EPA542-K-94-004

April 1995

In Situ Remediation Technology Status Report:

Treatment Walls

U.S. Environmental Protection Agency

Office of Solid Waste and Emergency Response

Technology Innovation Office

Washington, DC 20460
Acknowledgements

The authors would like to thank all the researchers and technology developers described in this report for

their assistance in its preparation. We especially would like to thank Steve McCutcheon at the U.S. EPA

Environmental Research Laboratory in Athens, Georgia; Robert Puls at the U.S. EPA Robert S. Kerr

Environmental Research Laboratory in Ada, Oklahoma; and Stephen Shoemaker at DuPont Engineering

for reviewing the draft document and making valuable suggestions for improvement.

For more information about this project, contact:

Rich Steimle

U.S. Environmental Protection Agency (5102W)

Technology Innovation Office

401 M Street, SW

Washington, DC 20460

703-308-8846

Notice

This material has been funded by the United States Environmental Protection Agency under contract

number 68-W2-0004. Mention of trade names or commercial products does not constitute endorsement or

recommendation for use.
i

Foreword

The purpose of this document is to describe recent field demonstrations, commercial applications, and

research on technologies that either treat soil and ground water in place or increase the solubility and

mobility of contaminants to improve their removal by pump-and-treat remediation. It is hoped that this

information will allow more regular consideration of new, less costly, and more effective technologies to

address the problems associated with hazardous waste sites and petroleum contamination.

This document is one in a series of reports on demonstrations and applications of in situ treatment

technologies. To order other documents in the series, contact the National Center for Environmental

Publications and Information at (513) 489-8190 or fax your request to NCEPI at (513) 489-8695. Refer to

the document numbers below when ordering.

EPA542-K-94-003 Surfactant Enhancements

EPA542-K-94-004 Treatment Walls

EPA542-K-94-005 Hydraulic/Pneumatic Fracturing

EPA542-K-94-006 Cosolvents

EPA542-K-94-007 Electrokinetics

EPA542-K-94-009 Thermal Enhancements

 ______________________________________ 

 Walter W. Kovalick, Jr., Ph.D.

Director, Technology Innovation Office
ii
iii

Contents

Introduction ....................................................................... 1

Purpose and Process .................................................... 1

Technology Needs ...................................................... 1

Technology Descriptions ................................................. 1

Completed Demonstrations ........................................................... 2

Waterloo Centre for Groundwater Research .................................. 2

Waterloo Centre for Groundwater Research .................................. 3

Ongoing and Future Demonstrations .................................................... 4

Waterloo Centre for Groundwater Research .................................. 4

EnviroMetal Technologies and Waterloo Groundwater Control

Technologies ...................................................... 5

EnviroMetal Technologies ............................................... 6

Waterloo Centre for Groundwater Research .................................. 7

Battelle Pacific Northwest Laboratories ..................................... 8

Barrier Membrane Corporation ............................................ 8

U.S. EPA Environmental Research Laboratory ................................ 9

Waterloo Centre for Groundwater Research . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

GEOCHEM (A Division of Terra Vac) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

Current Research . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

ManTech Environmental Research Services Corporation and U.S. EPA

Environmental Research Laboratory, Ada, OK . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

U.S. EPA, Environmental Research Laboratory, Athens, GA . . . . . . . . . . . . . . . . . . . . . 13

U.S. EPA, Environmental Research Laboratory, Athens, GA . . . . . . . . . . . . . . . . . . . . . 15

U.S. EPA, Environmental Research Laboratory, Athens, GA . . . . . . . . . . . . . . . . . . . . . 16

Battelle Pacific Northwest Laboratories . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

Oregon Graduate Institute of Science and Technology . . . . . . . . . . . . . . . . . . . . . . . . . . 17

Rust Geotech, Inc. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

New Mexico Institute of Mining and Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

Department of Civil Engineering, Stanford University . . . . . . . . . . . . . . . . . . . . . . . . . . 20

Martin Marietta Energy Systems and Oak Ridge National Laboratory . . . . . . . . . . . . . . 21

GE Corporate Research and Development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

Waterloo Centre for Groundwater Research . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

Los Alamos National Laboratory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24

General References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
iv

Abbreviations

BTEX = Benzene, Toluene, Ethylbenzene, Xylene

CERCLA = Comprehensive Environmental Response, Compensation, and Liability Act

DCE = Dichloroethene

DNAPL = Dense Non-Aqueous Phase Liquid

DOE = Department of Energy

PAH = Poly-Aromatic Hydrocarbon

PCE = Tetrachloroethylene

RCRA = Resource Conservation and Recovery Act

SITE = Superfund Innovative Technology Evaluation Program

SVE = Soil Vapor Extraction

SVOC = Semi-Volatile Organic Compound

TCA = 1,1,1-Trichloroethane

TCE = Trichloroethylene

TPH = Total Petroleum Hydrocarbon

VOC = Volatile Organic Compound
1

Introduction

Purpose and Process

The purpose of this document is to describe demonstrations, field applications, and research on treatment

walls for remediating contaminated ground water at waste disposal and spill sites. 

Information for this report came from computerized databases such as the Dialog Information Services and

the Environmental Protection Agency's (EPA) Vendor Information System for Innovative Treatment

Technologies (VISITT) and Alternative Treatment Technologies Information Center (ATTIC). Additional

materials were obtained from publications such as the Hazardous Substance Research Center Annual

Reports, Superfund Innovative Technology Evaluation Technology Profiles and Department of Energy's

Office of Technology Development Program Summary as well as conference summaries, proceedings and

compendiums. Personal interviews and discussions with representatives of other federal agencies,

academic research centers, and hazardous waste remediation consulting firms provided supplementary

information.

Technology Needs

Numerous hazardous waste sites have significant concentrations of metals, halogenated organic

compounds, and radionuclides that contaminate ground water. Traditional technologies, such as pump and

treat, require an external energy source and their cost is high. Subsurface residuals frequently remain at

undesirable levels. Thus, subsurface permeable treatment walls are being considered as a cost-effective in

situ water treatment alternative.

Technology Descriptions

Water permeable treatment walls are installed as permanent, semi-permanent, or replaceable units across

the flow path of a contaminant plume, allowing the plume to move passively through while precipitating,

sorbing, or degrading the contaminants. These mechanically simple barriers may contain metal-based

catalysts for degrading volatile organics, chelators for immobilizing metals, nutrients and oxygen for

microorganisms to enhance bioremediation, or other agents. Degradation reactions break down the

contaminants in the plume into harmless byproducts. Precipitation barriers react with contaminants to form

insoluble products that are left in the barrier as water continues to flow through. Sorption barriers adsorb

or chelate contaminants to the barrier surface. The reactions that take place in barriers are dependent on

parameters such as pH, oxidation/reduction potential, concentrations, and kinetics. Thus, successful

application of the technology requires characterization of the contaminant, ground-water flux, and

subsurface geology. Although most barriers are designed to operate in situ for years with minimal

maintenance and without an external energy source, the stability of aging barriers has not been established.

The following pages contain descriptions of completed, ongoing, and future demonstrations and

commercial applications as well as current research and testing of passive treatment walls.
2

Completed Demonstrations

Canadian Forces Base Borden, Ontario, Canada

Waterloo Centre for Groundwater Research, University of Waterloo

In Situ Permeable Reaction Wall

Description of Demonstration: Researchers installed a permeable reaction wall containing an iron-based

catalyst about 16.5 feet downgradient from the source of a contaminant plume to pilot test the capability of

the wall to degrade halogenated organic compounds. The plume was about 6.5 feet wide and 3.3 feet thick

with maximum concentrations along the axis of about 250,000 g/L trichloroethene (TCE) and 43,000

g/L tetrachloroethene (PCE). The source of the plume was located about 13 feet below ground surface

and 3.3 feet below the water table. (Investigators believe the wall can be installed to depths of 50 feet, but

no test results are available at this time to substantiate this.) 

