

Pierre Yves Robidoux, and Jalal Hawari (Biotechnology Research Institute); 

Sonia Thiboutot and Guy Ampleman (DRDC-Valcartier); Ronald T. Checkai and 

Roman G. Kuperman (U.S. Army, ECBC) 

ioaccumulation of cyclic nitramine explosives hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) 

and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) from soil can impact the higher 

trophic-level receptors through the food chain transfer. We investigated accumulation of these 

explosives by plants and earthworms from Sassafras sandy loam (SSL) soil having physicochemical 

properties (including low pH, clay and organic matter contents) that support high 

relative bioavailability of energetic materials (EMs). Earthworms Eisenia andrei were exposed in 

separate studies to unlabelled or 14 C-labeled RDX or HMX in soil for up to 14 days. Following 

the uptake phase in the studies with 14 C-labeled compounds, earthworms were transferred to soil 

without EMs to determine the elimination kinetics. Concentrations of each EM in the 

earthworms and soil were determined using a modified U.S. EPA Method 8330B. 

Bioaccumulation factors were determined using either the steady-state-based approach by 

estimating tissue-to-soil distribution coefficient (BAF), or the kinetic approach (BAF K ) by 

estimating the ratios of the uptake and elimination rate constants. The phytoconcentration 

potentials for either RDX or HMX were investigated using ryegrass Lolium perenne. Plants were 

grown from seed in freshly amended soil up to 35 days. Harvested tissues (roots or shoots) were 

extracted to quantify concentrations of each EM using a modified U.S. EPA Method 8330B. The 

uptake of each EM was determined using the steady-state-based BAF approach. 

Preliminary results for RDX established the BAF values of 6-7 based on the earthworm 

exposures to soil RDX concentration 10 mg/kg. Earthworms accumulated HMX to a lesser 

extent compared to RDX based on the interim BAF value of less than 1 estimated from exposure 

to HMX concentration 10 mg/kg. Ryegrass accumulated RDX and HMX in the shoots. The 

interim BCF values of 54 and 21 were determined for RDX and HMX, respectively, based on the 

results of plant exposures to either EM soil concentration of 10 mg/kg. These results are 

consistent with previous ecotoxicological studies which showed greater accumulation of RDX in 

plants and earthworms compared with HMX. This work was supported by the Strategic 

Environmental Research and Development Program (SERDP ER-1416). 

G-169


Energetics 


TOXICITY OF NITROGLYCERIN AND AMINODINITROTOLUENES TO 

POTWORM ENCHYTRAEUS CRYPTICUS IN A SANDY LOAM SOIL 

DR. ROMAN KUPERMAN 

U.S. Army Edgewood Chemical Biological Center 

5183 Blackhawk Road 

Aberdeen Proving Ground, MD 21010-5424 

(410) 436-4697 

roman.kuperman@us.army.mil 

CO-PERFORMERS: Dr. Ronald T. Checkai, Dr. Michael Simini, and Mr. Carlton T. Phillips 

(ECBC); Dr. Geoffrey I. Sunahara, Dr. Jalal Hawari, and Ms. Sylvie Rocheleau (Biotechnology 

Research Institute) 

W 

e are investigating the effects of N-based organic explosives 2-amino-4,6-dinitrotoluene 

(2-ADNT), 4-amino-2,6-dinitrotoluene (4-ADNT), and 1,2,3-trinitroglycerin (NG) on soil 

invertebrates. We designed our studies to develop toxicity benchmark values for deriving 

Ecological Soil Screening Levels (Eco-SSLs; U.S. EPA, 2005), for ecological risk assessment of 

energetic materials (EMs) at contaminated sites. We conducted toxicity tests under conditions 

that maximize compliance with Eco-SSL evaluation criteria, using a Sassafras sandy loam soil 

that supports high relative bioavailability of EMs. In this phase of investigation, we adapted the 

standardized toxicity test for the soil invertebrate potworm Enchytraeus crypticus 

(ISO/16387:2005) to establish toxicity benchmark data for 2-A-DNT, 4-A-DNT, and NG, 

independently weathered-and-aged in SSL soil, from one (NG) to three (ADNTs) months. 

Preliminary results for 2-ADNT yielded bounded NOEC and LOEC values 120 and 314 mg/kg, 

respectively, for adult survival; 76 and 90 mg/kg, respectively, for juvenile production by E. 

crypticus. Nonlinear regression analyses (Gompertz model) of toxicity data yielded respective 

interim EC20 and EC50 values for 2-ADNT of 332 and 878 mg/kg for adult survival; 76 and 103 

mg/kg for juvenile production. NG treatments did not impact the numbers of surviving adult E. 

crypticus, yielding results not significantly (p>0.05) different among acetone control and all 

positive treatments tested. These results established an unbounded NOEC for adult survival of 

122 mg/kg for NG. Juvenile production was significantly (p


Energetics 


M 

IMPLEMENTATION STATUS OF MULTI-INCREMENT SAMPLING 

AND METHOD 8330B 

ALAN D. HEWITT 

U.S. Army ERDC-CRREL 

72 Lyme Road 


(603) 646-4388 

Alan.D.Hewitt@erdc.usace.army.mil 

CO-PERFORMERS: Marianne E. Walsh, Michael R. Walsh, and Susan R. Bigl 

(U.S. Army ERDC-CRREL) 

ethod 8330B (http://www.epa.gov/epaoswer/hazwaste/test/new-meth.htm#8330B) was 

posted on the U.S. Environmental Protection Agency (EPA) web page in November of 

2006. This revised method was based on experiences gained through more than 30 training range 

studies conducted by ERDC-CRREL and others under the SERDP (ER-1155 and ER-1481), U.S. 

Army Garrison Alaska soil and water, and Corps of Engineers Distributed Source programs. 

Protocols recommended in EPA Method 8330B allow scientifically defendable project data 

quality objectives to be achieved. Prior to publication of this revised method, very little guidance 

was available for site characterization activities addressing the concentration and mass of 

energetic residues in military training range soils. The ESTCP (ER-0628) demonstration program 

established that some of the more common practices such as splitting samples in the field and 

inadequate sample processing typically results in data that are not representative of the sampling 

location, and only relevant to the subsample extracted and analyzed. To promote conformity 

among various government agencies, ESTCP held several workshops and two field 

demonstration projects and has supported numerous conference presentations and invited 

presentations to various governmental agencies. In addition, to help promote the use of method 

8330B prior to commercial availability, ERDC-CRREL provided sample-processing services to 

a few projects. Today, several commercial laboratories are equipped to pulverize large samples 

so that they can be representatively subsampled. These commercial services recently supported 

projects for the Military Munitions Response Program at Formerly Used Defense sites (MMRP- 

FUDs). Additional use of the multi-increment sampling (MIS) strategy is anticipated, as well as 

use of Method 8330B, when applicable, based on an increasing awareness within State 

Environmental Agencies and EPA Regions. This presentation will summarize the government 

agencies that recommend use of MIS and Method 8330B, and the programs and projects that 

implemented these two procedures. 

G-171


Energetics 


CAPACITIES OF CANDIDATE HERBACEOUS PLANTS FOR 

PHYTOREMEDIATION OF SOIL-BASED TNT AND RDX ON RANGES 

ELLY P.H. BEST 

U.S. Army Engineer Research and Development Center, Environmental Laboratory 



(601) 634-4246 

elly.p.best@usace.army.mil 

CO-PERFORMERS: Thomas Smith and Frank L. Hagen (U.S. Army ERDC, Construction and 

Engineering Laboratory); Dr. Jeffrey O. Dawson (University of Illinois); 

Alan J. Torrey (ERDC-EL) 

E 

xplosives, including TNT and RDX have been released from military operations into the 

environment. The long-term environmental impacts of exposure to elevated levels of these 

compounds are of concern. The U.S. Department of Defense recognizes the need for information 

on the environmental impact of explosives and related compounds, and is involved in studies 

aimed at minimizing their environmental effects. Promising in-situ technologies for 

contaminated soils include phytoextraction—the use of plants to take up (accumulate) and 

remove contaminants from the soil—and phytostabilization—the use of both plants and soil 

amendments to prevent the contaminants from migrating from the source area. Either 

phytoextraction or phytostabilization or a combination of both might be a cost-effective and 

ecologically compatible means of energetic contaminant management. 

A study was conducted to quantify the phytoextraction and phytostabilization capacities of TNT 

and RDX from spiked soil in selected herbaceous species. Dose-response experiments formed 

the basis for evaluating the uptake and tentative in-plant degradation of the soil-based energetics 

and biomass characteristics of the plants. In these experiments, plants were exposed for periods 

ranging from 55 to 83 days in the greenhouse. Biomass and evapotranspiration characteristics 

were determined, and residues of explosives parent compounds and metabolites were analyzed 

using HPLC techniques. Of the ten plant species tested, two grasses and four forbs were 

classified as TNT-tolerant. Total TNT-loss from soil by processes other than plant TNT uptake 

ranged from 18.4 to 33.2 kg TNT ha -1 in grasses and forbs, respectively. Plant TNT uptake 

ranged from 0.2 kg ha -1 in grasses to close to none in forbs. Four grasses took up and 

metabolized TNT and one forb showed some potential for TNT uptake and metabolism. All plant 

species were classified as RDX tolerant. Total RDX-loss from soil by processes other than plant 

RDX uptake ranged from 8.2 to 437 kg RDX ha -1 in grasses and forbs, respectively. Plant RDX 

uptake ranged from 3.4 kg ha -1 in grasses to 6.4 kg ha -1 in forbs. Four grasses and one forb 

metabolized RDX. Based on the results of this study, two plant species were recommended for 

further exploration of their phytoextraction/plant-assisted phytoremediation capacity, i.e., 

Sorghastrum nutans and Amaranthus retroflexus, both species being classified as uptakers and/or 

degraders. This work is funded by SERDP Project ER-1500. 

G-172


Energetics 


DEVELOPMENT OF A PORTABLE FIBEROPTIC SURFACE ENHANCED 

RAMAN SENSOR 

DR. BAOHUA GU 


P.O. Box 2008, MS-6036 

Oak Ridge, TN 37831 

(865) 574-7286 

gub1@ornl.gov 

CO-PERFORMERS: Dr. Pamela A. Mosier-Boss (Space and Naval Warfare Systems Center 

Pacific); Dr. Paul Hatzinger (Shaw Environmental, Inc.) 

R 

apid, in-situ field monitoring technologies are needed to identify potential areas of 

groundwater contamination with energetics at DoD sites. Current techniques for monitoring 

groundwater are expensive, and analytical results often are not available for several weeks after 

samples are collected. The goal of this project is to develop a new, cost-effective technique for 

in-situ quantification and monitoring of energetics such as perchlorate (ClO - 4 ), 2,4,6- 

trinitrotoluene (TNT), and N-trinitro-triazacyclohexane (RDX) in groundwater via fiberoptic 

surface enhanced Raman spectroscopy (SERS). Our specific objectives are to develop and 

fabricate sensitive and selective SERS substrates that can be used for detection of trace quantities 

of energetics, to construct a prototype fiberoptic SERS sensor that can be interfaced with a handheld 

Raman spectrometer, and ultimately to determine the performance and cost effectiveness of 

SERS technique for in-situ field screening and monitoring of contaminant energetics. To date, 

we have fabricated highly ordered SERS substrates using electron beam lithographic techniques 

as well as wet chemical synthesis techniques. These SERS substrates were found to be sensitive 

to detect TNT at concentrations as low as about 10-8 M (~2.3 µg/L) and about 10-9 M (~0.1 

µg/L) for perchlorate by using wet-chemical self-assembly techniques. A SERS probe is also 

constructed and being interfaced with a portable Raman spectrometer for initial laboratory 

testing. This project builds upon recent advances in large-scale nanofabrication of highly ordered 

SERS substrates and our understanding of surface modifications for improved selectivity and 

sensitivity of SERS. The technology has the potential to significantly reduce the cost for longterm 

monitoring at DoD sites due to decreased labor and analytical costs. This work is funded by 

SERDP Project ER-1602. 

