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EPA542-K-94-003
April 1995
In Situ Remediation Technology Status Report:
Surfactant Enhancements
ft
ft
U.S. Environmental Protection Agency
Office of Solid Waste and Emergency Response
Technology Innovation Office
Washington, DC 20460
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Acknowledgements
The authors would like to thank all the researchers and technology developisrs described in this report
for their assistance in its preparation. We especially would like to thank Dr. Candida West of the U.S.
EPA's R.S. Kerr Environmental Research Laboratory 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.
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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 Hydrofracturing/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
ce
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II
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Contents
Introduction
Purpose and Process .............. . * ........................... *
Technology Needs ........ . ..... ........................ *
Technology Description ............... ' ........................ *
Ongoing or Future Demonstrations and Commercial Applications
INTERA, Inc. and SUNY-Buffalo ............. '.'.'.'.'.'.'.'. ............ .....
INTERA, Inc., Montgomery Watson Corporation, SUNY-Buffalo .............. o
University of Oklahoma-Institute for Applied Surfactant Research ............. a
OHEA Associates, Inc .................. ............ J
University of Oklahoma-Institute for Applied Surfactant Research ............. t
U.S. Geological Survey and University of Virginia ............ .' ........... 5
Completed Demonstrations and Commercial Applications ......
SUNY Buffalo with Dupont Corporate Remediation Group .................. I
State University of New York (SUNY) Buffalo ............... L
General Motors NAO Research & Development Center .' \ '. '. '. '. '. '. ' .' .' .'.'.'.''"" 9
Current Research ................
University of Oklahoma-Institute for Applied Surfactant Research ............ !!
The University of Michigan ............... .......... u
Eckenfelder, Inc ............... ................. ' ............. *2
Howard University ................ ........................... ^
University of Michigan ............ ' . ........................... 14
Cornell University ................ ........................... ^
Michigan State University ....... ...... .............. ............. 15
........................... ; . . . . 16
General References .
................................................. 17
BTEX
CERCLA
DNAPL
DOE
PAH
PCE
RCRA
SITE
SVE
SVOC
TCA
TCE
TPH
VOC
Abbreviations
= Benzene, Ethylbenzene, Toluene, Xylene
= Comprehensive Environmental Response, Compensation, and Liability Act
= Dense Non-Aqueous Phase Liquid
= Department of Energy
= Poly-Aromatic Hydrocarbons
: Tetrachloroethylene
• Resource Conservation and Recovery Act
Superfund Innovative Technology Evaluation Program
Soil Vapor Extraction
Semi-Volatile Organic Compound
1,1,1 -Trichloroethane
Trichloroethylene
Total Petroleum Hydrocarbon
Volatile Organic Compound
111
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IV
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Introduction
Purpose and Process
Technology Needs
Technology Description
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Ongoing or Future
DOE Gaseous Diffusion Site, Portsmith, Ohio
INTERA, Inc. and SUNY-Buffalo
alluvium contaminated with high levels of DNAPL.
Wastes Treated: Mostly TCE with some PCBs and other chlorinated solvents.
Status: If approved, «££ ^ *£ ™£^£S
laboratory to determine he ™**f*™^™^L bPetWeen two existing wells that are currently
"
Preliminary Results: None yet.
Contacts:
Richard Jackson
INTERA, Inc.
6850 Austin Center Boulevard
Austin, TX 78731
512-346-2000
John Fountain
University at Buffalo
Department of Geology
772 Natural Science Complex
Buffalo, NY 14260
716-645-6800 X3996
Pickens, J.F. Deunninln, Locaton ant ComposUion «f I**
. U.S Paten. No. 5,319,966, 1994.
Technotegy Development Data Sheet from DOE's Movgantown Energy Techndogy Center (METC)
Report, September 1993.
Contamination 1(4) 1992, p 361-378.
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Hill Air Force Base, Utah
INTERA, Inc., Montgomery Watson Corporation, SUNV-Buffalo
Description of Demonstration: The project will be similar to a test conducted by the State University
of New York at the Canadian Forces Base Borden site. The main zone of ground-water contamination
is 24 feet deep. Researchers plan to enclose the demonstration zone within a steel cell 30 feet by 30
feet and within this they will place a line of five injection and five extraction wells. The site was a
former fire training pit. The Air Force has hired the Montgomery Watson Corporation to do a
treatability study for remediation of light non-aqueous phase liquids (LNAPLs) on the base. INTERA
is a subcontractor to Montgomery Watson and is responsible for numerical simulation of NAPL
solubilization and test hydraulics.
Wastes Treated: BTEX, PCBs
Status: As of July 1994, researchers were doing laboratory work. Field work is scheduled to begin in
Summer 1995.
Demonstration Results: None yet.
Contacts:
John Fountain
University at Buffalo
Department of Geology
772 Natural Science Complex
Buffalo, NY 14260
716-645-6800 X3996 '
Richard Jackson
INTERA, Inc.
6850 Austin Center Boulevard
Austin, TX 78731
512-346-2000 '
References: None yet.