Using sealable joint sheet piling, a rectangular cell was constructed on the surface and driven to a depth of

32 feet, the cell was sealed and dewatered and the native sand was replaced by the reactive material

consisting of 22% by weight granular iron and 78% by weight course sand. The sand, which was coarser

than the native materials, ensured that the wall would be more permeable than the surrounding sand. After

installing the reactive material, the sheet piling was completely removed and natural flow conditions were

achieved. The wall dimensions were 18 feet long, 5.2 feet thick, and 7.2 feet deep and it was positioned

3.3 feet below the water table. 

Wastes Treated: VOCs

Status: The pilot test was completed in 1993. The Waterloo Centre for Groundwater Research is part of

Ontario's Centres of Excellence program, a government sponsored partnership with academia and

industry.

Demonstration Results: Multilevel monitoring wells were located 1.6 feet upgradient of the wall, in the

wall at distances of 1.6 and 3.3 feet, and 1.6 feet downgradient of the wall for a total of 348 sampling

points. Concentration distributions through the wall were determined on 13 occasions over 474 days,

during which there was no decline in the effectiveness of the barrier. Most of the mass loss occurred

within the first 50 cm of the wall; at greater distances into the wall, performance was below that expected.

However, the reaction wall reduced the TCE concentration by 95% and the PCE concentration by 91%.

No vinyl chloride was detected in the samples. Increased chloride concentrations downstream of the wall

were consistent with the quantity of TCE and PCE that had been degraded. Only trace amounts of

dichloroethene (DCE) were detected downstream of the wall. 

Contacts:

Stephanie F. O'Hannesin

Waterloo Centre for Groundwater Research

University of Waterloo

Waterloo, Ontario N2L 3G1 Canada

519-885-1211 x3159
3

References:

O'Hannesin, S.F. A Field Demonstration of a Permeable Reaction Wall for the In Situ Abiotic

Degradation of Halogenated Aliphatic Organic Compounds. Master's Thesis, University of Waterloo,

Waterloo, Ontario, Canada. 1993.

O'Hannesin, S.F. and Gillham, R.W. “A Permeable Reaction Wall for In Situ Degradation of Halogenated

Organic Compounds.” 45th Canadian Geotechnical Society Conference, Toronto, Ontario, October 25-28,

1992.

O'Hannesin, S.F. and Gillham, R.W. “In Situ Degradation of Halogenated Organics by Permeable

Reaction Wall.” Ground Water Currents, March 1993, EPA/542/N-93/003.

Borden Aquifer, Ontario, Canada

Waterloo Centre for Groundwater Research, University of Waterloo

In Situ Permeable Reaction Wall

Description of Demonstration: Researchers field tested a proprietary solid peroxide formulation (an

oxygen-releasing compound) to determine whether it could provide dissolved oxygen in a controlled

steady manner to enhance biodegradation of BTEX-contaminated ground water. Benzene and toluene

were injected into ground water to represent BTEX compounds, and their fate was monitored over several

weeks along four lines of monitoring wells. 

Wastes Treated: BTEX

Status: Completed.

Demonstration Results: The results indicate that the oxygen releasing compound can support

biodegradation of benzene and toluene at concentrations typical of those found at petroleum contaminated

sites.

Contacts:

Stephanie F. O'Hannesin

Waterloo Centre for Groundwater Research

University of Waterloo

Waterloo, Ontario N2L 3G1 Canada

519-885-1211

References:

Bianchi-Mosquera, G.C.; Allen-King, R.M.; and Mackay, D.M. “Enhanced Degradation of Dissolved

Benzene and Toluene Using a Solid Oxygen-Releasing Compound” Ground Water Monitoring and

Remediation, Winter 1994, p 120-128.
4

Ongoing and Future Demonstrations

Canadian Forces Base Borden

Waterloo Centre for Groundwater Research, University of Waterloo

In Situ Permeable Reaction Wall

Description of Demonstration: Researchers are field testing an in situ semipassive permeable wall into

which nutrient solutions that enhance biodegradation of organics are introduced. The wall is installed

across the path of a contaminant plume in an unconsolidated aquifer.

Wastes Treated: TCE, carbon tetrachloride

Status: Ongoing

Demonstration Results: Results indicate that by adding substances in the wall, the mixing with ground

water is maximized to produce a stable microbial population that can be supported at some distance

downgradient from the wall. An anaerobic population supporting this led to complete carbon tetrachloride

removal from ground water, but did not transform TCE. Work is continuing to overcome this limitation. 

Contact:

Stephanie F. O'Hannesin

Waterloo Centre for Groundwater Research

University of Waterloo

Waterloo, Ontario N2L 3G1 Canada

519-885-1211

Reference:

Devlin, J.F. and Barker, J.F. “A Semipassive Nutrient Injection Scheme for Enhanced In Situ

Bioremediation.” Ground Water, 32 (3), 1994, p 374.

General Electric, Sunnyvale, California

EnviroMetal Technologies

Metal-Enhanced Abiotic In Situ Treatment of VOCs

Description of Demonstration: An above-ground field test reactor containing 50% iron was installed at

this semiconductor manufacturing facility to test the feasibility of installing an in situ permeable reactive

zone. Ground water was pumped through the reactor at a rate of 4 feet/day for 9 months. Initial

concentrations of contaminants were 50-200 ppb trichloroethene (TCE), 450-1000 ppb cis-1,2-

dichloroethene (cis-DCE), 100-500 ppb vinyl chloride (VC), and 20-60 ppb Freon-113. The time required

to degrade one-half of the contaminant mass in the above-ground field test was <1.7 hours for TCE, 1-4

hours for cis-DCE, 2-4 hours for VC, and <1.6 hours for Freon-113. Mineral precipitation, hydrogen gas

production, and microbial effects also were evaluated. 

Wastes Treated: TCE, DCE, vinyl chloride, Freon-113

Status: Based on the feasibility tests described above, a full-scale in situ permeable treatment wall was

approved by the state regulatory agency and was installed in December 1994. The permeable reactive
5

zone, which will be 4 feet thick, 40 feet long, 10 feet high, and about 25-30 feet deep, will contain 100%

reactive iron. It will be installed using a trench box design. The estimated cost is projected to be $175,000-

$200,000. Patents governing the in situ application of the metal enhanced dehalogenation are held by the

University of Waterloo. EnviroMetal Technologies, Inc. holds an exclusive license with the University of

Waterloo for this treatment technology.

Demonstration Results: None yet

Contact:

John Vogan

EnviroMetal Technologies, Inc.

42 Arrow Road

Guelph, Ontario N1K 1S6 Canada

519-824-0432

Reference:

Gillham, R.W. and O'Hannesin, S.F. “Metal Catalyzed Abiotic Degradation of Halogenated Organic

Compounds.” Ground Water, 29 (5), 1991, p 752.

Industrial Facility, New York State

EnviroMetal Technologies and Waterloo Groundwater Control Technologies

Metal-Enhanced Abiotic In Situ Treatment of VOCs

Using Funnel-and-GateTM System

Description of Demonstration: VOCs will be degraded using the EnviroMetal process (metal-enhanced

reductive dehalogenation) in a pilot-scale Funnel-and-GateTM in situ treatment system at a former plating

facility contaminated with chlorinated solvents. The reactive zone, containing 100% granular iron, will be

10 feet wide, 3 feet thick, and installed at a depth of 15 feet, which is below the water table and near the

source of the contaminant plume. Ground water will be directed towards the zone by 15 linear feet of

Waterloo Barrier sheetpiling on either side. There is a confining layer of clay at 15 feet. 

Wastes Treated: VOCs and SVOCs, including TCE, PCE, DCE, and vinyl chloride

Status: A pilot-scale unit was installed in May 1995. After the system is operating, the demonstration is

expected to run for 6 months. The New York State Department of Environmental Conservation and U.S.

EPA's SITE program are overseeing the demonstration. EnviroMetal Technologies Inc. holds an exclusive

license with the University of Waterloo, the patent holder, for the commercial application of this treatment

technology. Waterloo Groundwater Control Technologies, Inc. is commercializing the Funnel-and-GateTM

system (patents pending) developed at the Waterloo Centre for Groundwater Research. 