G-173


Energetics 


IMPRINTED NANOPOROUS ORGANOSILICAS FOR SELECTIVE ADSORPTION 

OF NITROENERGETIC TARGETS 

M 

DR. BRANDY J. WHITE 

Naval Research Laboratory 

Center for Bio/Molecular Science and Engineering 

4555 Overlook Avenue, SW 


(202) 404-6100 

brandy.white@nrl.navy.mil 

CO-PERFORMER: Paul T. Charles (Naval Research Laboratory) 

aterials for the concentration of nitroenergetic targets from groundwater are sought for 

monitoring and remediation applications. For this work, periodic mesoporous 

organosilicas incorporating diethylbenzene bridges in their pore walls were applied for the 

adsorption of nitroenegetic targets from aqueous solution. The materials were synthesized by cocondensing 

1,4-bis(trimethoxysilylethyl)benzene (DEB) with 1,2-bis(trimethoxysilyl)ethane to 

improve structural characteristics. Molecular imprinting of the pore surfaces was employed 

through the use of a novel target-like surfactant to further enhance selectivity for targets of 

interest (tri- and dinitrotoluenes) over targets of similar structure (p-cresol and p-nitrophenol). 

The head group of the commonly used alkylene oxide surfactant Brij®76 was modified by 

esterification with 3,5-dinitrobenzoyl chloride. This provided a target analog which was readily 

miscible with the Brij®76 surfactant micelles used to direct a material’s mesopore structure. The 

impact of variations in precursor ratios and amounts of imprint molecule was evaluated. The use 

of 12.5% of the modified Brij surfactant with a co-condensate employing 30% DEB was found 

to provide the best compromise between total capacity and selectivity for nitroenergetic targets. 

These results were applied in the development of organosilica materials possessing organization 

on both the meso and macro scales. The incorporation of macropores provides a material with 

enhanced flow through characteristics, thereby reducing back pressure when used in column 

formats. This work is funded by SERDP Project ER-1604. 

G-174


Energetics 


T 

DEPOSITION OF NITROGLYCERINE FROM THE LIVE FIRING OF 

M72 A5 66-MM ROCKETS 

SONIA THIBOUTOT 

Defence Research and Development - Valcartier 

2459 Pie XI Blvd North 

Québec, QC G3J 1X5 CANADA 

(418) 844-4000, Ext. 4283 

sonia.thiboutot@drdc-rddc.gc.ca 

CO-PERFORMERS: Dr. Guy Ampleman, Mr. André Marois, Ms. Annie Gagnon, and 

Major Denis Gilbert (DRDC-Valcartier) 

his study is part of a larger effort undertaken in the context of sustaining operational military 

activities. The Armed Forces need to be informed about the environmental impacts of 

activities such as live firing. This is critical to ensure that training can be conducted on a 

sustainable basis, with minimal adverse impacts. Live fire training range characterizations 

demonstrated that propellant residues reached levels of concern at the firing positions. At these 

locations, the propellant included in the cartridge is ignited to propel the projectile toward the 

impact zone, and unburned propellant is deposited in the firing area. This study was aimed at 

measuring the deposition of propellant residues both from the rearward and front blast of 66-mm 

M72 antitank rockets, a weapon that is frequently fired in Canadian ranges. The 66-mm 

recoilless rocket consists of an open tube that propels an explosive warhead with a flat and short 

trajectory upon ignition of the propellant charge. DRDC-Valcartier participated in a live firing 

exercise of the 22nd Canadian regiment to sample the residues generated by the firing of ninetyeight 

M72 66-mm rounds. Samples were collected using particle traps up to 10 m in front and 30 

m behind the weapons. The area available for sample collection was relatively limited due to site 

constraints. The samples are presently processed and the poster will present the results obtained 

for the dispersion rate of nitroglycerine from antitank M72 66-mm rockets. This work was 

supported by the Sustain Thrust of DRDC, and the Strategic Environmental Research and 

Development Program (SERDP ER-1481, follow-on), Washington, D.C. USA. 

G-175


Energetics 


A 

ASSESSMENT OF GASEOUS AND PARTICULATE PROPELLANT RESIDUES 

RESULTING FROM SMALL ARMS LIVE FIRING 

DR. SYLVIE BROCHU 

Defence Research and Development Canada - Valcartier 

2459, Pie XI North 

Quebec, QC G3J 1X5 CANADA 

(418) 844-4000, Ext. 4333 

sylvie.brochu@drdc-rddc.gc.ca 

CO-PERFORMERS: Isabelle Poulin and Dominic Faucher (DRDC-Valcartier); 

Michael R. Walsh (U.S. Army ERDC-CRREL) 

large number of small arms ranges have been characterized in Canada and the U.S. to 

assess propellant residue accumulation in near-surface soils at firing point areas. From 

range characterization data, the evaluation of the extent of contamination associated with the use 

of a specific ammunition/weapon system is impossible (none is used for a single type of 

munitions, historic information is limited, and soil is often contaminated from past activities). 

Not only is there a lack of information on the buildup of propellant residues on the ground, but 

also there is little information on the gaseous emissions resulting from the live firings. In order to 

properly advise the U.S. and Canadian Forces to sustain military training, and to help design 

alternative gun propellant formulations with better combustion properties than current ones, there 

is a need to better understand the gun propellant combustion and the parameters having an 

influence on the propellant efficiency. A study was thus undertaken to estimate the amount of 

unburned energetic residues deposited per round fired for 15 different caliber/weapon systems 

involving 9 mm, 7.62 mm, 5.56 mm, .50 cal, and .338 cal. For all trials, samples were collected 

in aluminum plates strategically located in front of the gun. To identify the most common air 

contaminants and their concentrations, air samples were also collected for the three most 

commonly used systems using pumps and enclosure bags to optimize sampling. All samples 

were analyzed for nitroglycerin (NG) and 2,4-dinitrotoluene. Also, gas samples were analyzed 

for polycyclic aromatic hydrocarbons, total cyanides, the BTEX suite, aldehydes, and nitric acid. 

The percentage of unburned NG per round was found to vary between 0.001% and 3.90%, and 

up to 2.03 mg NG per round was deposited, depending on the caliber/weapon used. This makes 

the burning efficiency of most small arms better than mortars, but worse than some artillery 

rounds. Although the amount of dispersed NG per round seems low, the large amount of small 

caliber ammunition fired in military training as compared to medium and large caliber 

ammunition can lead to the rapid accumulation on the surface of the soil. Moreover, the small 

arms residues accumulate in a much smaller area than those of mortars and artillery, leading to a 

higher concentration buildup. This work was supported by the Sustain Thrust of DRDC, Canada 

and the Strategic Environmental Research and Development Program (SERDP ER-1481), 

Washington D.C., USA. 

G-176


Energetics 


DEVELOPMENT OF TOXICITY DATA FOR MUNITION COMPOUNDS TO 

SUPPORT TOXICITY REFERENCE VALUE DERIVATIONS FOR WILDLIFE 

DR. MARK S. JOHNSON 

U.S. Army Center for Health Promotion 

and Preventive Medicine 

5158 Blackhawk Road 

ATTN: MCHB-TS-THE 

Aberdeen Proving Ground, MD 21010-5403 

(410) 436-5081 

Mark.S.Johnson@us.army.mil 

CO-PERFORMERS: Craig A. McFarland, Michael J. Quinn, Jr., Matthew J. Bazar, Emily May 

LaFiandra, and Larry G. Talent (Oklahoma State University); Amy L. Hawkins (NFESC); 

Ronald C. Porter (Noblis, Inc.); Robert M. Gogal, Jr. (Virginia Tech) 

T 

he DoD is the steward of extensive land holdings, many of which encompass land uses such 

as training (e.g., firing ranges), munition manufacturing, and demilitarization operations. 

Due to the large size of these areas, their relative habitat value, and the occurrence of munition 

compounds found in the soil, sediment, and surface water at these installations, it is important 

that the DoD can address issues associated with exposures to these substances to valued wildlife 

species. This work (SERDP-funded project ER-1420) represents a tiered approach to provide the 

needed data for the most prevalent munition compounds and constituents for wildlife to aid in a 

risk assessment. Wildlife laboratory models were developed and exposed to various munition 

compounds in a controlled regime and investigated for adverse effects. From these data, safe 

thresholds for exposure are determined for RDX, TNT, DNT, and amino-dinitotoluenes for birds, 

mammals, reptiles and amphibians. 

G-177


Sediments 


REVIEW OF ENHANCED MONITORED NATURAL RECOVERY AT 

CONTAMINATED SEDIMENT SITES 


U.S. Navy-SPAWAR-SSC, Environmental Sciences Branch 

SPAWAR Systems Center San Diego, Code 2375 

53560 Hull Street 


(619) 553-5333 


CO-PERFORMERS: Ms. Victoria Kirtay (Navy); Dr. Victor Magar and Dr. Jason M. Conder 

(ENVIRON); Dr. Marc Greenberg (EPA); Dr. Gui Lotufo (U.S. Army Engineer Research & 

Development Center); Dr. J. Germano (Germano & Associates, Inc.) 

E 

nvironmental restoration of active and abandoned military installations poses a major 

challenge for the United States Department of Defense (DoD) due to the sheer number and 

diversity of facilities and past activities that have released contaminants into the environment. 

Contaminated sediment issues can be significant for DoD installations located near ecologicallysensitive 

aquatic environments, with costs totaling over one-billion dollars for remedies that 

utilize traditional dredging and capping techniques. This presentation examines sediment 

management projects that have employed Enhanced Monitored Natural Recovery (EMNR), also 

know as thin layer capping (TLC). Although TLCs are generally much thinner than isolation 

caps (e.g., only 6-12 inches thick), TLCs serve many of the same purposes as isolation caps, 

namely, creating a clean sediment surface, reducing sediment scour potential, and increasing the 

physical barrier between contaminated sediment and the ecological environment. Additionally, 

TLCs accelerate natural recovery processes by rapidly providing a cleaner sediment surface and 

benthic environment. In addition to several ongoing applications at minor sites, the presentation 

reviews EMNR remedial applications at Wyckoff/Eagle Harbor Superfund Site in Bainbridge 

Island (WA), Ketchikan Pulp Company Site in Ketchikan (AK), and Bremerton Naval Complex 

in Bremerton (WA). The variety of sites at which EMNR has been applied underscore EMNR’s 

applicability in addressing a variety of Remedial Action Objectives related to several different 

contaminants of concern in a variety of hydrological conditions. Accurate and precise placement 

of TLCs at the sites, as well as the verification of remedial design, remains a challenge. In terms 

of cap placement, results highlight the fact that significant water depth, bottom slope, and 

organic-enrichment of the sediment do not necessarily preclude the placement of a stable and 

successful thin layer cap. Verifying TLC thickness to address achievement of design 

specifications and monitoring stability over time can be difficult (e.g., when TLC material is 

similar to underlying sediment). Source control is a critical issue for remedial success. In cases 

where ongoing sources are expected, monitoring should focus on resolving chemical deposition 

from the water column from mixing of the TLC with underlying sediment. Whereas all sites 

reviewed demonstrated considerable improvements in surface sediment concentrations following 

EMNR implementation, not all applications can be said to have equally achieved the projects’ 

stated remedial goals, although shortcomings are more due to source control issues rather than 

failure of EMNR itself. 


G-178


Sediments 


MONITORING PLAN DESIGN FOR VALIDATION OF ENHANCED 

MONITORED NATURAL RECOVERY OF CONTAMINATED SEDIMENT 


U.S. Navy-SPAWAR-SSC, Environmental Sciences Branch 

SPAWAR Systems Center San Diego, Code 2375 

53560 Hull Street 


(619) 553-5333 


CO-PERFORMERS: Ms. Victoria Kirtay (Navy); Dr. Victor Magar and Dr. Jason M. Conder 

(ENVIRON); Dr. Marc Greenberg (EPA); Dr. Gui Lotufo (U.S. Army Engineer Research & 

Development Center); Dr. J. Germano (Germano & Associates, Inc.) 