Hill Air Force Base, Utah
University of Oklahoma—Institute for Applied Surfactant Research
Description of Demonstration: The University of Oklahoma is preparing a permit application for the
construction of eight 3-meter by 2-meter steel-walled cells to test various in situ technologies. Two
cells will be used to test the use of surfactants for solubilization and mobilization. (Other tests will
include cosolvent flooding, steam injection, and air injection treatments.) The walls of the test cells are
driven several feet into a clay layer that starts about 30 feet below ground level. The saturated zone is
3 to 5 feet thick on top of the clay layer. The sandy, cobble-filled soil has made drilling and retrieving
test cores difficult.
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Two well configurations are under consideration: (1) four injection wells and three extraction wells at
opposite ends of the cell or (2) a single vertical circulation well used for both injection and extraction.
Wastes Treated: LNAPL (a mixture of chlorinated and non-chlorinated VOCs, naphthalene,
pesticides, PCBs, dioxins, JP4)
Status: Upon permit approval, construction of the cells will begin. By late summer 1995, some tracer
tests will be conducted.
Demonstration Results: None yet.
Contacts:
Robert Knox
Department of Civil Engineering
University of Oklahoma
Norman, OK 73019
405-325-5911
References: None yet.
An Operating Facility of a Major U.S. Corporation
GHEA Associates, Inc.
Description of Demonstration: This is a commercial application of an on-site system for cleaning
leachates and reconstituting surfactants for an in situ soil flushing remediation project. The project is
supported by a New Jersey program to encourage collaboration between New Jersey firms and
universities. GHEA Associates has a contract with "a major U.S. corporation" to participate in the
cleanup of an industrial site at a working facility. The site is used for machining operations and the
soil is contaminated with a mixture of chlorinated organic solvents and BTEX at levels of 1,000 to
2,000 ppm. The water table is about 10 feet from the surface and the soil is very clayey. Researchers
will employ slurry walls to isolate the treatment zone and install feed trenches alternated with
extraction wells. Because of the limited permeability of the soil, a dense network of feed trenches and
extraction wells will be employed. There have not been regulatory barriers at this site. Regulators were
satisfied with the installation of monitoring wells.
Wastes Treated: VOCs, SVOCs, BTEX
Status: Some wells were installed, but the project is "on hold" as of April 1995.
Demonstration Results: None yet.
Contact:
Itzhak Gotlieb
New Jersey Institute of Technology
138 Warren Street
Newark, NJ 07102
201-226-4642
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References:
SITE Program Technology Profiles, Sixth Edition, EPA/540/R-93/526, November 1993.
Gotlieb, I.; Bozzelli, J. W.; Gotlieb, E. "Soil and Water Decontamination by Extraction with
' Surfactants." Separation Science and Technology, 28 (1-3) January-February 1993, p 793-804.
Traverse City Coast Guard Base, Michigan
University of Oklahoma—Institute for Applied Surfactant Research
Description of Demonstration: The primary objective of the field project at the Traverse City Coast
Guard Base is to demonstrate the efficiency of surfactant recovery using a novel single well
injection/extraction system. Soil at the base is contaminated by PCE, TCE, and BTEX. The secondary
objective will be to demonstrate the efficiency of removal of these contaminants from the soil using
surfactant flushing. The innovative hydraulic system both injects a surfactant solution and extracts the
ground-water/contaminant/surfactant fluid from a single borehole. Simultaneous injection to, and
extraction from, a common vertical borehole creates a circulating flow pattern that can be used to
capture mobilized contaminants that migrate vertically. The two peripheral wells will serve as
monitoring wells and peizometers. The demonstration area will be 10 feet by 10 feet and the depth to
ground water is 15 feet. The Dow Chemical Co., a manufacturer of surfactants, has formed a
partnership with the investigators to promote the development of this technology. The test will use
surfactants having FDA approval for use as indirect food additives. Surfactant and contaminants will
be removed and concentrated using micellar-enhanced ultrafiltration and then disposed of by a licensed
contractor. The remainder of the effluent will be directed to a carbon treatment system currently in
operation at the site.
Wastes Treated: PCE, TCE, BTEX
Status: Site reconnaissance began in September 1994. System installation and conservative tracer tests
were completed in October 1994. The demonstration is planned for summer 1995. Data collection and
analysis is to be completed by late 1995.
Demonstration Results: None yet.
Contact:
Candida West
R.S. Kerr Environmental Research Laboratory
Box 1198 |
Ada, OK 74820
405-436-8551
Picatinny Arsenal, New Jersey i
U.S. Geological Survey and University of Virginia
Description of Demonstration: At Picatinny Arsenal, TCE was used for years as a degreasing solvent
and has contaminated a sand and gravel aquifer. The water table is 10 feet below the surface and a
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lower confining unit 10 to 15 feet thick is another 40 feet from the water table. This project is funded
by EPA's Office of Exploratory Research. The site was recently listed as a Superfund site and a pump-
and-treat system was installed as an interim remedy.