Demonstration Results: None yet
6

Contacts:

John Vogan

EnviroMetal Technologies, Inc.

42 Arrow Road

Guelph, Ontario N1K 1S6 Canada

519-824-0432

Robin Jowett

Waterloo Groundwater Control Technologies, Inc.

P.O. Box 385

Rockwood, Ontario NOB 2KO Canada

519-856-1352 

Reference:

Gillham, R.W. and O'Hannesin, S.F. “Metal Catalyzed Abiotic Degradation of Halogenated Organic

Compounds.” Ground Water, 29 (5), 1991, p 752.

Semiconductor Manufacturing Facility, New Jersey

EnviroMetal Technologies 

Metal-Enhanced Abiotic In Situ Treatment of VOCs

Description of Demonstration: Batch and column tests using 50% and 100% iron in the reactive media

and ground water flowing at 1.5 feet/day were conducted to establish reaction conditions for a pilot-scale

above-ground field trial (now underway). These tests are for the future installation of an in situ treatment

wall.

Wastes Treated: TCE, PCE, DCE, vinyl chloride

Status: An above-ground field trial began in November 1994 under the EPA SITE demonstration program

and is still operating. The field trial results should be published by the end of 1995.

Additional sites where feasibility studies have been completed or are underway include:

 Twin Cities Army Ammunition Plant in St. Paul, Minnesota (sponsored by the Minnesota Pollution

Control Agency) to treat TCE, PCE, and cis-1,2-dichloroethene

 Closed landfill in New Mexico

 Industrial facilities in Massachusetts, California, and New York

 Air Force facilities in Utah and Washington State (large-scale field tests scheduled to occur in 1995 at

Hill AFB, Utah, will involve the use of a funnel-and-gate system with the iron filings to treat TCE)

Demonstration Results: Results are not yet available. The column test results showed half-life

degradation rates of 0.7 hours for PCE (4000 to 12000 ppb initially) at 50% iron and 0.4 hours at 100%

iron; and for TCE (400 to 1000 ppb initially) 1.1 hours at 50% iron and 0.5 hours at 100% iron.

Contact:
7

John Vogan

EnviroMetal Technologies, Inc.

42 Arrow Road

Guelph, Ontario N1K 1S6 Canada

519-824-0432

Reference:

Gillham, R.W. and O'Hannesin, S.F. “Metal Catalyzed Abiotic Degradation of Halogenated Organic

Compounds.” Ground Water, 29 (5), 1991, p 752.

AFB/Massachusetts Military Reserve, Falmouth, Massachusetts

Waterloo Centre for Groundwater Research, University of Waterloo

Metal-Enhanced Abiotic Treatment of VOCs Using a Funnel-and-GateTM

Description of Demonstration: A pilot-scale test using granular iron in a Funnel-and-GateTM system is

planned to treat a large and deep contaminant plume containing VOCs. The system will be installed near

the leading edge of the plume, which is 40 to 100 feet thick and 180 feet deep.

Wastes Treated: VOCs

Status: A preliminary test was conducted in the spring of 1995.

Demonstration Results: The test failed to reach the 180 foot depth. Consequently, the reaction zone and

Funnel-and-GateTM system will not be pilot tested on that deep plume. Other options for the deep plume

are under consideration by the National Guard, who is sponsoring the demonstration. The reaction zone

and Funnel-and-GateTM system may be tested on two other, more shallow, plumes at the site.

Contact:

Stephanie O'Hannesin

Waterloo Centre for Groundwater Research

University of Waterloo

Waterloo, Ontario N2L 3G1 Canada 

519-885-1211 x3159

Reference:

Gillham, R.W. and O'Hannesin, S.F. “Metal Catalyzed Abiotic Degradation of Halogenated Organic

Compounds.” Ground Water, 29 (5), 1991, p 752.
8

Hanford 100D Area, Washington

Battelle Pacific Northwest Laboratories

In Situ Redox Manipulation Project

Description of Demonstration: Field experiments are planned for the Arid Soils VOC Integrated

Demonstration to test the feasibility of in situ redox manipulations with chemical reagents using a forced

gradient, single well, reactive tracer test. Field experiments will involve injecting the reagent sodium

dithionite into the aquifer creating a 60 to 100 foot diameter geochemical barrier in advance of a

contaminant plume. After allowing 5 to 30 days for the reaction to occur, water containing the reaction

byproducts and any remaining reagent will be pumped out. The longevity of the system to maintain a

reducing environment also will be evaluated. 

Wastes Treated: Chromium

Status: The demonstration is scheduled for summer 1995. The researchers have conducted an initial site

characterization using existing monitoring wells and have submitted a draft test plan to DOE, EPA, and

the State of Washington Department of Ecology. The Department of Energy is sponsoring the research.

Contact:

J.S. Fruchter

Battelle Pacific Northwest Laboratories

Battelle Boulevard

P.O. Box 999

Richland, WA 99352

509-376-3937

Reference:

Fruchter, J.S. In Situ Redox Manipulation: Enhancement of Contaminant Destruction and Immobilization.

Semi-Annual Office of Technology Development (OTD) Information Meeting (2nd), Houston, Texas,

January 26-28, 1993, NTIS Order Number DE93007877, 7p.

DOE Savannah River, South Carolina

Barrier Membrane Corporation

Treatment Wall

Description of Demonstration: Researchers are constructing a gravel trench 300 feet long by 30 feet deep

that will intersect the highest contaminant concentration of a contaminant plume. Pumping wells will be

constructed within this wall to remove contaminated ground water but the major focus is to study the

hydraulics. The studies are designed to investigate ground-water retention time in the wall and problems

associated with injecting a treatment medium in the gravel matrix. The contaminant plume is shallow and

the surrounding soils are interbedded clays and sands.

Wastes Treated: Chromium, nickel, lead and cadmium 

Status: Under construction. Pump tests are scheduled for July and August 1995.
9

Contact:

Mark Phifer

Westinghouse SRC/SRS

Building 773-42A

Aiken, SC 29808

803-725-5222

Fax: 803-725-7673

Coast Guard Air Station, Elizabeth City, North Carolina

U.S. EPA Environmental Research Laboratory, Ada, OK

Treatment Wall

Description of Demonstration: A series of large-diameter augered holes in a staggered 3-row array were

located within an aquifer to intercept a contaminant plume of chromate and chlorinated organics. A

mixture (by volume) of 50% iron filings (two types), 25% clean coarse sand, and 25% aquifer material

was poured down hollow-stem augers from 22 feet to 10 feet below ground surface. Each iron column was

approximately 8 inches in diameter and a total of twenty-one columns were installed in a 60 square foot

area. The mixed waste contaminant plume is between 14 and 20 feet below ground surface and the water

table ranges from 5 to 6 feet below ground surface. One iron type was shown to be an effective reductant

for chromate in a two-year laboratory study by RSKERL scientists, while the other iron has been shown to

be more effective in the reductive dechlorination of the organics. This field experiment is evaluating the

effectiveness of this method of treatment wall emplacement and is providing additional in situ field data

for full field-scale implementation.

Wastes Treated: TCE, DCE, vinyl chloride, and Cr+6

Status: The demonstration has been in operation since September 1994.

Preliminary Results: Preliminary results show complete reduction of Cr to below detection (<0.01 mg/ +6

L) limits and greater than 75% reduction in initial TCE concentrations and reduction of vinyl chloride

concentrations to less than 1 g/L. These results are very promising, especially for the chlorinated

organics, because the experiment was primarily designed to optimized chromate remediation, not the

chlorinated organics. Longer residence times are planned for the latter in the full field scale test to be

installed in August 1995.