W 

ell defined remediation goals and performance criteria are critical for developing 

successful long-term monitoring programs following implementation of remedies that 

leave contaminated sediments in place. This is especially true since detailed monitoring 

frameworks are lacking, little is known about the long-term efficacy of previously implemented 

sediment remediation efforts, and costs involved in implementation of remedial actions and postmonitoring 

can be elevated. We will present a remedy-specific monitoring approach designed to 

evaluate the performance of Enhanced Monitored Natural Recovery (EMNR) at a DoD sediment 

site (Quantico Marine Corps Base, Virginia to promote a broader understanding of EMNR while 

developing a set of tools for long-term monitoring. 

The site where the EMNR remedy is being implemented is Quantico Embayment, a semi-circular 

inlet of the Potomac River at the Quantico Marine Corps Base (MCB), Virginia. Covering 190 

acres, the Embayment is adjacent to the Quantico MCB Site 4 Old Landfill that was operational 

until 1971. In 2002, analyses of surface sediment grab samples, subsurface sediment core 

samples and biological samples collected within the Embayment revealed that DDT and daughter 

compounds were elevated to be of concern for piscivorous birds. Habitat enhancement capping 

with monitored natural recovery was found to be the preferred alternative, involving the 

placement of a thin layer (6-9 inches) of clean sediment within a remedial footprint delineation. 

This layer facilitates recovery by providing an initial foothold for benthic biota and creating a 

positive chain reaction where surface sediment concentration reductions promote additional 

colonization and recovery. As the clean sediment layer mixes with underlying sediments, 

recovery extends to deeper layers and ultimately results in ecosystem recovery at higher trophic 

levels. 

This presentation will detail the various monitoring approaches to assess the physical stability of 

thin layer caps (TLC), the rate and extent to which TLC material is mixed into the sediment bed 

and the rate and extent of benthic community recovery following TLC application. The effect of 

EMNR in reducing surface contaminant of concern (COC) concentration, toxicity and 

bioaccumulation will also be addressed. 


G-179


Sediments 


GUIDANCE FOR MONITORED NATURAL RECOVERY AT 

CONTAMINATED SEDIMENT SITES 

DR. VICTOR MAGAR 

ENVIRON International Corporation 

123 N. Wacker Drive, Suite 250 

Chicago, IL 60606 

(312) 288-3840 

vmagar@environcorp.com 

CO-PERFORMERS: Dr. D. Bart Chadwick (U.S. Navy-SPAWAR-SSC); Dr. Jason M. Conder 

(ENVIRON); Dr. Tim Dekker (LimnoTech); Dr. Jeff A. Steevens and Dr. Todd Bridges 

(U.S. Army Engineer Research and Development Center); Dr. Marc Mills (U.S. Environmental 

Protection Agency, ORD-NRMRL) 

E 

nvironmental restoration of active and abandoned military installations poses a major 

challenge for the United States Department of Defense (DoD) due to the sheer number and 

diversity of facilities and past activities that have released contaminants into the environment. 

Contaminated sediment issues can be significant for DoD installations located near ecologicallysensitive 

aquatic environments, with costs totaling over one-billion dollars for remedies that 

utilize traditional dredging and capping techniques. A multi-disciplinary team of experts from 

industry, DoD, including U.S. Navy, U.S. Army Corps of Engineers, and U.S. Environmental 

Protection Agency have drafted a guidance to facilitate the understanding and application of 

monitored natural recovery (MNR) at DoD sites with contaminated sediments. MNR involves 

leaving contaminated sediments in place while monitoring the performance of the natural 

physical, chemical, and biological processes that physically isolate, transform, and/or reduce the 

bioavailability and mobility of the contaminants. Although MNR usually requires a much more 

intensive monitoring program than capping or dredging, MNR avoids construction costs while 

retaining the potential to achieve remedial action objective at many sites, resulting in potential 

DoD cost savings of hundreds of millions of dollars. This presentation will provide a brief 

overview of each of the MNR guidance topics, including: (1) key definitions, processes, 

objectives, and considerations for MNR; (2) conceptual site models that highlight natural 

recovery processes; (3) lines of evidence used to investigate the feasibility of MNR as a potential 

remedy during the remedial investigation/feasibility study process; (4) the application of 

quantitative modeling to predict natural recovery performance and interpret natural recovery 

monitoring results; and (5) goal-focused frameworks for long-term MNR monitoring designs. 

The technical and strategic topics of the guidance are presented to assist site managers and 

remedial project managers in assessing the feasibility of MNR as a remedy and implementing 

successful MNR monitoring plans. 


G-180


Sediments 


I 

USING PERFORMANCE REFERENCE COMPOUNDS TO CALIBRATE 

POLYETHYLENE PASSIVE SAMPLERS FOR MEASURING MIXTURES OF 

HYDROPHOBIC ORGANIC COMPOUNDS (HOCS) 

IN SEDIMENT POREWATERS 

PHILIP GSCHWEND 

Massachusetts Institute of Technology 

77 Massachusetts Avenue 

48-216 

Cambridge, MA 02139 

(617) 253-1638 

pmgschwe@mit.edu 

CO-PERFORMERS: Loretta Fernandez, John MacFarlane, and Kathleen Fleming 

(Massachusetts Institute of Technology) 

n order to make the polyethylene (PE) passive sampling methodology useful for a wide range 

of HOCs (e.g., PCB congeners, alkylated PAHs) for which performance reference compounds 

(PRCs) are not readily available, we have sought to extend the method for cases in which the 

PRCs could not be assumed the same as the target compounds of interest in key mass transfer 

properties. The method requires that diffusivity of the target compound in PE be known, as well 

as its PE-water partition coefficient, K PEW , and the site-specific sediment-water sorption 

coefficient, K d . PE diffusivities of several alkylated PAHs and PCBs were measured, and a 

method to estimate PE diffusivity from chemical structure was developed. A mass transfer model 

and observations of PRC losses in specific sediments were used to estimate K d for target 

chemicals. These parameters, along with K PEW values, measured or estimated from structure, 

allowed us to deduce the freely-dissolved porewater concentrations of alkylated PAHs and PCBs 

in a sediment sample from a coal tar contaminated site. The PE-deduced concentrations were 

compared to concentrations measured in porewaters that had been physically separated from the 

sediments and corrected for colloid-associated fractions. 


G-181


Sediments 


D 

INTEGRATED FORENSICS APPROACH TO FINGERPRINT PCB SOURCES 

USING RAPID SCREENING CHARACTERIZATION AND ADVANCED 

CHEMICAL FINGERPRINTING 

JIM LEATHER 

Navy Spawar Systems Center 



(619) 553-6240 

jim.leather@navy.mil 

CO-PERFORMERS: Greg Durell (Battelle); Glenn Johnson (University of Utah); 

Marc Mills (EPA); Keith Forman (NAVFAC) 

etermining the original source of contamination for a heterogeneous matrix such as 

sediments is a requirement for both cleanup and compliance programs within the military. 

The technology to be demonstrated includes two primary components: (1) rapid sediment 

characterization (RSC) screening technologies that provide for wide spatial and temporal 

coverage to delineate sediment contaminant heterogeneity in a cost-effective manner and 

(2) advanced chemical fingerprinting (ACF) on a selected subset of these samples to develop 

fingerprints and delineate sources. The techniques for the RSC of polychlorinated biphenyls 

(PCBs) in sediments have been adapted from methods developed for use in soils. The techniques 

are modifications of the current standard immunoassay methods described under EPA Method 

4020 (Screening for PCBs by Immunoassay) that have been adapted to work on the wet, organic 

rich matrix found in many sediments. ACF has evolved into state-of-the-art PCB analytical 

methods using high-resolution gas chromatography and low-resolution mass spectrometry 

operating in selected ion monitoring mode (HRGC/LRM-SIM) that are highly cost-effective and 

provide detailed, high-quality data. The methods employ components of EPA Method 680 

(HRGC/LRMS PCB homologue and total PCB method) and Method 1668a (HRGC/HRMS PCB 

congener method). The base methods have been modified to include many nonstandard, 

environmentally important, and diagnostic PCB congeners that will permit data analysis for 

differentiating potential sources. PCB forensics data reduction and analysis include various types 

of statistical and other numerical analyses, including the application of sophisticated receptor 

modeling methods to help tease out source relationships. The overall objective of the project is to 

provide guidance on integrating chemical techniques into a cost-effective forensics program to 

apportion regulatory costs among principal responsible parties (PRPs) and/or ensure all 

contaminant sources have been identified prior to mitigation efforts. 


G-182


Sediments 


BENTHIC COMMUNITY RESPONSE TO SEDIMENT AMENDMENTS 

DR. Y. MERIAH ARIAS-THODE 

SPAWAR Systems Center, Pacific 

Code 7175 



(619) 553-2671 

yolandam@spawar.navy.mil 

CO-PERFORMERS: Gunther Rosen and Dr. Jim Leather (SPAWAR PAC); Dr. Jinjun Kan, 

Dr. Anna Obraztsova, Yanbing Wang, and Dr. Kenneth Nealson (University of Southern 

California); Dr. Kirk Scheckel (EPA Ohio) 

T 

he amendments apatite, organoclay, acetate, chitin, and geotextile reactive mats containing 

apatite and apatite and organoclay are currently under examination for remediation of 

contaminated sediments. The objective of this research is to evaluate toxicity to several estuarine 

and marine benthic community surrogates exposed to the amendments singly, and in 

combination. Amphipods (Eohaustorius estuarius), polychaetes (Neanthes arenaceodentata), 

sheepshead minnows (Cyprinodon variegatus), and purple sea urchins (Strongylocentrotus 

purpuratus) were exposed to the various amendments (at concentrations up to 5% by weight) in 

uncontaminated sediment for up to 28 days in the laboratory. Bacterial counts and basic 

microbiology were performed in the overlying water column. The geotextile mats had no 

observable effects on any of the organisms except bacterial growth. Although not statistically 

significant, there was an increase in sea urchin fertilization success observed in all treatments 

that included loosely mixed apatite. Acetate treatments resulted in reduced polychaete survival in 

some beakers, as well as reduced minnow growth. Polychaete mortality was attributed to a 

temporary, but sharp, decline in dissolved oxygen concentration (to 1.3 mg/L) that was observed 

on Day 5 of the exposure. Enhanced growth of N. arenaceodenatata relative to controls, 

however, was observed in acetate treatments. Chitin treatments resulted in overlying water and 

pore water ammonia concentrations substantially higher than any of the other treatments. 

Microbial activities play critical roles in remediation in natural environments. Results indicate 

that bacterial cell counts (~ 2 H 10 5 cell mL -1 ) in the overlying water did not change significantly 

over time for treatments, except those containing acetate, chitin, and apatite. By day 28, cell 

counts in the presence of acetate increased by three orders of magnitude, while counts in chitin 

treatments increased one order of magnitude. It was concluded by the authors that there was no 

inherent toxicity associated with the amendments. Toxicity to the macro benthic community 

from acetate and chitin likely resulted from the increase in bacterial growth and the subsequent 

impairment of water quality. 