Contact:

Bob Puls

U.S. EPA

Robert S. Kerr Environmental Research Laboratory

Box 1198

Ada, OK 74820

405-436-8543

References:

Puls, R.W.; Powell, R.M.; and Paul, C.J. “In Situ Remediation of Ground Water Contaminated with

Chromate and Chlorinated Solvents Using Zero-Valent Iron: A Field Study.” Proceedings of the 209th

American Chemical Society National Meeting, Anaheim, California, April 2-7, 1995. 35 (1), p 788-791.
10

Several Sites in Canada and the United States

Waterloo Centre for Groundwater Research

In Situ Permeable Reaction Wall for Treatment of Inorganics

Description of Demonstration: Inorganic contaminants in ground water are treated using in situ porous

reactive walls. Wall materials are placed in the path of the plume and react with the contaminant via

reduction and precipitation. This technology is being developed for treating mine and industrial wastes,

and septic system and agricultural effluent.

Wastes Treated: Inorganics, especially metals, SO and PO radionuclides 4 4

Status: Field trials are ongoing to remove dissolved Cr, Fe, SO and PO 4 4

Results: Preliminary results indicate contaminant concentrations are decreased by orders of magnitude and

to below drinking water levels.

Contacts:

D.W. Blowes

Waterloo Centre for Groundwater Research

University of Waterloo

Waterloo, Ontario, Canada

519-888-4878

Fax: 519-746-5644

C.J. Ptacek

Waterloo Centre for Groundwater Research

University of Waterloo

Waterloo, Ontario, Canada

519-885-1211 x2230

Fax: 519-746-5644

References:

Blowes, D.W. and Ptacek, C.J. “Geochemical Remediation of Groundwater by Permeable Reactive Walls:

Removal of Chromate by Reaction with Iron-Bearing Solids.” Proceedings of the Subsurface Restoration

Conference, Third International Conference on Groundwater Quality Research, June 21-24, 1992, Dallas,

Texas, p 214-216.

Blowes, D.W. and Ptacek, C.J. System for Treating Contaminated Groundwater (Redox Curtain). United

States Patent 5,362,394. 1994.

Blowes, D.W.; Ptacek, C.J.; Bain, J.G.; Waybrant, K.R.; and Robertson, W.D. “Treatment of Mine

Drainage Water Using In Situ Permeable Reactive Walls.” Proceedings of the Sudbury 1995 Mining and

the Environment Conference, May 28-June 1, 1995, Sudbury, Ontario.
11

Valley Wood Treating, Turlock, California

In Situ Remediation of Chromium in Ground Water

GEOCHEM (A Division of Terra Vac)

Description of Technology Use: The process removes chromium from contaminated ground water using

a variation of traditional pump-and-treat methods. Contaminated ground water is brought to the surface

and treated using conventional treatment systems such as ferrous iron. A reductant is added to the treated

water which is reinjected around the plume margin where it reacts and reduces residual levels of

chromium, forming a precipitate. Such reinjection creates a “barrier” of elevated water levels around the

plume, enhancing the gradient and associated hydraulic control. The reinjection also allows for in situ

reduction and subsequent fixation of residual chromium.

Wastes Treated: Cr+6

Status of Demonstration and Development: The technology was accepted into the SITE Program in the

summer of 1992. Arrangements are being made to demonstrate the technology in 1995.

Demonstration Results: None yet.

Contacts:

Douglas Grosse 

U.S. EPA

National Risk Management Research Laboratory

26 West Martin Luther King Drive

Cincinnati, OH 45268

513-569-7844

Fax: 513-569-7676

Jim Rouse

GEOCHEM (A division of Terra Vac)

12596 West Bayaud, Suite 205

Lakewood, CO 80228

303-988-8902

Fax: 303-988-0288
12

Current Research

Reaction Mechanisms in Permeable Reactive Barriers

ManTech Environmental Research Services Corporation and U.S. EPA

Environmental Research Laboratory, Ada, OK

Description of Research: Research during the past three years has evaluated the impact of subsurface

geochemistry and mineralogy on chromate reduction by zero-valent metals in permeable reactive barriers.

When reduced from Cr(VI) to Cr(III) the chromium becomes less toxic and its mobility is reduced due to

precipitation and adsorption, effectively remediating the aquifer. This research had multiple objectives,

which were to determine:

1) whether corrosion processes, including cathodic reduction, are responsible for the removal of solution

CrO by elemental metals, primarily iron, 4

2-

2) if removal would occur in systems incorporating aquifer materials, 

3) the rates and mechanisms of the CrO removal, 4

2-

4) the form and location of the removed chromium,

5) how iron type, geochemical, and mineralogical differences affect these reactions and,

6) whether this remediation approach is suitable for a CrO plume at the U.S. Coast Guard Air Support 4

2- 

Center, Elizabeth City, North Carolina.

Numerous stirred batch reactor and shaken batch bottle experiments to test chromate reduction have been

performed using two different aquifer sediments and a silica sand, seven types of iron, titanium,

magnesium, aluminum, various metal pretreatments and seven aluminosilicate minerals. Aluminosilicate

dissolution in these systems has also been evaluated. Chromate adsorption and desorption studies as well

as electron probe microscopic analyses of the reacted materials have been carried out.

The results have shown that CrO in solution can be reduced to Cr(III) by corrosion mechanisms in the 4

2-

presence of elemental iron. The rate and completeness of chromate reduction are dependent on a complex

interaction between metal type, mass, surface area, pretreatment, and aquifer material mineralogy.

Exploratory data analysis was performed across several variables for one iron and aquifer material system

that reduced chromate rapidly. The resulting multiple regression model showed that 94% of the variation

in the chromate reduction half-life was explained by the iron mass and solid:solution ratio.

These corrosion reactions can only proceed when suitable e acceptors, such as protons, are present to form -

an appropriate couple and prevent the accumulation of electric charge. An electrical double-layer model

analogue for the metal filing surface has been proposed to explain the reactions that occur. Some types of

iron, particularly impure and partially corroded forms, are far more reactive than others for reducing CrO 4

2-

. Certain aquifer materials contribute more significantly to these reactions due to their mineralogy.

Aluminosilicates appear able to provide e accepting protons through dissolution, maintaining the -

corrosion process. A cycle can develop in which rust formation through corrosion promotes additional

aluminosilicate dissolution.
13

Research is continuing on these topics for chromium, along with the potential for enhancing the

remediation of other metals using permeable reactive barriers.

Wastes Treated: Chromium

Contact:

Bob Puls, Ph.D.

U.S. Environmental Protection Agency

R.S. Kerr Environmental Research Laboratory

P.O. Box 1198

Ada, OK 74820

405-436-8543

References:

Powell, R.M. Geochemical Effects on Chromate Reduction and Remediation Utilizing the Thermodynamic

Instability of Zero-Valence-State Iron. Master's Thesis. University of Oklahoma, Norman, Oklahoma

1994.

Powell, R.M.; Puls, R.W.; Hightower, S.K.; Clark, D.A. “Corrosive and Geochemical Mechanisms

Influencing In Situ Chromate Reduction by Metallic Iron.” American Chemical Society, Division of

Environmental Chemistry, Preprints of Papers Presented at the 209th ACS National Meeting, Anaheim,

California, April 2-7, 1995. 35 (1), p 784-787.

Powell, R.M.; Puls, R.W.; Hightower, S.K.; Sabatini, D.A. “Coupled Iron Corrosion and Chromate

Reduction: Mechanisms for Subsurface Remediation.” In press for the August 1995 Environmental

Science and Technology.

Puls, R.W.; Powell, R.M.; Paul, C.J. “In Situ Remediation of Ground Water Contaminated with Chromate

and Chlorinated Solvents Using Zero-Valent Iron: A Field Study.” American Chemical Society, Division

of Environmental Chemistry, Preprints of Papers Presented at the 209th ACS National Meeting, Anaheim,

California. April 2-7, 1995. 35 (1), p 788-791.

Powell, R.M.; Puls, R.W.; Paul, C.J. “Chromate Reduction and Remediation Utilizing the Thermodynamic

Instability of Zero-Valence-State Iron.” Water Environment Federation Specialty Conference Series

Innovative Solutions for Contaminated Site Management. March 6-9, 1994, Miami, Florida.