G-183


Sediments 


E 

GEOCHEMICAL AND PHYSIOLOGICAL INFLUENCES ON METAL 

ACCUMULATION IN DEPOSIT-FEEDING POLYCHAETES 

NICHOLAS FISHER 

Marine Sciences Research Center 

Stony Brook University 

Stony Brook, NY 11794-5000 

(631) 632-8649 

nfisher@notes.cc.sunysb.edu 

CO-PERFORMERS: Zofia Turek (Stony Brook University); 

Gregory Cutter (Old Dominion University) 

stuarine sediments in industrialized and urbanized areas are enriched in potentially toxic 

contaminants, among them Cd, As, Cr, and Pb and can be a significant source of these 

metals for benthic organisms. Benthic animals are exposed to metals via two routes: aqueous, 

and from ingested sediment. In order to evaluate the risks associated with contaminated 

sediments, it is necessary to assess the extent to which contaminants bound to sediments are 

available for uptake and assimilation in resident organisms. The overall goal of this research is to 

explain bioaccumulation of sediment-associated Cd, As, Cr and Pb in the ubiquitous depositfeeding 

polychaete Nereis succinea, by addressing three questions: (1) What is the geochemical 

fate of metal(loid)s within natural sediment, and how does it change over time; (2) How does a 

metal’s association with a particular sediment fraction (e.g., iron oxides or the organic fraction) 

influence its assimilation in this worm and how efficient is the gut fluid of these worms in 

extracting metals from the sediment; and (3) How does bioaccumulation of metal from ingested 

sediment compare to uptake from pore water Answers to those questions provide a mechanistic 

understanding of processes underlying metal bioaccumulation and may enable quantitative 

predictions of metal bioaccumulation in polychaetes on a site-specific basis. Experiments 

addressing these questions employed gamma-emitting radioisotopes to measure metal uptake and 

retention using environmentally realistic metal concentrations. The assimilability and solubility 

in the gut fluid of metal bound to natural sediments was contrasted with that from specific pure 

phases comprising the sediments; thus metal assimilation from organic phases was compared to 

that in iron oxide or sulfide phases. Aqueous uptake was also assessed. The relative importance 

of dietary vs. aqueous sources of metal for polychaetes was compared. The assimilation 

efficiency (AE) of ingested metal(loid)s in N. succinea were generally higher from sediments 

enriched with phytodetritus than from natural sediments; AEs decreased significantly with 

sediment aging. The AEs of Cd and As bound to Norfolk Harbor sediment ranged from 40-70% 

for freshly labeled sediment, in contrast to that of Cr which was 99% of all metals is obtained from ingested sediment. 


G-184


Sediments 


T 

ASSESSING BIOAVAILABILITY AND BIOACCUMULATION 

WITH FIELD DEPLOYABLE SPME 

DR. DANNY REIBLE 

University of Texas 

1 University Station C1786 

Austin, TX 78712 

(512) 471-4642 

reible@mail.utexas.edu 

CO-PERFORMERS: David Lampert and XiaoXia Lu (University of Texas) 

he ultimate sink for many hydrophobic organic contaminants such as polycyclic aromatic 

hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) is often sediments. Recent 

studies have indicated that the bioavailable fraction of these contaminants, as indicated by the 

fraction leading to toxicity and bioaccumulation, is indicated by the interstitial or pore water 

concentrations even if the route of uptake is ingestion. Direct analysis of pore water 

concentrations is often impossible due to the hydrophobic nature of PAHs and PCBs. Solid phase 

microextraction (SPME) provides a means of quantifying pore water concentrations at the parts 

per trillion level. Previously, laboratory efforts to characterize the kinetics and equilibrium 

uptake on fibers were reported as well as studies confirming the ability of fiber uptake to indicate 

bioaccumulation in benthic organisms. A field SPME sampling device was also developed for 

quantifying pore water profiles in situ. The current poster will report on efforts to extend and 

confirm these studies both in the laboratory and in the field. The emphasis will be on the 

application of the field deployable SPME sampling device and comparison of the results of field 

bioassays to porewater concentration measurements. This device was deployed at several sites 

with simultaneous deployment of caged benthic organisms. This poster summarizes the findings 

to date. 


G-185


Sediments 


T 

IN SITU-BASED MONITORING APPROACH FOR IMPROVED RISK 

ASSESSMENT OF CONTAMINATED SEDIMENTS 

DR. G. ALLEN BURTON 


Cooperative Institute for Limnology and Ecosystem Research 

440 Church Street 

Ann Arbor, MI 48109-1041 

(734) 763-3010 

burtonal@umich.edu 

CO-PERFORMERS: Gunther Rosen and Dr. D. Bart Chadwick (SPAWAR Systems Center 

Pacific); Dr. Marc Greenberg (EPA Environmental Response Team) 

raditional laboratory-based aqueous and sediment toxicity and bioaccumulation testing have 

been extensively evaluated and have their merits, but concern remains with respect to their 

relevance as accurate measures of exposure and effects in the field. Among the inherent 

limitations of laboratory-based tools are the possibility of altered exposure in the lab via sample 

manipulation, and in some cases, loss of the exposure source (e.g., upwelling contaminated 

groundwater or episodic exposure associated with storm events). Two novel in-situ-based 

monitoring tools are described for potentially improving the assessment of ecological risk and 

recovery at contaminated, or previously contaminated, sediment sites: (1) Toxicity screening on 

in-situ collected interstitial water samples for rapid mapping of “hot spots”; and (2) deployment 

of multi-parameter in-situ platforms. The Trident probe is a multi-sensor sediment probe device 

that samples pore water in-situ and has been field tested at multiple Superfund sites. Its use has 

been modified to provide samples for chemical and toxicological analyses; reducing artifacts 

associated with collection of interstitial water using ex-situ processes. Several short-term, small 

volume, standard and novel bioassays were compared for use as cost effective, rapid mapping 

tools. Task 1 identified an optimal suite of assays and exposure designs comparing sensitivity to 

toxicants, temperature, salinity, currents and field deployments. For in-situ toxicity and 

bioaccumulation testing, a platform was developed that houses various exposure chamber 

designs, allowing for simple deployment in shallow environments and diver-supported 

deployments at depth. Different compartments of exposure (i.e., water column, sediment-water 

interface, surficial sediment) were assessed over 48 hours, or more, using multi-parameter 

sensors and a variety of estuarine/marine amphipods, polychaetes, mussels, and mysid shrimp. 

The platform also included biomimetics (solid phase microextraction [SPME] fibers and 

diffusion gradient in thin-films [DGTs]) for potentially simpler assessments of exposure. Task 2 

deployments in San Diego Bay, CA were successful, with 48 hour exposures of all assays and 

supplemental comparisons to SPME, mussel and polychaete uptake at 21 days. Toxicity 

responses varied between species (42 to 100% survival) and stations. Results revealed that some 

in-situ assay exposures were not practical for routine use. Since chemical exposure and 

biological effects are assessed together in-situ, potentially more accurate, multiple-line-ofevidence-based 

risk assessments can be performed. The timely results allow for decisions on site 

ranking and second tiered testing needs more effectively than current approaches. 


G-186


Sediments 


THE DETERMINATION OF SEDIMENT POLYCYCLIC AROMATIC 

HYDROCARBON (PAH) BIOAVAILABILITY USING DIRECT PORE WATER 

ANALYSIS BY SOLID-PHASE MICROEXTRACTION (SPME) 

DR. DAVID NAKLES 

ENSR 

4075 Monroeville Blvd., Corporate One Office Park, Building II, Suite 400 

Monroeville, PA 15146 

(412) 380-0140 

dnakles@ensr.aecom.com 

CO-PERFORMERS: Amy Hawkins (Naval Facilities Engineering Service Center); 

Steven Hawthorne (Energy and Environment Research Center); Todd Bridges and J. Daniel 

Farrar (U.S. Army Engineer Research and Development Center); Upal Ghosh (University of 

Maryland Baltimore County); David Thal (Test America) 

R 

ecent data have shown that PAHs in sediments from urban and industrial sites are often 

much less toxic than is generally assumed by generic bulk sediment screening values, and 

toxicity is often not related to the concentration of total extractable PAHs using EPA standard 

methods. To increase the scientific understanding of what governs chemical exposure in 

sediments and how to measure it, the Sediment Contaminant Bioavailability Alliance (SCBA) 

initiated a program to develop a comprehensive database evaluating the bioavailability of 

hydrophobic organic compounds in aquatic sediments. 

To date, the SCBA has completed 16 case studies, with measurements of PAH bioavailability on 

over 200 sediment samples. In a recent publication, the SCBA demonstrated that 73 of 97 (75%) 

of sediment samples analyzed exceeded the probable effect concentration (PEC) value for total 

PAHs (22.8 mg/kg); however, only 23 (32%) resulted in reduced survival to the aquatic 

amphipod Hyalella azteca. 

Concurrent with this effort, the SCBA has supported the development of a new analytical 

technique for estimating PAH bioavailability that involves the measurement of dissolved PAHs 

in sediment pore water using solid phase microextraction (SPME). ASTM and EPA (Office of 

Solid Waste and Office of Water) approval of this method is being pursued with the conduct of 

interlaboratory validation studies. To date, a provisional ASTM standard (D7363 – 07) and an 

EPA method (SW846 Method SW-8272) are already in place. 

ESTCP Project ER-0709 used the SCBA methodology to assess the bioavailability of PAHs in 

sediments from the Anacostia River, proximate to the Washington Navy Yard. The results of this 

case study indicated that the use of PAH sediment screening levels, as well as the EPA 

Equilibrium Partitioning Method, did not adequately predict toxicity and non-toxicity to a 

benthic test organism (Hyalella azteca), and that their use would vastly overstate the volume of 

sediment requiring further action. The direct measurement of PAHs in sediment porewater 

corresponded to toxicity to H. azteca, and provided an accurate assessment of the potential effect 

of sediment PAHs on toxicity to benthic organisms. 

G-187


Sediments 


EVALUATION OF MULTIFUNCTIONAL AMENDMENTS FOR 

SIMULTANEOUS BIOAVAILABILITY REDUCTION OF 

PCBS AND HEAVY METALS IN SEDIMENT 

UPAL GHOSH 

University of Maryland Baltimore County 

1000 Hilltop Circle 

Baltimore, MD 21250 

(410) 455-8665 

ughosh@umbc.edu 

CO-PERFORMERS: Seokjoon Kwon, Jeff Thomas, and Brian E. Reed (University of Maryland 

Baltimore County); Laura Levine and Victor Magar (ENVIRON); 

Cynthia Gilmour (Smithsonian Environmental Research Center); Todd Bridges and 

Daniel Farrar (U.S. Army ERDC) 

I 

n-situ sediment remediation techniques that are less energy-intensive, cost effective, and less 

destructive to the ecosystem are attractive due to limitations of conventional risk management 

strategies such as dredging and capping. Recent studies found that the addition of activated 

carbon (AC) effectively stabilized polychlorinated biphenyls (PCBs) in sediments by reducing 

porewater concentrations and contaminant biouptake in benthic organisms. However, 

contaminated sediment sites often contain complex mixtures of organics and metals that require 

simultaneous remediation. Therefore, multifunctional or multiple amendments are needed to 

address the remediation of such complex sites. 

In this study several sorbents were tested for the stabilization of heavy metal contaminants in 

sediments. The selection procedure for heavy metal amendments included: (1) a literature 

review; (2) a series of aqueous phase sorption studies; (3) toxicity studies; and (4) laboratory 

biouptake measurements using a freshwater oligochaete (Lumbriculus variegatus) and a 

freshwater clam (Corbicula flumineae). The literature study followed by the sorption study 

allowed the selection of several promising engineered metal sorbents. Biouptake reduction of Cd, 

Pb, and Hg was most effective when sediment was amended with a mixture of AC and thiol 

group functionalized mesoporous silica (Th-SAMM). Laboratory scale mesocosms were also 

conducted using field sediment contaminated by both mercury and PCBs. Individual sorbents 

and sorbent mixtures were amended to field sediment and allowed to equilibrate for a month 

before conducting bioaccumulation and leaching tests. Field sediment amended with 3% AC and 

Th-SAMMS demonstrated 90% reduction in PCB biouptake in the freshwater oligochaete. 

Detailed analysis for mercury, methyl mercury, and sorptive properties among treated and 

untreated field sediments are ongoing and will be presented in this poster. 