Powell, R.M. and Puls, R.W. “Abiotic Reduction of Chromate from Zero-Valent Iron Dissolution:

Reaction Rates and the Effects of Aquifer Materials.” Metal Speciation and Contamination of Aquatic

Sediments Workshop, Jekyll Island, Georgia, 1993. 

In Situ Process Based on Zero-Valent Iron

U.S. EPA, Environmental Research Laboratory, Athens, GA

Description of Research: Stainless steel columns have been designed to address a number of unresolved

issues in applying reactive iron treatment walls. These columns provide a greater level of experimental

control than those typically being used in reactive iron pilot studies. The columns are designed to measure

pH and treatment efficiencies along the length of the column to understand why iron treatment walls lose

effectiveness after movement through 10 to 50 cm of media. Innovative iron mixtures are being tested to
14

overcome pH problems and the inability to achieve drinking water standards and other MCLs. Long-term

stability testing is underway (3 to 6 months). Contaminated water from the DOE Savannah River Plant

TNX facility will be used for testing in concert with feasibility testing at the University of Waterloo. Data

from Waterloo/EnviroMetal pilot tests at Hill AFB have been reviewed, especially those tests where trace

amounts of vinyl chloride were observed. These data and results from column studies are being used to

develop preliminary guidance on the design and application of funnel-and-gate systems, and other reactive

wall configurations. Other efforts focus on the kinetics of the reaction.

Experiments are currently underway to identify and estimate the parameters that control the dechlorination

rate of trichloroethene and similar volatile organic compounds in flowing systems exposed to zero-valent

iron. These studies examine the effects of mass transfer on the observed conversion rates for various flow

velocities, pH, and contaminant concentrations. A rigorous description of the dependence of the

conversion rate on the system operating conditions facilitates the development and implementation of this

technology. Such detailed knowledge of the physical and chemical factors that control the degradation of

ground-water contaminants by granular iron will lead to improved designs of in situ treatment processes. 

Potentiostatic and potentiodynamic electrochemical approaches are planned to investigate surface

coverage, sorbed species, effects of hydrogen formation, and the elementary rate determining step.

Wastes Treated: TCE, PCE, other chlorinated solvents

Contact:

Steven C. McCutcheon, Ph.D., P.E.

Ronald A. Holser, Ph.D.

U.S. EPA 

Environmental Research Laboratory-Athens

960 College Station Road

Athens, GA 30605-2720

706-546-3160

Fax: 706-546-3340

Email: EPASM@Athens.ath.epa.gov or Rholser@Athens.ath.epa.gov

References:

Holser, R.A.; McCutcheon, S.C.; Wolfe, N.L. “The Application of a Rate Expression for the Reductive

Dehalogenation of TCE-Contaminated Groundwater to the Design and Performance of a Funnel and Gate

System.” Federal Environmental Restoration IV and Defense Cleanup Southeast, Atlanta, Georgia,

March 14-15, 1995.

Holser, R.A.; McCutcheon, S.C.; Wolfe, N.L. “Mass Transfer Effects on the Dehalogenation of

Trichloroethene by Iron/Pyrite Mixtures.” Extended Abstract and Invited Presentation, Division of

Environmental Chemistry, American Chemical Society, Anaheim, California, April 2-7, 1995.

Reduction of Halogenated Hydrocarbons by Metallic Iron

U.S. EPA, Environmental Research Laboratory, Athens, GA

Description of Research: Kinetic studies have been conducted on the redox reactions of the common

ground-water contaminants, tetrachloroethene and trichloroethene in an effort to delineate the reaction

mechanism and to identify the degradation products. The dependence of the reaction rate on factors such
15

as temperature, pH, iron surface area, oxygen concentration, and competing species has been investigated.

The focus of the work is to accurately predict the fate of these chlorinated pollutants and to investigate

new remediation methods. New reactive iron mixtures have been derived. This study was the first to

obtain a rigorous mass balance and pathway analysis of the reductive iron process. Firm hypotheses have

been obtained for the nature of the sorption reaction and dechlorination process. Some of the work has

been done in collaboration with David Burris of the Air Force Armstrong Laboratory located at Tyndall

Air Force Base, Florida.

Wastes Treated: PCE, TCE, other chlorinated solvents

Contact:

N.L. Wolfe, Ph.D.

U.S. EPA Environmental Research Laboratory

960 College Station Road

Athens, GA 30605-2720

706-546-3429

Fax: 706-546-3636

Email: Wolfe@Athens.ath.epa.gov

References:

Carreira, L. and Wolfe, N.L. “Abiotic Reductions: A Biochemical Approach.” 23rd Annual Symposium

on Environmental-Analytical Chemistry, Jekyll Island, Georgia, June 14, 1993.

Cipollone, M.G.; Hassan, S.M.; Wolfe, N.L.; Burris, D.R.; Jeffers, P.M. in review. “Reduction of

Halogenated Hydrocarbons with Iron: I. Kinetic Observations.”

Cipollone, M.G. and Wolfe, N.L. Extended Abstract and Invited Presentation, Division of Environmental

Chemistry, American Chemical Society, Anaheim, California, April 2-7, 1995.

Hatfield, K.; Burris, D.R.; Wolfe, N.L. “Heterogenous Reactions in Flow-Through Porous Media I.

Analytical Model.” submitted to American Society of Civil Engineer's Journal of Environmental

Engineering.

Wolfe, N.L.; Carreira, L.; Burris, D. “Potential for In Situ Remediation of Dissolved Halogenated Solvents

Using Biochemical Redox Components.” Second International Symposium on In Situ and On-Site

Bioremediation. San Diego, California, April 5-8, 1993.

Wolfe, N.L.; Peijnenburg, W.; d Hollander, H.; Verboom, H.; v d Meent, D. submitted for publication

“Structure Reactivity Relationships for Predicting Reductive Transformation Rate Constants of

Halogenated Hydrocarbons in Anoxic Sediment Systems.” Environmental Toxicology and Chemistry,

1994.

Wolfe, N.L.; Peijnenburg, W.; d Hollander, H.; Verboom, H.; v d Meent, D. submitted for publication

“Kinetics of Reductive Transformations of Halogenated Hydrocarbons Under Anoxic Reaction

Conditions.” Environmental Toxicology and Chemistry, 1994.

Dechlorination of Pesticides

U.S. EPA, Environmental Research Laboratory, Athens, GA
16

Description of Research: The degradation of chlorinated pesticides by anaerobic bacteria and separately

by zero-valent metals is being studied. Sediment samples have been collected and compared to known

contaminated sediments to identify environmental factors that are responsible for anaerobic degradation.

These studies have focused on the combination of extraction and reaction to release the bound contaminate

from the soil matrix and degrade the solubilized compound. They are also designed to improve analytical

methods. 

Wastes Treated: Toxaphene, chlordane, DDT and dieldrin

Contact:

N.L. Wolfe, Ph.D.

U.S. EPA 

Environmental Research Laboratory-Athens

960 College Station Road

Athens, GA 30605-2720

706-546-3429

Fax: 706-546-3636

Email: Wolfe@Athens.ath.epa.gov

In Situ Redox Barriers

Battelle Pacific Northwest Laboratories

Description of Research: Researchers at Battelle Pacific Northwest Laboratories have been studying the

ability of different reagents and microbial nutrient systems to immobilize inorganics or destroy organics in

the ground water and solid materials of an unconfined aquifer. The Department of Energy is sponsoring

the research. 

In the laboratory studies, completed in 1994, microbes exhibited the ability to degrade carbon tetrachloride

and other chlorinated solvents when the redox potential was reduced to the point where nitrate or iron

instead of oxygen acts as an electron acceptor. Chromate could be immobilized by reduction to highly

insoluble chromium hydroxide or iron chromium hydroxide.