G-188


Sediments 


QUANTIFYING ENHANCED MICROBIAL DEHALOGENATION IMPACTING 

THE FATE AND TRANSPORT OF ORGANOHALIDE MIXTURES IN 

CONTAMINATED SEDIMENTS 

PROFESSOR MAX HAGGBLOM 


Department of Biochemistry and Microbiology 

76 Lipman Drive 


(732) 932-9763 

haggblom@aesop.rutgres.edu 

CO-PERFORMERS: Joong-Wook Park, Young-Beom Ahn, Hui Liu, Donna E. Fennell, 

Valdis Krumins, Fang Liu, Lisa Rodenburg, and Lee J. Kerkhof (Rutgers University); 

Kevin Sowers, Birthe Kjellerup, and Kate Gillespie (University of Maryland Biotechnology 

Institute) 

A 

quatic sediments are ultimate receptors of many halogenated contaminants, including 

polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins and dibenzofurans 

(PCDD/Fs), and chlorinated pesticides. Sediment treatment is currently limited primarily to 

dredging with ex-situ treatment or sequestration and new methods are needed for in-situ 

containment and degradation of contaminants. Although microbially mediated reductive 

dehalogenation of organohalides is well established, methods for treating aquatic sediments 

contaminated with organohalide mixtures are not yet readily available. The overall objective of 

this project is to stimulate anaerobic biological dechlorination, which offers the most promising 

approach towards eventual detoxification and complete degradation of halogenated contaminant 

mixtures. Our results from micro- and mesocosm experiments indicate that the Anacostia River, 

Kearny Marsh, and Kymijoki River sediments contain a diverse population of dehalogenating 

microorganisms. We have refined and optimized a suite of molecular tools for rapid highthroughput 

detection, enumeration and diversity characterization of bacterial populations that 

reductively dehalogenate the target organohalides. Active dechlorinating populations are present 

in these sediments and biostimulation may enhance the activity of both native Dehalococcoides 

and bioaugmented Dehalococcoides species. We provide evidence for a combined 

bioaugmentation/biostimulation approach to the bioremediation of sediments contaminated with 

chlorinated biphenyls, diphenyl ethers, dibenzo-p-dioxins and/or dibenzofurans. The addition of 

halogenated coamendments might be one tool to enhance dechlorination of PCBs and PCDD/Fs 

in historically contaminated sediments and the halogenated amendments are potentially useful 

for producing exogenous dehalogenating biomass for bioaugmentation. The anticipated endresult 

is an understanding of the microbial in-sediment processes involved in biodegradation of 

organohalide mixtures. This work is funded by SERDP Project ER-1492. 

G-189


Sediments 


SUSTAINED ENHANCEMENT OF DECHLORINATOR POPULATIONS AND 

REDUCTIVE DECHLORINATION ACTIVITY IN PCB- AND CHLORINATED 

W 

PESTICIDE-CONTAMINATED SEDIMENT 

DR. VALDIS KRUMINS 


14 College Farm Road 


(732) 932-9800, Ext. 6122 

krumins@envsci.rutgers.edu 

CO-PERFORMERS: Dr. Joong-Wook Park, Dr. Max M. Häggblom, Dr. Lee J. Kerhkof, 

Dr. Lisa A. Rodenburg, and Dr. Donna E. Fennell (Rutgers University) 

e investigated potential enhancements to reductive dechlorination of polychlorinated 

biphenyls (PCBs) and chlorinated pesticides in sediments from two contaminated sites: 

the Anacostia River, a tidal freshwater waterway in Washington, D.C. containing 2.1 mg/kg total 

PCBs, and from Kearny Marsh, a freshwater impoundment in the New Jersey Meadowlands with 

1.2 mg/kg total PCBs, along with various chlorinated pesticides including p,p'-DDT. Sediment 

microcosms (200 mL) were amended with electron acceptors, haloprimers (tetrachlorobenzene 

or pentachloronitrobenzene), and/or Dehalococcoides ethenogenes strain 195. These treatments 

were evaluated as a means to increase dechlorinator populations and dechlorination activity for 

in-situ bioremediation. To determine if the enhancements were sustained over time, subcultures 

were taken after approximately 14 months of incubation, and dechlorination potential was tested 

by spiking subcultures with PCB116 and observing subsequent dechlorination rates. 

Treatment effectiveness was assessed by examining changes in the chlorination level of the preexisting 

PCBs and pesticides in the sediment, and by tracking DNA-based markers of 

dechlorinating bacteria. Nested polymerase chain reaction targeting Chloroflexi coupled to 

DGGE showed that biostimulation with haloprimers increased the incidence of a native species 

with 16S rRNA gene sequence identical to Dehalococcoides sp. strain CBDB1. D. ethenogenes 

strain 195 was detected only in microcosms bioaugmented with that strain. Twelve primer sets 

were also developed from published reductive dehalogenase (rdh) gene sequences. Several rdh 

genes were detected in unamended sediment from both sites, and biostimulation increased 

incidence of a subset of these. 

Bioaugmentation with D. ethenogenes strain 195 and biostimulation with 

pentachloronitrobenzene both significantly (p


Sediments 


MOLECULAR PHYLOGENETIC ANALYSIS OF ANAEROBIC DECHLORINATION 

OF POLYCHLORINATED COMPOUNDS 

JOONG-WOOK PARK 


76 Lipman Drive, Room 222 


(732) 932-9763, Ext. 222 

JWPark@aesop.rutgers.edu 

CO-PERFORMERS: Dr. V. Krumins, Dr. D.E. Fennell, Dr. L.J. Kerkhof, Dr. L.A. Rodenburg, 

and Dr. M.M. Häggblom (Rutgers University); Dr. B.V. Kjellerup, K.M. Gillespie, and 

Dr. K.R. Sowers (University of Maryland) 

P 

olychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and biphenyls (PCBs) 

are of concern because of their high toxicity and wide distribution. Both PCDD/Fs and PCBs 

with multiple chlorine substituents are more stable and thus resistant to biodegradation; however, 

the compounds’ toxicity depends on the number and position of chlorination. Therefore, 

microbial dechlorination may play an important role in detoxification of environmental PCDD/F 

and PCB contamination. Dehalococcoides ethenogenes strain 195 has been shown to 

dechlorinate PCDD/Fs and PCBs. Dehalococcoides sp. strain CBDB1 has been shown to 

dechlorinate PCDDs. In addition to these Dehalococcoides species, other dechlorinating 

Chloroflexi have also been shown to either directly dechlorinate PCBs or to be likely candidates 

for PCDD/F and PCB dechlorination. Several sets of putative dechlorinating Chloroflexi-specific 

PCR primers were developed and optimized for broad range detection of putative dechlorinating 

Chloroflexi species by using nested PCR denaturing gradient gel electrophoresis (DGGE). 

Nested PCR-DGGE analysis could detect various putative dechlorinating Chloroflexi species, 

most of which could not be detected by conventional DGGE or terminal restriction fragment 

length polymorphism (tRFLP) analysis, in several sediments. Twenty-three bands from nested 

PCR-DGGE were randomly selected and DNA was sequenced, all showed high similarity with 

known Chloroflexi species. With this nested PCR-DGGE, we analyzed 135 day samples from 

microcosms prepared with Anacostia River sediment containing 2.1 mg PCBs/kg dry weight. D. 

ethenogenes strain 195 was detected in bioaugmented microcosms, but not in any other 

microcosms. Certain native Chloroflexi species were detected only in haloprimer-treated 

microcosms, whose partial 16S rRNA gene sequences (128 bp) were identical to group of 

Dehalococcoides species including Dehalococcoides sp. strain CBDB1. Gas chromatography - 

electron capture detection (GC-ECD) analysis demonstrated enhanced dechlorination of PCBs 

only in microcosms where D. ethenogenes strain 195 and/or native Dehalococcoides were 

detected by nested PCR-DGGE analysis. Putative dechlorinating Chloroflexi-specific PCR 

primers developed here were also applied to setup: (1) tRFLP and (2) nested PCR denaturing 

high performance liquid chromatography (dHPLC) analyses. 


G-191


Sediments 


M 

MERCURY BIOACCUMULATION AND TROPHIC TRANSFER IN 

RESIDENT ESTUARINE FOOD WEBS 

DR. CELIA CHEN 

Dartmouth College 

Department of Biological Sciences 

HB 6044 


(603) 646-2376 

celia.chen@dartmouth.edu 

CO-PERFORMERS: Mr. Jason Williams and Dr. Vivien Taylor (Dartmouth College) 

eHg is a global pollutant known to be a potent neurotoxin to which humans are exposed 

largely through the consumption of marine fish and shellfish. Estuarine sediments are 

known repositories of metal contaminants and may be important sites of biotransfer of metals to 

estuarine food webs. Mercury concentrations in estuarine biota depend in part on 

bioaccumulation and trophic transfer patterns within estuarine food webs. We analyzed food web 

structure and organism total Hg and MeHg burden in six resident estuarine food webs in sites 

(4 in the Gulf of Maine, 2 in Naragansset Bay) spanning a gradient of sediment Hg 

contamination. Our goal was to identify sediment and food web characteristics which predict 

metal concentrations in biota. Benthic infauna and epifauna including snails, crabs, mussels, 

polychaetes, and fish were collected at each site and analyzed for inorganic Hg and MeHg, and 

stable isotopes (delta 15N and 13C). Sediment samples were collected and analyzed for total Hg 

and % total organic carbon (%TOC). Across sites, sediment %TOC showed a negative 

relationship with taxa sediment bioaccumulation factors, suggesting organic carbon regulates the 

bioavailability of total Hg. Although food web structures differed between sites, both 13C and 

15N signatures were related to Hg in biota across sites. Taxa mean 13C values showed a 

significant negative relationship with taxa mean MeHg burdens, indicating MeHg burden is 

higher for taxa with more pelagic 13C signatures. In addition, mean taxa %MeHg had a 

significant positive relationship with mean taxa 15N signature (adjusted for site differences), 

indicating %MeHg increases with trophic level across sites. The results of this study show the 

importance of food web characteristics in determining the fate of metals such as mercury in the 

marine environment. This work is funded by SERDP Project ER-1503. 

G-192


Sediments 


MEASUREMENT AND MODELING OF ECOSYSTEM RISK AND RECOVERY FOR 

IN SITU TREATMENT OF CONTAMINATED SEDIMENTS 

DR. RICHARD G. LUTHY 

Stanford University, Department of Civil and Environmental Engineering 

473 Via Ortega, 313B 

Stanford, CA 94305 

(650) 723-3921 

luthy@stanford.edu 

CO-PERFORMERS: Yeo Myoung Cho, Jeanne Tomaszewski, Sungwoo Ahn, and Elisabeth 

Janssen (Stanford University); Amy Oen (Norwegian Geotechnical Institute); Janet Thompson 

and Samuel Luoma (USGS, Menlo Park) 

S 

ERDP Project ER-1552 addresses strategies to assess the ecological recovery of a 

contaminated site after in-situ treatment by activated carbon amendment, as at Hunters Point, 

San Francisco Bay, CA. A biodynamic modeling approach is being developed to predict the 

uptake of PCBs by three important classes of benthic organisms with different feeding strategies. 

Once the species-specific physiological coefficients have been defined, the applicability of the 

biodynamic model will be demonstrated in the field. Three regional surveys will determine the 

benthic species recruitment pool for the Hunters Point area at locations with similar physical 

habitats. Biodynamic modeling will result in a general predictive ecosystem recovery model that 

is directly applicable to any contaminated sediment site, given some knowledge of the local 

recruitment pool and basic information about taxa-specific biodynamics for the contaminants of 

interest. Rapid assessment tools to measure PCB sediment pore water concentrations are being 

tested to correlate aqueous concentrations of PCBs with reduced bioavailability. Polyethylene 

sampling devices (PEDs) and a PCB immunoassay technique are being tested in the laboratory 

and validated in the field, and the results correlated with those obtained using conventional 

methods. Further work with thin polyoxymethylene (POM) sampling devices will demonstrate 

the utility of this method to measure the vertical pore water profile in the sediment. These data 

will compare the variation with depth in pore water concentration with the variation in black 

carbon content. 

We are developing a new method to assess pore water movement within the tidal mud flat. We 

employ a novel approach based on temperature probes and heat transfer modeling. A mass 

transfer model to estimate PCB uptake by activated carbon could then incorporate sediment pore 

water movement and heterogeneous activated carbon distribution. 

Establishing correlations between conventional and alternative measurement tools (passive 

sampling) in the field will allow members of the scientific community and DoD users to 

confidently use the rapid, inexpensive tools in the future to assess the status of a contaminated 

sediment site after treatment or during a monitored natural recovery. Ideally, future researchers 

and DoD users will need only to measure contaminant pore water concentrations and collect 

information concerning the benthic organism recruitment pool to predict the extent of ecosystem 

recovery following remediation. Related studies point to the need for continued work on in-situ, 

contaminant mass transfer models to assess the efficacy and long term benefits of in-situ 

treatments to sequester persistent contaminants in sediments. 

G-193


Sediments 


T 

APPLICATION OF TOOLS TO MEASURE PCB MICROBIAL 

DECHLORINATION AND FLUX INTO WATER DURING IN-SITU 

TREATMENT OF SEDIMENTS 

JOEL BAKER 

University of Washington, Tacoma 

1900 Commerce Street 

Tacoma, WA 98402-3100 

(253) 692-5659 

jebaker@u.washington.edu 

CO-PERFORMERS: Andrew Chang (University of Maryland Center for Environmental 

Science); Upal Ghosh, Sonja Fagervold, and Piuly Paul (University of Maryland Baltimore 

County); Birthe Kjellerup and Kevin R. Sowers (University of Maryland Biotechnology 

Institute) 

his SERDP-funded research project (ER-1502) is quantifying the two most important longterm 

loss processes of Polychlorinated Biphenyls (PCBs) in sediments: (1) microbial 

degradation and (2) diffusive and re-suspension related losses to the water column. Based on this 

the following questions are addressed: (a) how is natural PCB microbial degradation activity in 

sediment affected by activated carbon sequestration and (b) how is addition of activated carbon 

altering the PCB mobility The laboratory findings will be integrated into a model developed in 

the current project describing the sediment-water exchange. 

High throughput molecular and activity analyses of Grasse River sediment showed an in-situ 

enriched microbial population consisting of Dehalococcoides phylotypes with a high 

dechlorination potential and a high concentration of congeners containing unflanked chlorine 

substitutions. In microcosms spiked with Aroclor 1260 congeners were reductively dechlorinated 

in all samples independent of GAC sequestration. The dominant dechlorination products formed 

in GAC treated samples were mono and di-chlorinated congeners. In untreated samples the main 

products were tetra-chlorinated congeners. Aerobic slurries of the sediment showed a significant 

decrease in the mass of di, tri, and tetrachlorobiphenyls as compared to an abiotic control after 60 

days of incubation. Activated carbon amended sediment showed slower biodegradation and also 

a decrease in the volatilization of PCBs. Studies on the effect of GAC on dechlorination of 

weathered PCBs are ongoing. 

The potential impact of activated carbon addition on both the erodibility of the sediments and the 

PCB desorption rates is being explored with a sediment-water exchange model. Dynamic 

partitioning to sediment particles ranging in size from 2 to 1,000 microns suspended in the water 

and in surficial (0.1 cm) and consolidated (0.1-5 cm) sediments is modeled. A unique feature of 

this model is that the particles form aggregates and diffusion-controlled exchange of PCBs from 

these flocs to the surrounding water is simulated. Activated carbon is currently being added as a 

state variable to this model. 

This poster will present results from the first 2 years of this study, including the initial sediment 

characterization, initiation of microbial dehalogenation incubations, and model development. 

G-194


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METHODS FOR EVALUATING THE LIFE SPAN OF BIOPOLYMERS USED FOR 

B 

CONTAMINANT SEQUESTRATION AND EROSION CONTROL 

DR. ANNA S. KNOX 


Savannah River Site 

773-42A, Room 231 


(803) 725-7021 

anna.knox@srnl.doe.gov 

CO-PERFORMERS: Dr. Charles E. Turick and Michael H. Paller 

(Savannah River National Laboratory) 

iopolymers are high molecular weight compounds with repeated sequences that may 

become multiple reactive sites with high opportunity for chemical interaction with other 

compounds. Research suggests that cross-linked biopolymers are stable in soil/sediment, and that 

stability may increase over time, sometimes resulting in the entrapment of contaminants in stable 

geopolymers. However, the stability of biopolymers and their life span may be affected by 

environmental conditions indicating a need for further evaluation before this technology is 

deployed for remediation. 

Commercially available biopolymers were treated with cross-linking agents to produce crosslinked 

biopolymers that stabilize contaminants in soil/sediment while improving soil/sediment 

structure to reduce physical processes (e.g., erosion) that result in contaminant dispersal. The 

cross-linked biopolymers were evaluated alone and in combination with soil/sediment for 

stability of these materials over time. Specific research included evaluation of the stability of 

cross-linked biopolymers at elevated temperatures and moisture levels to simulate accelerated 

weathering, microbial effects on the properties of cross-linked biopolymers, and the long-term 

effects of cross-linked biopolymers on the mobility and retention of contaminants in soil and 

sediment. Biopolymer biodegradability was measured at two temperatures with a soil inoculum 

and a basal salts growth medium employing the biopolymers as sole sources of carbon. 

Microbial activity was measured as CO 2 release using GC/MS biweekly for eight weeks. 

Controls consisted of uninoculated wet and dry polymers and inoculum only. Microbial density 

was determined by direct microscopic counts and dilution plating using low and high nutrient 

concentrations. 

Several biopolymer formulations exhibited substantial CO 2 release associated with bacterial 

activity, and CO 2 release was generally greater under wet than dry conditions. However, xanthan 

and chitosan cross-linked with CaCl 2 (XC c ), released little CO 2 indicating resistance to 

biodegradation. This was confirmed by microscopic counts, which indicated that bacterial 

densities in this material did not increase with time. A six month evaluation showed that XC c 

released less organic carbon to sediments and water than other biopolymers suggesting it was 

less biodegradable. Slurries of biopolymers mixed with sand showed high erosion resistance 

indicating they have the potential to stabilize active caps used to remediate contaminated 

sediments. The methods developed in this study, including CO 2 release, microbial density 

methods, and evaluation of organic carbon, produced consistent results and are promising tools 

for monitoring the long-term stability of biopolymer products in active cap applications. 

G-195


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ACTIVE CAPS FOR REMEDIATION OF SEDIMENT CONTAMINANTS AND 

RESISTANCE TO EROSION 

DR. ANNA S. KNOX 


Savannah River Site 

773-42A 


(803) 725-7021 

anna.knox@srnl.doe.gov 

CO-PERFORMERS: Dr. M. H. Paller and K. L. Dixon (Savannah River National Laboratory); 

Dr. D. D. Reible (University of Texas); Dr. I. G. Petrisor (Haley & Aldrich, Inc.); 

Dr. J. D. Roberts (Sandia National Laboratory) 

A 

ctive caps for the remediation of sediment contaminants and resistance to erosion were 

investigated in the laboratory for two years under SERDP project ER-1501. These studies 

investigated the effects of sequestering agents on metal bioavailability and retention, erosion 

resistance, and toxicity as a basis for identifying the best active cap components and 

composition. Phosphate amendments, some organoclays, and biopolymers effectively removed 

metals from both fresh and salt water. Metals were strongly retained by the amendments 

suggesting little potential for their remobilization. 

Numerical modeling based on measured and assumed material and transport properties was used 

to examine the diffusion of metals and organic contaminants through experimental active caps. 

These studies showed that active caps composed of apatite or organoclay can delay the 

breakthrough of metals and organic contaminants due to diffusion by hundreds or thousands of 

years compared with passive caps composed of sand. Advective transport studies involving 

laboratory column experiments supported by modeling showed that metals and organic 

contaminants were strongly sorbed by apatite or organoclay and contaminant breakthrough due 

to advection in an apatite or organoclay columns was greatly delayed compared with sand. 

Biopolymer products for inclusion in active caps were evaluated on the basis of resistance to 

biodegradation, sorption capacity for organic and inorganic contaminants, and potential for 

erosion control. An Adjustable Shear Stress Erosion and Transport (ASSET) flume was used to 

evaluate the ability of biopolymers to improve the erosion resistance of active caps. Materials 

mixed with biopolymers were very cohesive, and some biopolymer products became more 

cohesive and erosion resistant with time. The resistance of biopolymer products to erosion 

suggests that they have potential as a stand-alone active cap or as armament for other 

amendments. 

Amendment performance data collected in the laboratory are now being used to develop cap 

designs for transition to a small-scale field evaluation. The field deployment is being conducted 

in Steel Creek, a third order stream on the Savannah River Site, SC. The experimental plan for 

the field deployment includes eight caps representing four treatments. Each cap will be about 6 

feet wide, 6 feet long, and 6 inches thick. The caps will be evaluated for 10 to 12 months for 

contaminant immobilization, erosion, and effects on benthic organisms. 

G-196


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DEVELOPING METHODS TO STIMULATE DECHLORINATION OF 

HISTORICAL POLYCHLORINATED DIBENZO-P-DIOXINS AND 

DIBENZOFURANS IN CONTAMINATED SEDIMENT 

HUI LIU 


76 Lipman Drive 


(845) 664-8228 

huilmb@gmail.com 

CO-PERFORMERS: Dr. Lisa A. Rodenburg, Dr. Donna E. Fennell, and Dr. Max M. Häggblom 

(Rutgers University) 

P 

olychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are 

unwanted byproducts from various industrial processes. They are of major concern due to 

their extreme toxicity and high resistance to microbial degradation. Anaerobic bacteria are 

known to dechlorinate PCDD/Fs, but their activity is low. To develop methods to stimulate the 

reductive dechlorination of aged PCDD/Fs we established micro- and mesocosms with 

contaminated sediment from Kymijoki River, Finland. In 30-liter anaerobic mesocosms we 

detected the dechlorination from octa-CDF to hepta- and hexa-CDF congeners, as well as 

production of non-2,3,7,8- substituted tetra- and penta-CDFs from hexa-CDFs after 3 years 

incubation. Whether the dechlorination of PCDD/Fs could be stimulated by different 

amendments was examined in 200 ml microcosms. The effects of spiked 1,2,3,4- 

tetrachlorodibenzo-p-dioxin (1,2,3,4-TeCDD), 1,2,3,4-tetrachlorobenzene (1,2,3,4-TeCB) and 

1,2,3,4,5-pentachloronitrobenzene (1,2,3,4,5-PeCN) as “haloprimers” in the presence of 

combined electron donors were examined. Vegetable oil was tested for the effect on enhancing 

dechlorination of historical PCDD/F congeners in the sediments with and without 

bioaugmentation of Dehalococcoides ethenogenes strain 195. A similar production of non- 

2,3,7,8- substituted tetra- and penta-CDFs were observed in microcosms after 18 months. 

Extensive reductive dechlorination of spiked 1,2,3,4-tetrachlorodibenzo-p-dioxin and 1,2,3,4- 

tetrachlorodibenzofuran indicated that the sediments contained active populations of native 

dechlorinating bacteria. The results suggest ways to enhance dechlorination of historical 

PCDD/Fs contaminants by indigenous microbial populations and can be used for identification 

of potential dechlorinating microbes for in-situ bioremediation of PCDD/F contaminated 

sediments. 