Bench-scale studies, completed in 1994, were intended to determine the nature of the reactions that occur

and the efficiency with which they are induced by reagents or nutrients. The potential of cultured ironreducing bacteria for remediating subsurface environments contaminated with carbon tetrachloride and

chromium has been tested, and sodium dithionite was found to reduce structural ferric iron in Hanford

soils, the planned area for a field demonstration. Further experiments indicate that the half-life of the

dithionite ion is about two or three days in the Hanford confined aquifer. This half-life is adequate for

reducing the contaminants in the plume, while ensuring that dithionite does not remain as a contaminant in

the ground water for an extended time.

Wastes Treated: Chromium, chlorinated solvents

Contact:

J.S. Fruchter

Battelle Pacific Northwest Laboratories

Battelle Boulevard

P.O. Box 999
17

Richland, WA 99352

509-376-3937

Remediation with Zero-Valent Iron

Oregon Graduate Institute of Science and Technology

Description of Research: The primary purpose of the research is to explain how iron degrades

chlorinated solvents such as PCE, TCE, and carbon tetrachloride in ground water. Laboratory

experimental systems and columns have been used to study the reaction between chlorinated methanes and

their degradation by pure iron. The laboratory systems show that zero-valent iron participates in reductive

dechlorination predominantly by direct reduction at the iron surface, a process similar to metal corrosion.

Additional work has shown that iron reacts with nitro-aromatic groups, common in some types of

munitions like TNT. Researchers are investigating the many conditions and complicating factors that

affect remediation of chlorinated solvents and nitro-aromatic compounds using iron.

Wastes Treated: Chlorinated solvents, nitro-aromatic compounds

Contact:

Paul Tratnyek

Department of Environmental Science and Engineering

Oregon Graduate Institute of Science and Technology

P.O. Box 91000

Portland, OR 97291-1000

503-690-1023

References:

Agrawal, A. and Tratnyek, P.G. “Abiotic Remediation of Nitro-Aromatic Ground-Water Contaminants by

Zero-Valent Iron.” Preprints of Papers Presented at the 207th ACS National Meeting in San Diego,

California, March 13-18, 1994. American Chemical Society, Division of Environmental Chemistry 34 (1),

1994, p 492-494.

Johnson, T.L. and Tratnyek, P.G. “A Column Study of Carbon Tetrachloride Dehalogenation by Iron

Metal.” Proceedings of the 33rd Hanford Symposium on Health & the Environment—In Situ Remediation:

Scientific Basis for Current and Future Technologies. Pasco, Washington, 1994, p 931-947.

Matheson, L.J. and Tratnyek, P.G. “Processes Affecting Reductive Dechlorination of Chlorinated Solvents

by Zero-Valent Iron.” Preprint of Papers Presented at the 205th ACS National Meeting in Denver,

Colorado, March 28-April 2, 1993. American Chemical Society, Division of Environmental Chemistry,

33, p 3-4.

Matheson, L.J. and Tratnyek, P.G. “Reductive Dehalogenation of Chlorinated Methanes by Iron Metal.”

Environmental Science and Technology, 28 (12), 1994, p 2045-2053.

Matheson, L.J. and Tratnyek, P.G. “Abiotic and Biotic Aspects of Reductive Dechlorination of

Chlorinated Solvents by Zero-Valent Iron.” Preprints of Papers Presented at the 207th ACS National

Meeting in San Diego, California, March 13-18, 1994. American Chemical Society, Division of

Environmental Chemistry 34 (1) p 414-415.
18

Permeable Chemical Reactive Barriers

Rust Geotech, Inc.

Description of Research: For about 5 years, researchers at Rust Geotech, Inc. have been conducting

laboratory batch and column studies of aquifer permeability, and two-dimensional tank and modeling

experiments on chemical reactive barriers that sorb such elements as uranium, molybdenum, copper, lead,

zinc, and radium. The primary purpose is to determine the applicability of chemical reaction barriers to in

situ remediation of uranium tailings, which threaten ground water at many DOE mill sites. Some

important areas under investigation are the sorption capacities for a variety of contaminants and the

relative immobility of the sorbing phase under aquifer flow conditions. Tests have been conducted on

barriers containing primarily low-cost materials such as hydrated lime, fly ash, barium chloride, calcium

phosphate, titanium oxide, peat, lignite, ferric oxyhydroxide, ferrous hydroxide, hydrophobic zeolite,

hydrated iron oxide, and ferrous sulfate. Extraction rates for uranium (initial concentration 30 mg/L) were

greater than 99% using hydrated lime, fly ash, barium chloride, calcium phosphate, titanium oxide, peat,

and lignite. More than 96% of the molybdenum (initial concentration 8.9 mg/L) was extracted by ferrous

sulfate, ferric oxyhydroxide, titanium oxide, peat, hematite, calcium chloride, and barium chloride. The

most extensive research effort has centered around the use of ferric oxyhydroxide to immobilize metals

and uranium. The studies have shown that ferric oxyhydroxide (1) is an inexpensive sorbent for uranium

and metals, (2) can be injected into ground water, (3) should remain immobile once emplaced, and (4)

once emplaced, should not reduce aquifer permeability. All of these issues are important to the successful

implementation of a subsurface reactive barrier.

Rust Geotech conducts its research at the Environmental Sciences Laboratory in Grand Junction,

Colorado. This lab is part of the Department of Energy's Grand Junction Project Office.

Wastes Treated: Uranium, molybdenum, arsenic, copper, lead, zinc, cadmium, chromium, and radium

Contact:

Stan J. Morrison

Rust Geotech, Inc.

Environmental Sciences Laboratory

Grand Junction Projects Office

P.O. Box 14000

Grand Junction, CO 81502

303-248-6373

References:

“Chemistry Can Contain Contamination.” Groundwater Newsletter, 22, 1993.

“Industrial Materials Can Be Combined for a Barrier to Protect Groundwater at Uranium Tailings Sites.”

Groundwater Newsletter. 21 (22), 1992.

Morrison, S.J. and Spangler, R.R. “Chemical Barriers for Controlling Groundwater Contamination.”

Environmental Progress. 12 (3), 1993, p 175.

Morrison, S.J. and Spangler, R.R. “Extraction of Uranium and Molybdenum from Aqueous Solutions: A

Survey of Industrial Materials for Use in Chemical Barriers for Uranium Mill Tailings Remediation.”

Environmental Science and Technology. 26, 1992, p 1922-1931.
19

Morrison, S.J.; Spangler, R.R.; Tripathi, V.S. in press. “Adsorption of Uranium (VI) on Amorphous Ferric

Oxyhydroxide at High Concentrations of Dissolved Carbon (IV) and Sulfur (VI).” Journal of

Contaminant Hydrology.

Morrison, S.J.; Tripathi, V.S.; Spangler, R.R. in press. “Coupled Reaction/Transport Modeling of a

Chemical Barrier for Controlling Uranium (VI) Contamination in Ground Water.” Accepted for

publication in Journal of Contaminant Hydrology.

Zeolites as Permeable Barriers

New Mexico Institute of Mining and Technology

Description of Research: The Institute is developing a permeable barrier of altered zeolite that retains

some major classes of ground-water contaminants while allowing ground water to pass through. The

barrier is selective for major classes of soluble organics such as benzene and trichloroethylene, inorganic

cations such as lead and cadmium, and inorganic anions such as chromate and arsenate. Raw zeolite,

which has a high adsorptive capacity for positively charged contaminants, is treated with cationic

surfactants that increase its ability to adsorb organics and negatively charged inorganic contaminants. The

hydraulic properties of the surface-altered zeolite can be tailored for specific needs. Researchers are

characterizing the properties of the altered zeolite and its stability and adsorptive characteristics as a

function of environmental variables such as pH and temperature. Pilot scale tests in a permeable barrier

system, and a field demonstration are planned.

Wastes Treated: Soluble organics, inorganic cations and anions

Contact:

Robert S. Bowman

Department of Earth and Environmental Science

New Mexico Institute of Mining and Technology

Socorro, NM 87801

505-835-5992

References:

Bowman, R.S.; Flynn, M.; Haggerty, G.M.; Huddleston, R.G.; Neel, D. “Organo-Zeolites for Sorption of

Nonpolar Organics, Inorganic Cations, and Inorganic Anions.” Proceedings of the Joint CSCE-ASCE

National Conference on Environmental Engineering, July 12-14, 1993, Montreal, Quebec, Canada, p

1103-1109.

Bowman, R.S.; Haggerty, G.M.; Huddleston, R.G.; Neel, D.; Flynn, M. “Sorption of Nonpolar Organics,

Inorganic Cations, and Inorganic Anions by Surfactant-Modified Zeolites.” In: Sabatini, D.A.; Knox,

R.C.; and Harwell, J.H. eds. Surfactant-Enhanced Remediation of Subsurface Contamination. ACS

Symposium Series 594, American Chemical Society, Washington, DC, 1995, p 54-64.

Haggerty, G.M. and Bowman, R.S. “Sorption of Inorganic Anions by Organo-Zeolites.” Environmental

Science and Technology, 28, 1994, p 452-458.

Neel, D. and Bowman, R.S. “Sorption of Organics by Surface-Altered Zeolites.” Proceedings 36th of the

Annual New Mexico Water Conference, November 7-8, 1991, Las Cruces, New Mexico, p 57-61.
20

Sullivan, E.J.; Bowman, R.S.; Haggerty, G.M. “Sorption of Inorganic Oxyanions by Surfactant-Modified

Zeolites.” Proceedings SPECTRUM '94, Nuclear and Hazardous Waste Topical Meeting, August 14-18,

1994, Atlanta, Georgia, p 940-945.

Teppen, B.J.; Hunter, D.B.; Bertsch, P.M.; Sullivan, E.J.; Bowman, R.S. “Modeling Organic Modification

of a Natural Zeolite Surface.” Paper presented on August 20-24, 1995, American Chemical Society

Annual Meeting, Chicago, Illinois, 1995.

Hydrodehalogenation of Chlorinated Substances in Water

Department of Civil Engineering, Stanford University

Description of Research: Catalytic hydrodehalogenation using palladium and hydrogen is showing

promise in laboratory studies as a viable method for treating water contaminated with chlorinated

hydrocarbons even in the presence of oxygen, nitrite, sulfate, and chloride. In other laboratory scale

studies, the transformation of chlorinated organic compounds, such as tetrachloroethylene, by iron and

manganese powders in buffered water and in landfill leachate is being investigated.

Wastes Treated: TCE, PCE, other chlorinated solvents

Contact:

Martin Reinhard

Western Region Hazardous Substance Research Center

Department of Civil Engineering

Stanford University

Stanford, CA 94305-4020

415-723-0308

References:

Schreier, C.G. and Reinhard, M. “Catalytic Hydrodehalogenation of Chlorinated Ethylenes Using

Palladium and Hydrogen for the Treatment of Contaminated Water.” accepted for publication in

Chemosphere, June 14, 1995.

Schreier, C.G. and Reinhard, M. “Transformation of Chlorinated Organic Compounds by Iron and

Manganese Powders in Buffered Water and in Landfill Leachate.” Chemosphere, 29 (8), 1994, p 1743-

1753.

Remedial Applications of Zero-Valence Metals

Martin Marietta Energy Systems and Oak Ridge National Laboratory

Description of Research: Researchers have been conducting laboratory batch and column studies on

zero-valent iron during the past 2 years to establish the feasibility of using the metal for dechlorinating

organic solvents and removing radionuclides in situ at the Department of Energy's Paducah Gaseous

Diffusion Plant. Success in treating ground water contaminated with trichloroethene and technetium have

led to a plan to implement a year-long Superfund treatability study of ground water at the Plant.

Additional research by this group involves laboratory investigations of bimetallic processes that increase
21

the dehalogenation reaction rate for TCE and improve the rate of dehalogenation of less-chlorinated

compounds, such as dichloromethane. These studies are showing success.

Wastes Treated: TCE, DCE, Vinyl Chloride, and Technetium

Contacts:

Jay L. Clausen

Martin Marietta Energy Systems

761 Veterans Avenue

Kevil, KY 42053

502-441-5090

Nic E. Korte

Environmental Sciences Division

Oak Ridge National Laboratory

Grand Junction Office, 2597 B 3/4 Rd

Grand Junction, CO 81503

303-248-6210

References:

Clausen, J.; Richards, W.L.; Korte, N.E.; Liang, L. “ORNL/MMES Research into Remedial Applications

of Zero-Valence Metals: 3) Removal of TCE, cis-1,2-DCE, Vinyl Chloride, and Technetium.” Preprint

Extended Abstract. Presented before American Chemical Society, April 2-7, 1995, Anaheim, California.

Korte, N.; Muftikian, R.; Grittini, C; Fernando, Q; Clausen, J.; Liang, L. “ORNL/MMES Research into

Remedial Applications of Zero-Valence Metals: 2) Bimetallic Enhancements.” Preprint Extended

Abstract. Presented before American Chemical Society, April 2-7, 1995, Anaheim, California.

Ground Water Restoration with Iron Metal

GE Corporate Research and Development

Description of Research: Researchers at GE Corporate Research and Development have been studying

the process by which iron metal and other iron-bearing minerals degrade chlorinated solvents, such as

TCE, DCE, and VC in water. This research was undertaken to gain a fundamental mechanistic

understanding of the chlorinated solvent/iron corrosion process and to determine the factors that affect

dechlorination rate and long-term performance in ground-water treatment.

Reduction of chlorinated solvents promoted by iron metal surfaces was studied in laboratory experiments

and columns with particular emphasis on reaction rates, product mass balances, ground-water treatability,

and characterization of iron metal surfaces. A well-instrumented pilot-scale column system was used to

predict chemical and hydraulic lifetime of commercial iron filings and to demonstrate that target effluent

concentrations could be attained. Aging effects, such as those caused by mineral precipitation and

potential biofouling, were accelerated by using flow velocities much higher than those typical of ground

waters. Researchers continue to investigate other factors that affect the design and operability of permeable

walls or columns composed of iron metal and iron minerals.

Wastes Treated: Chlorinated solvents
22

Contact:

Joseph J. Salvo

GE Corporate Research & Development

1 River Road

P.O. Box 8, Bldg. K1, 3C21

Schenectady, NY 12301-0008

518-387-6123

References:

Eykholt, G.R.; Baghel, S.S.; Sivavec, T.M.; Mackenzie, P.D.; Horney, D.P. “Conservative Flow Tracers

for Iron Column Studies.” Preprint Extended Abstract. Presented at the 209th ACS National Meeting in

Anaheim, California, April 2-7, 1995. American Chemical Society, Division of Environmental Chemistry,

35 (1), 1995, p 818-821.

Mackenzie, P.D.; Baghel, S.S.; Eykholt, G.R.; Horney, D.P.; Salvo, J.J.; Sivavec, T.M. “Pilot-Scale

Demonstration of Reductive Dechlorination of Chlorinated Ethenes by Iron Metal.” Preprint Extended

Abstract. Presented at the 209th ACS National Meeting in Anaheim, California, April 2-7, 1995.

American Chemical Society, Division of Environmental Chemistry, 35 (1), 1995, p 796-799.

Sivavec, T.M. and Horney, D.P. “Reductive Dechlorination of Chlorinated Ethenes by Iron Metal.”

Preprint Extended Abstract. Presented at the 209th ACS National Meeting in Anaheim, California, April

2-7, 1995. American Chemical Society, Division of Environmental Chemistry, 35 (1), 1995, p 695-698.

In Situ Permeable Reaction Wall

Waterloo Centre for Groundwater Research, University of Waterloo

Description of Research: Extensive bench-scale, batch and column studies over the past four years show

that zero-valent iron can enhance the degradation by abiotic reductive dechlorination of halogenated

organic compounds. The University has tested fourteen chlorinated methanes, ethanes, and ethenes using a

variety of metals. Substantial degradation rates were obtained using iron for all tested compounds except

dichloromethane. Many degradation rates were several orders of magnitude greater than those reported in

the literature for abiotic and biotic degradation. Bench-scale laboratory batch experiments and treatability

column experiments conducted with sand aquifer material confirmed halogen degradation in the presence

of iron. The success of these studies has led to the testing of above-ground and in situ applications of

permeable reaction walls for remediating contaminated ground-water and to patents. 