G-197


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DECHLORINATION PATTERN AUGMENTATION AND BAYESIAN MODELING 

OF POLYCHLORINATED BIPHENYL (PCB) DECHLORINATION IN SEDIMENT 

N 

AMANDA HUGHES 



129 Baker Hall 


(215) 421-4564 

ahughes@cmu.edu 

CO-PERFORMERS: J.M. VanBriesen and M.J. Small (Carnegie Mellon University) 

atural anaerobic degradation of PCBs is preferentially carried out by largely unidentified 

populations of microorganisms. Microbial specificity is believed to be governed by the 

nature of the microbial populations, the physical and chemical characteristics of the site, and the 

structure and concentration of PCBs. Current dechlorination models incorporate neither this 

specificity nor the biogeochemical parameters that affect it. Inclusion of these parameters in a 

novel congener-specific Bayesian belief network (BBN) model can significantly improve the 

accuracy of anaerobic PCB dechlorination predictions. This model exploits congener 

relationships, called tracker pair ratios, established during the Aroclor manufacturing process; 

thereby eliminating the inclusion of and subsequent uncertainty associated with source 

contaminating Aroclors. It also exploits patterns of dechlorination pathways, called processes 

that connect the 209 congeners through the loss of a chlorine atom. To date, eight processes have 

been identified via trend analysis of laboratory and field data. Processes give an overview of 

microbial specificity without requiring the identification of dechlorinating microorganisms or 

knowledge of dechlorination mechanisms. They contain 106 of the 840 theoretically possible 

dechlorination pathways, which are likely incomplete due to limited data and the inability to 

distinguish coeluting congeners in gas chromatograph analyses. A preliminary construction of 

the BBN revealed that dechlorination predictions using only these 106 pathways were 

inadequate. Thus, decision trees were used to identify the discriminating congener properties of 

process inclusion and additional pathways for each process. The trees, which have excellent true 

positive rates, augment the number of dechlorination pathways in processes with 551 pathways. 

These augmented processes are capable of producing more accurate predictions and exceeding 

dechlorination levels, measured in average chlorines per biphenyl, beyond those currently 

measured at most contaminated sites. 

Because degradation processes have been linked to biogeochemical parameters, the BBN is 

expected to lead to more accurate site-specific predictions of PCB dechlorination. Specifically, 

it produces an indication of dechlorination endpoints, the probability of individual dechlorination 

pathways, and a demonstration of toxicity reduction in spite of maintained total PCB 

concentrations. Further, it will provide decision makers with insight into the relationships among 

PCB congener distributions, sediment geochemistry, and populations of microorganisms in a 

sediment system. This work, funded under SERDP Project ER-1495, can reduce cost and risks 

to human health and the environment by providing evidence for the use of monitored natural 

recovery or cap-and-treat technologies rather than dredging. 

G-198


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T 

BACTERIAL COMMUNITIES ANALYSIS WITH Q-PCR IN PCB- 

CONTAMINATED SEDIMENT CORE 

YAN XU 


Civil and Environmental Engineering 



(412) 268-5811 

yanxu@cmu.edu 

CO-PERFORMERS: Dr.Youngseob Yu, Professor Kelvin Gregory, and Professor Jeanne 

VanBriesen (Carnegie Mellon University) 

o characterize the bacterial communities in a polychlorinated biphenyls (PCBs) 

contaminated river, a sediment core was collected from the Grasse River (Massena, NY) in 

2006. Quantitative polymerase chain reaction (Q-PCR) was applied to quantify total bacteria and 

some specific microbial populations related to anaerobic reductive dechlorination of PCBs. We 

selected 14 segments from the sediment core. For each core segment, 16S rRNA gene copy 

numbers of bacteria (BAC), Chloroflexi group (CHL), Dehalococcoides group (DHC), PCB 

dechlorinators (o-17 /DF-1 clade) and three sulfate reducing bacteria groups [Desulfovibrionales 

(DSV), Desulfobacterales (DSB) and Desulfuromonales (DSM)] were obtained. In brief, all 

bacterial groups were detected in the sediment core and the concentrations ranged from 2.77×10 4 

copy/gram wet sediment to 1.16×10 10 copy/gram wet sediment. Sulfur reducing bacteria were 

much more abundant than PCB dechlorinators, which indicated the existence of other electron 

acceptors in this sediment core. Together with PCB congener identification and total organic 

carbon (TOC) analysis, relatively extensive dechlorination was observed in older (deeper) 

sediments. 

G-199


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CONGENER TRACKER-PAIR ANALYSIS FOR EVALUATION OF 

REDUCTIVE DECHLORINATION OF POLYCHLORINATED BIPHENYLS (PCBS) 

IN RIVER SEDIMENTS 

DR. JEANNE M. VANBRIESEN 



Porter Hall 119 


(412) 268-4603 

jeanne@cmu.edu 

CO-PERFORMERS: Mitchell J. Small, Gregory Lowry, Kelvin Gregory, Edwin Minkley, and 

Sandra Karcher (Carnegie Mellon University) 

T 

racker Pairs are pairs of PCB congeners that maintain the same ratio across multiple Aroclor 

mixtures and lots. Using the data of Frame et al (1996), we elucidated a set of tracker pairs 

that can be used to determine if an environmental sample from a sediment is “aroclor-like” or has 

changed from the relative concentrations that were originally deposited to the river (Karcher, 

Small, and VanBriesen, 2004). 

The method was used to evaluate the likelihood of dechlorination in the Hudson River using data 

from the Hudson River Low Resolution Sediment Coring Project (Karcher, VanBriesen, and 

Small, 2007). In order to assess the transferability of the method, we used datasets from the 

Comprehensive Characterization of the Grasse to evaluate the method of developed by Karcher 

et al. (2004) on a distinctly different sediment system. Two hundred and fifty-five (255) samples 

were available. 

Evaluation of these Grasse River data show strong statistical support for the conclusion that the 

sediments experienced ongoing reductive dechlorination during the time period evaluated: 255 of 

the 272 tracker pairs show shifts away from Aroclor-like relationships while 17 pairs did not 

show significant changes. This analysis provides strong support that the tracker pair method 

developed by Karcher et al. (2004) is applicable to sediments systems beyond the original 

application in the Hudson River. Further, this field-based analysis provides significant 

information as it considers only what has happened in the environment rather than what can 

happen in the laboratory under ideal conditions. Weathered PCBs in this system are undergoing 

predictable reductions in chlorination level, very likely through biological activity. This work is 

funded by SERDP Project ER-1495. 

1. Frame, G. M., J. W. Cochran, and S. S. Bowadt. 1996. Complete PCB congener distribution for 17 Aroclor 

mixtures determined by 3 HRGC systems optimized for comprehensive, quantitative congener-specific 

analysis. HRC-J High Res Chrom 19: 657-68. 

2. Karcher, S. C., M. J. Small, and J. M. VanBriesen. 2004. Statistical method to evaluate the occurrence of 

PCB transformations in river sediments with application to Hudson River Data. Environmental Science and 

Technology 38: 6760-6766. 

3. Karcher, S. C., J. M. VanBriesen, and M. J. Small. 2007. Numerical method to elucidate likely target 

positions of chlorine removal in anaerobic sediments undergoing polychlorinated bipheny dechlorination. 

Journal of Environmental Engineering - ASCE 133, no. 3: 278-86. 

G-200


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T 

EVALUATION OF SORBENTS AND GEOTEXTILE MATERIALS FOR 

REACTIVE CAPPING OF CONTAMINATED SEDIMENTS 

KEVIN GARDNER 

University of New Hampshire 

336 Gregg Hall 

Durham, NH 03824 

(603) 862-4334 

kevin.gardner@unh.edu 

CO-PERFORMERS: Amy Hawkins (Naval Facilities Engineering Service Center); 

Gregory Tracey (Science Applications International Corporation); Jeffrey S. Melton, 

Bhawana Sharma, and Rafael Prieto (University of New Hampshire) 

he main objective of this research is to develop and evaluate a composite active capping 

system consisting of apatite minerals, which sequester heavy metals, with other sorbent 

materials, which sequester hydrophobic organic contaminants, within an engineered geotextile 

mat. The technical objectives of this research include characterization of sorbents and sorbent 

mixture, characterization of the clogging potential and gas transmission of the geotextile 

materials and composites, and determination of interferences caused by different fractions of 

natural organic matter present in typical site conditions. In this study the performances of 

activated carbon and organoclay were evaluated as reactive cap sorbents that can be used to 

sequester organic contaminants in the presence of natural organic materials that are present in 

sediment porewaters. Results showed significant effect of Aldrich humic acid on 2, 2N, 5, 5Ntetrachlorobiphenyl 

adsorption on both the sorbents. The effect of Suwannee River humic acid 

and fulvic acid varied with sorbent and there was no effect of NOM on either of the sorbents for 

2, 2N, 5, 5N-tetrachlorobiphenyl adsorption. In the case of phenanthrene adsorption, no effect of 

any fraction of natural organics was noticed for organoclay but similar reducing effects of 

Aldrich humic acid, Suwannee River humic acid, Suwannee River fulvic acid and Suwannee 

River NOM were noticed for activated carbon. A significant effect of Hudson River porewater 

(high in humic content) was observed on the performance of both the sorbents for both the 

contaminants, although only a small effect was found for the Passaic River porewater (which 

was low in humics). Geotechnical performance of a number of materials was evaluated with the 

gradient ratio test and materials with low clogging potential were selected for field testing. 

Results of geotechnical and environmental performance of mats retrieved from a field 

deployment will also be presented. 


G-201


Sediments 


REACTIVE CAPPING MAT DEVELOPMENT AND EVALUATION FOR 

SEQUESTERING CONTAMINANTS IN SEDIMENT 

GREGORY A. TRACEY, PH.D. 

SAIC, Inc. 

221 Third Street 

Newport, RI 02840 

(401) 848-4631 

traceyg@saic.com 

CO-PERFORMERS: Kevin Gardner, Ph.D. and Jeffrey Melton, Ph.D. (Environmental Research 

Group, University of New Hampshire) 

T 

he SAIC/UNH/NFESC team is working to develop a reactive geotextile mat system as a 

chemically effective, mechanically stable and cost efficient technology for reducing 

ecological risks by sequestering contaminants in sediment, thereby avoiding the need for 

dredging and offsite placement. The mat system, if successful, would be deployed in a wide 

variety of environmental settings to prevent both metals and organic contaminants from entering 

overlying surface waters while simultaneously allowing both groundwater flux and surficial 

biological colonization. As part of the pilot study, various mixtures of reactive amendments to 

potentially absorb different classes of sediment contamination have been evaluated in a 

laboratory setting and the optimal combination (0.28 lb/sf activated carbon, 0.23 lb/sf apatite, 

0.28 lb/sf organoclay) has been placed within prototype mats consisting of woven geotextile tops 

and a non-woven geotextile backs to be positioned on top of sediments of concern. Cottonwood 

Bay in Grand Prairie, Texas was selected as the most suitable project test site based on a variety 

of chemical, physical, biological and logistical factors. A comprehensive geophysical 

investigation, including bathymetry, side-scan sonar, sediment profile imaging and groundwater 

seep surveys, was conducted to characterize this site and identify a specific target area for mat 

placement featuring a substantial groundwater plume. Gradient ratio testing and finite element 

modeling experiments were conducted in a laboratory setting using both clean geotextiles 

delivered to the laboratory and field weathered small scale (6 ft H 6 ft) test mats retrieved from 

Cottonwood Bay to identify the non-woven geotextile most resistant to biofouling (8 oz/sq. yd 

polypropylene with 80 apparent opening size) to be used for construction of a prototype mat 

system. A full-scale mat system featuring four 25 ft H 25 ft test arrangements (bare single layer 

geotextile, single layer geotextile with sand cap, bare double layer geotextile, sand cap only) and 

an undisturbed control area was then deployed in Cottonwood Bay in April 2008. In September 

2008, following five months of soak time, the contaminant sequestering effectiveness of the 

various test arrangements within this system will be monitored by passive samplers (semipermeable 

membrane devices, peepers) to be placed within each treatment area for 30 days. 

Preliminary conclusions derived from field testing will be discussed as well as plans for an 

additional groundwater seepage survey to quantify flux through the mat after one year of 

deployment. 


G-202


Sediments 


IN SITU WETLAND REMEDIATION DEMONSTRATION 

AMY L. HAWKINS 

NAVFAC ESC 



(805) 982-4890 

amy.hawkins@navy.mil 

CO-PERFORMERS: John Bleiler, Dr. Emese Hadnagy, and Steve Atter (ENSR); 

Dr. Kevin Gardner (University of New Hampshire); Dr. Doris Anders (HQ AFCEE); 

David Barclift (NAVFAC LANT); Kristen Harstad (NAVFAC Washington); Dr. Mark Johnson 

(USACHPPM); Dr. Trudy Estes (USACE) 

W 

etlands owned by the Department of Defense (DoD) often act as sinks for contaminants 

including persistent, bioaccumulative, and toxic (PBT) compounds (e.g., DDT and PCBs), 

as well as inorganic constituents (e.g., copper and lead). Remediation of contaminated wetlands 

traditionally has involved excavation of hydric soils and off-site transport of excavated materials 

for treatment and disposal. This type of remediation is both ecologically destructive and 

expensive. The newly funded ESTCP Project ER-0825 investigates an alternative remedial 

approach that allows targeted in-situ remediation of wetlands through the application of various 

sequestration agents, a technology that has the potential to reduce costs tremendously with the 

added benefit of minimizing impacts on ecosystem components. Several sequestration agents are 

currently being evaluated at the laboratory scale to determine which material provides the most 

cost-effective and environmentally protective solution. All the chosen materials are known for 

their chemical properties which can limit bioavailability and mobility of organic contaminants 

and metals. Laboratory tests are underway to test the contaminant removal capacity of up to eight 

sequestration agents including activated carbon, zero valent iron, organoclays, and apatite. 

Results of these experiments will be summarized in a treatability study and guidance manual 

which will help inform the field demonstration phase of work. Field demonstration will evaluate 

the efficacy of different application technologies including dry broad-casting and slurry delivery 

systems. The main goal of this program is risk reduction, not mass removal, therefore 

performance in the field application will be gauged through several measures of reduction of 

contaminant bioavailability (e.g., solid-phase microextraction, bioassays, instream impairment 

studies) following addition of the sequestration agents. 

G-203


Sediments 


F 

SEDIMENT AND CONTAMINANT TRANSPORT ASSOCIATED WITH 

THE LAC SAINT PIERRE EXPERIMENTAL FIRING RANGE 

DR. PATRICK McLAREN 

GeoSea Consulting 

7236 Peden Lane 

Brentwood Bay, BC V8M 1C5 CANADA 

(250) 652-1334 

patrick@geosea.ca 

CO-PERFORMER: Major Matthew Braid (Canadian Department of National Defence) 

or 50 years (1950-2000) the south half of Lac Saint Pierre, a widening of the St. Lawrence 

River between Montreal and Quebec, was used as an experimental firing range. It is 

estimated that some 300,000 shells were fired into the lake of which about 8000 are thought to be 

unexploded explosive ordnance (UXO), potentially containing energetic materials. Furthermore, 

the lake itself is potentially the recipient of other contaminants associated with industrial wastes 

and agricultural runoff. The Canadian Department of National Defence (DND), in order to 

research appropriate clearance-approaches programs, instigated a large sediment transport study 

(sediment trend analysis or STA) to determine both sediment and contaminant sources and sinks, 

and to assess the possible environmental consequences of various clearance options. 

STA is not a numerical model; rather it is an empirical technique whereby patterns of sediment 

transport and dynamic behavior are derived from relative changes in grain-size distributions. 

About 1,000 samples were collected at 500 meter spacing encompassing the entire firing range. 

The lake bottom contained a complex number of sediment types ranging from “ancient” late 

glacial deposits, recent mud and sand, and a variety of mixtures. The STA identified the 

significance of the late glacial deposits as the dominant source for the sediments contained in the 

lake. The latter showed complex patterns of transport that originated from the ancient sediments 

and terminated on well-sorted sand. The findings demonstrated that anthropogenic contaminants 

were unlikely to be deposited in the lake sediments, or if they were, self-cleaning by natural 

processes would likely be rapid. Furthermore, trace metals were strongly associated with the 

ancient sediments evidently originating from an underlying anaerobic black shale formation. The 

STA provides an important framework to understand the chemistry of the sediments and their 

dynamics and helps to define the context within which the UXO clearance and environmental 

remediation options can be developed. 

G-204


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T 

DEVELOP ACCURATE METHODS FOR CHARACTERIZING AND 

QUANTIFYING COHESIVE SEDIMENT EROSION UNDER COMBINED 

CURRENT-WAVE CONDITIONS 

DR. JOSEPH GAILANI 

USACE ERDC-CHL 



(601) 634-4851 

joe.z.gailani@erdc.usace.army.mil 

CO-PERFORMERS: Jesse Roberts (Sandia National Laboratory); 

Thomas Borrowman (USACE ERDC-EL) 

he goal of SERDP-funded project ER-1497 is to develop laboratory methods to reliably 

measure time-varying wall shear stress in an oscillatory flume and develop methods to 

manipulate flow such that generated shear stress time history represents shear stress on the 

sediment bed in combined wave and current environments. Cohesive sediment bed erosion 

parameterization requires field laboratory testing of cores extracted from the sediment bed. It is 

not possible to cost-effectively build an open-surface wave flume for field testing. Therefore, 

experiments are performed within a closed channel. Erosion is quantified as a function of shear 

stress. If wall shear stress in an enclosed channel replicates wave-current shear stress time 

history, erosion experiments can be performed. This method has been demonstrated for unidirectional 

flow. However, the combined near-bottom oscillatory motion of a wave coupled with 

a uni-directional current is quite complex and wall shear stress must be measured within a thin 

boundary layer to assure that desired wave/current shear stress conditions are replicated. These 

methods will utilize the USACE SEAWOLF flume. The shear stress conditions for erosion 

measurements in the flume will replicate those for non-breaking waves in estuarine, harbor, and 

coastal environments. The objective of the project is to directly measure the shear stress time 

histories that occur in the SEAWOLF flume so that flume pumps and pistons can be 

programmed to represent prescribed wave/current-induced bottom shear stress time history. 

Wave/current bottom shear stress time history is well known. Methods for replicating this in the 

laboratory must be developed. Therefore, a novel high-magnification particle-based velocimetry 

system has been developed and applied to measure shear stress time history in SEAWOLF. 

Particle Image Velocimetry (PIV) is used to measure the overall velocity profiles throughout the 

SEAWOLF oscillating flow cycle. Particle Tracking Velocimetry (PTV) is used to measure nearwall 

velocity profiles to within 7 mm of the wall throughout the cycle. Velocity profiles from 

time histories constructed from PIV and PTV data are used to estimate bottom shear stress time 

histories. Simultaneously, a relatively new high-sensitivity a floating element sensor was 

modified for application within the flume. This sensor, if properly applied, provides direct 

physical shear stress measurement. Demonstration of this floating element sensor application 

permits confirmation of PIV/PTV estimates. PIV and PTV results are in good agreement with 

floating element sensor results. 

G-205


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P 

FIELD TESTING OF ACTIVATED CARBON MIXING AND IN SITU 

STABILIZATION OF PCBS IN SEDIMENT 

DR. RICHARD G. LUTHY 



473 Via Ortega, 313B 

Stanford, CA 94305 

(650) 723-3921 

luthy@stanford.edu 

CO-PERFORMERS: Yeo-Myoung Cho (Stanford University); Upal Ghosh (UMBC); 

Alan J. Kennedy and Todd S. Bridges (ERDC) 

rior laboratory studies and a preliminary field pilot-scale study showed that the addition of 

activated carbon (AC) to sediment contaminated with polychlorinated biphenyls (PCB) 

significantly reduced the chemical and biological availability of PCBs. Extending those results, 

we recently completed a field-scale project (ER-0510) that explored use of two large-scale AC 

mixing technologies for incorporating AC into sediment at a tidal mud flat. We considered longterm 

treatment effects, assessed sediment mixing and resuspension, measured PCB 

bioaccumulation in indigenous organisms, and evaluated the cost effectiveness of the AC 

application techniques. Using two commercial equipment devices, AC was successfully 

incorporated into the test plots to a nominal 1 ft depth at a dose of 2 to 3% depending on 

sampling locations. This was verified by the increases in total organic carbon and black carbon 

contents in AC-amended sediment. In-situ 28-day semi-permeable membrane device (SPMD) 

uptake studies showed 50%-66% reduction in PCB uptakes in AC-amended test plots depending 

on AC dose. In-situ bioassays with the clam Macoma nasuta also showed the effectiveness of 

AC treatment, though the in-situ assay results were sometimes confounded due to field 

conditions resulting from newly deposited sediment, heat stress, and shallow burrowing depth. 

To overcome these factors, ex-situ bioassays with M. nasuta were conducted with field sediment 

in the laboratory and showed about 50% reduction in PCB bioaccumulation with 2% AC dose. 

Field-exposed AC retained a strong capability to reduce aqueous equilibrium PCB 

concentrations by about 90%, which supports the long-term effectiveness of AC in the field at 

least up to 18 months. The AC dose has a pronounced affect on PCB availability and biouptake 

with increasing reductions with increasing AC content. Neither PCB resuspension from the test 

plots nor observable adverse impacts to indigenous amphipods and benthic community were 

observed during the assessment periods. Additional mixing during or after AC deployment, 

sequential deployment of AC dose, or reducing AC particle size may accelerate overall 

effectiveness. Modeling studies are in progress to assess the slow mass transfer of PCBs in 

quiescent pore water in the field and to aid predictions of the long-term effectiveness of the AC 

amendment to stabilize PCBs. If ongoing sources are eliminated and freshly deposited sediments 

are clean, AC amendment to contaminated sediments can provide a suitable in-situ method for 

contaminant release to the water column and exposure to biota. 

Funding is provided through ESTCP Project ER-0510. 

G-206


Recently Added Poster – Wednesday 

Chlorinated Solvents — Site Characterization, Monitoring, and Processing 

NON-INVASIVE PLUME DELINEATION USING TREE CORING ANALYSIS 

MATT SHURTLIFF, CHMM 

The Forrester Group Inc. 

500 Chesterfield Center, Suite 300 

Chesterfield, MO 63017 

(636) 728-1034, Ext. 212 

matt@forrestergroup.com 

CO-PERFORMER: Joel B. Burken, Ph.D. (Missouri University of Science and Technology) 

T 

he science of tree coring to detect the uptake of chemicals of environmental concern has 

matured significantly in recent years and tree coring is now being deployed for rapid, precise 

contaminant source and plume delineation. 

By combining tree core analysis with highly accurate GPS mapping of trees on-site, plume maps 

can be generated at a fraction of the cost of conventional investigation techniques. The spatial 

resolution that can be achieved leads to maps that can precisely locate plume boundaries and 

source areas in a single mobilization for sites of multiple acres in scale. Maps can be provided 

within days, compared to the weeks or months required for conventional investigative 

techniques. Groundwater contaminant delineation can also be accomplished at difficult locations 

that are inaccessible to direct push or drilling rigs, with minimal mobilization costs. 

Case studies and methodologies will be presented to show how The Forrester Group and the 

Missouri University of Science and Technology have used tree coring at chlorinated solvent and 

Manufactured Gas Plant (MGP) sites, and what information can be gained. Limitation of the 

methods, including compounds that can be analyzed and site characteristics that can be limiting 

to application, will be discussed and overviewed. 

G-207

Wednesday (Group 2) - SERDP-ESTCP - Strategic Environmental ...

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