Investigators at the University are continuing to develop various in situ barrier treatment designs for a

wide variety of common organic and inorganic ground-water contaminants including chlorinated solvents,

petroleum-derived contaminants such as BTEX, metals, nitrate, and phosphate. Several prototype systems

have been field tested, and designs for some full-scale systems have been developed. 

It is expected that many of the new treatment barriers will be used with the Funnel-and-GateTM system

developed initially at the Waterloo Centre for Groundwater Research and further developed and marketed

by Waterloo Groundwater Control Technologies, Inc. The various design options of the Funnel-andGateTM are intended to direct contaminant plumes to the reactive media and direct clean water around the

plume. 

Field demonstrations are planned on the following types of reactions for in situ treatment walls:
23

 Promote denitrification of nitrate in a contaminant plume emanating from a septic tank by using an

organic carbon source;

 Promote biologically mediated, reductive dechlorination of selected solvents by periodic injection of a

carbon-amended solution;

 Remove iron, sulfate, and heavy metals in ground water from mine tailings using chemically active

organic carbon to promote sulfate reduction;

 Remove phosphate by precipitation using a permeable iron oxyhydroxide solid; and

 Remove electroactive metals, such as hexavalent chromium, using zero-valent iron.

The Waterloo Centre for Groundwater Research is part of Ontario's Centres of Excellence program, a

government sponsored partnership with academia and industry.

Wastes Treated: Numerous organic compounds such as carbon tetrachloride, chloroform, TCE, PCE, and

BTEX; as well as metals, nitrate, and phosphate 

Contact:

Stephanie O'Hannesin

Waterloo Centre for Groundwater Research

University of Waterloo

Waterloo, Ontario N2L 3G1 Canada 

519-885-1211

References:

Blowes, D.W. and Ptacek, C.J. “Geochemical Remediation of Ground Water by Permeable Reactive

Walls: Removal of Chromate by Reaction with Iron-Bearing Solids.” Proceedings of the Subsurface

Restoration Conference, 3rd International Conference on Ground Water Quality Research, June 21-24,

1992, Dallas, Texas, p 214-216.

Devlin, J.F. and Barker, J.F. “A Semipassive Nutrient Injection Scheme for Enhanced In Situ

Bioremediation.” Ground Water, 32 (3), 1994, p 374.

Gillham, R.W. and O'Hannesin, S.F. “Metal Catalyzed Abiotic Degradation of Halogenated Organic

Compounds.” Ground Water 29 (5), 1991, p 752.

Gillham, R.W. and Burris, D.R. “In Situ Treatment Walls—Chemical Dehalogenation, Denitrification, and

Bioaugmentation.” Proceedings from the Subsurface Restoration Conference, Dallas, Texas, June 21-24

1992. Houston: Rice University, Department of Environmental Science and Engineering, p 66-68.

Gillham, R.W.; O'Hannesin, S.F.; Orth, W. Scott. “Metal Enhanced Abiotic Degradation of Halogenated

Aliphatics: Laboratory Tests and Field Trials.” Paper presented on March 9-11, 1993, HazMat Central

Conference, Chicago, Illinois, 1993.

Smyth, D.J.A.; Cherry, J.A.; Jowett, R.J. “Funnel-and-Gate for In Situ Groundwater Plume Containment.”

Presented at Superfund XV, Washington, DC, November 28-December 1, 1994.
24

Permeable Reactive Barriers

Los Alamos National Laboratory

Description of Research: Researchers have evaluated the applicability of gel materials in barriers to

enhance natural biologic communities and to test chemical tracers and remote monitoring of hydrologic

systems. Investigators have used zeolite, silica gel, sand, bentonite, aluminum crosslink polyacrylamide,

and peat in permeable barriers. Approaches to managing biologic communities on the margins of a site in

combination with other barrier systems are being evaluated. Barriers used as part of post-closure

monitoring systems serve to warn of impending contaminant migration. 

Post-closure monitoring experiments will focus on the evaluation of water saturation and chemical

transport using tracers such as common anions, soluble organic acids, semivolatile organic acids,

fluorescein, chromium, EDTA, and toluene labeled with carbon-13 for the bio-barrier. 

The first barrier and monitoring systems were installed in 1992. Field tracer tests were scheduled for

completion in early 1994, however, Department of Energy funding was discontinued after the first year.

The research was conducted in partnership with the Universities of Houston and New Mexico and the

DuPont and Pfizer Chemical Companies.

Contact:

Ken Bostick or Dave Janecky

Los Alamos National Laboratory

Mail Stop J495, Organization EES-15

Los Alamos, NM 87545

505-667-8483 (Bostick) or 505-665-0253 (Janecky)

References:

DOE-AL. Technology Information Profile (Rev.2), Technical Name: Barriers and Post-Closure

Monitoring. DOE ProTech Database, TTP Reference Number: AL-1211-25, February 26, 1993.

Hansen, W.; Bostick, K.; Janecky, D. Barriers and Post-Closure Monitoring. Briefing Chart, Los Alamos

National Laboratory, Los Alamos, NM. TTP Reference Number AL-1212-25, October 10 1992.
25

General References

“Canada Pushes Innovative Remediation Technology: Permeable Reaction Wall Used for In Situ

Degradation of Halogenated Organic Compounds.” Chemical Engineering Progress, June 1993, p 14.

Gillham, R.W.; Blowes, D.W.; Ptacek, C.J.; O'Hannesin, S.F. “Use of Zero-Valent Metals for In Situ

Remediation of Contaminated Ground Water.” In: Proceedings of the 33rd Hanford Symposium on Health

and the Environment—In Situ Remediation: Scientific Basis for Current and Future Technologies. Pasco,

Washington. November 11, 1994. Columbus, Ohio: Battelle Press, 1994.

Gillham, R.W. and O'Hannesin, S.F. “Enhanced Degradation of Halogenated Aliphatics by Zero-Valent

Iron.” Ground Water, 32 (6), 1994, p 958-967.

Henderson, T. “Geochemical Reduction of Hexavalent Chromium in the Trinity Sand Aquifer.” Ground

Water, 32 (3), May-June 1994, p 477-486.

McCalady, Donald (ed). “Chemical Mediation of Pollutant Transport in Aqueous Systems.” Journal of

Contaminant Hydrology, 9 (1-2), January 1992. 

“Metal-Enhanced Reductive Dehalogenation (MERD), a Simple, Passive Technology for Reductive

Dehalogenation of Organics” Environmental Science and Technology, June 1994, p 254.

Starr, R.C. and Cherry, J.A. “Funnel-and-Gate System Directs Plumes to In Situ Treatment.” Ground

Water Currents, EPA/542/N-93/006, June 1993.

Starr, R.C. and Cherry, J.A. “In Situ Remediation of Contaminated Groundwater: The Funnel-and-Gate

System.” Ground Water, 32 (3), 1994, p 46.

Taylor, R.T.; Durham, W.B.; Duba, A.G.; Jackson, K.J.; Knapp, R.B.; Knezovich, J.P.; Wijesinghe, A.M.;

Bishop, D.J.; Hanna, M.L.; Jovanovich, M.C.; Shannard, D.R. “In Situ Microbial Filters.” Proceedings of

In Situ Bioremediation Symposium '92, Niagara-on-the-Lake, Ontario, Canada, September 20-24, 1992.

Burlington, Ontario Canada: Wastewater Technology Centre, p 66-67.

Waterloo Center for Groundwater Research. Groundwater Notes. 7 (1), 1994, p 1-12. Published by

Waterloo Centre for Groundwater Research, University of Waterloo, Waterloo, Ontario N2L 3G1 Canada.

Zotter, K. and Licsko, I. “Removal of Chromium (VI) and Other Heavy Metals from Groundwaters in

Neutral and Alkaline Media.” Water Science and Technology, 26 (1-2), 1992, p 207-216.