This is a small-scale field test. Researchers will inject surfactants to cause the desorption of TCE from
soil and will monitor the increase of TCE levels in the ground water. The test site is upgradient from
the pump-and-treat systems, so surfactant and TCE will be removed there. Three injection wells have
been installed perpendicular to the ground-water flow. Three monitoring wells are located
downgradient and one monitoring well upgradient from the injection wells. The treatment area is 60
feet by 20 feet. The Picatinny Arsenal was chosen by the U.S. Geological Survey in 1986 as a
National Research Site.
Wastes Treated: TCE
Status: Laboratory work has been completed to determine the best surfactant and concentration to use.
Wells have been installed and the results of tracer tests confirmed hydraulic control of the test area.
Researchers expect to start the demonstration in summer 1995. The demonstration will last four to
eight weeks. Data analysis should be complete in late 1995.
University of Virginia researchers have a "preproposal" in to the U.S. EPA's SITE.program for doing
a project at Picatinny Arsenal in which soils will be flushed with surfactants to make sorbed TCE
more amenable to oxygen-enhanced bioremediation.
Demonstration Results: None yet.
Contacts:
Jim Smith
Department of Civil Engineering
University of Virginia
Charlottesville, VA 22903-2442
804-924-7991
Tom Imbrigiotta
U.S. Geological Survey
402 East State Street
Trenton, NJ 08628
609-771-3900
References:
Di Cesare, D. and Smith, J.A. "Effects of Surfactants on the Desorption Rate of Nonionic Organic
Compounds from Soil to Water." Reviews of Environmental Contamination and Toxicology, 134, 1994,
p 1-29.
Deitsch, J.J. and Smith, J.A. "Surfactant Enhanced Remediation of Ground Water at Picatinny Arsenal,
New Jersey." in Morganwalp, D.W. and Aronson, D.A., eds., £7.5. Geological Survey Toxics
Substances Hydrology Program—Proceedings of the Technical Meeting, Colorado Springs, Colorado,
September 20-24, 1993, U.S. Geological Survey Water-Resources Investigations Report 94-4015, 1994.
Deitsch, J.J. and Smith, J.A. "Effect of Triton X-100 on the Rate of Trichloroethene Desorption from
Soil to Water." Environmental Science and Technology, 29 (4), April, 1995.
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Completed Demonstrations and Commercial Applications
Corpus Chrisfi Dupont Site
SUNY Buffalo with Dupont Corporate Remediation Group
Description of Demonstration: A pilot field test for the remediation of an aquifer contaminated with
DNAPLs was undertaken at a chlorocarbons manufacturing facility in Corpus Christi, Texas. The site
was selected because: it is known to have DNAPLs present in a zone at shallow depths; the
contaminated zone has adequate hydraulic conductivity; and the target zone is underlain by a thick
clay unit that forms a barrier to further vertical migration. The target zone at this site was a 12 foot
sand lens within a thick regional clay unit. It extends from approximately 12 to 24 feet below the
ground surface. It is comprised of a very well-sorted fine sand with variable amounts of smectite clays
and a low carbon content. The test area was 25 feet by 35 feet.
The process involves adding surfactant to the extracted ground water at the surface, injecting the
mixture through an array of distribution wells and withdrawing it through extraction wells. The
contaminants are then separated by air stripping and the surfactant solution reinjected. The surfactant
used was not a food-grade additive but is approved for use in "food preparation procedures," has low
toxicity, and is readily biodegradable under aerobic and anaerobic conditions.
The surfactant flushing system requires only minor modifications of typical pump-and-treat design.
The only additional components are mixing and feed tanks for preparation and distribution of the
surfactant solution. Ground water is extracted and sent through an air stripper. The stripped solution is
then mixed with surfactant to bring the concentration to the desired level (1% for this test) and the
solution is then reinjected into the aquifer. The cycle is repeated until the end of the test. The test was
conducted in four phases. Phase I (6/91-8/91) used a 1% surfactant solution delivered through a well
array consisting of six delivery wells and one central extraction well. Sanding of one extraction well
required the installation of a new well for Phase II (3/92-6/92). High sorption of the original surfactant
and rapid biofouling of surface tanks and delivery wells resulted in a change of surfactant for Phase III
(6/92-10/92). Because of low flow rates due to a depressed regional water table, a smaller area
comprising the northern half of the original cell was treated during Phase IV (1/93-2/93).
Wastes Treated: Carbon tetrachloride (CTET)
Status: Completed.
Demonstration Results: Prior to the test, CTET was present at greater than 1,000 ppm in both core
and water samples from the test zone. During the test, the average effluent concentration of CTET
decreased from 790 ppm during Phase I to 219 ppm in Phase IV. A total of approximately 73 gallons
of CTET was removed during the project after 12.5 pore volumes were injected. Analysis of three
monitoring well nests within the DNAPLs source zone indicated that DNAPLs were rapidly being
removed. By increasing the contaminant solubility with the addition of surfactants, the DNAPLs
removal progressed at a rate considerably faster than would be expected with standard pump-and-treat
techniques. Researchers also concluded that although surfactant flushing is initially more expensive
than standard pump-and-treat, the large reduction in time required to complete the remedial treatment
greatly reduces the operating and maintenance costs.
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Contact:
John Fountain
University at Buffalo
Department of Geology
772 Natural Science Complex
Buffalo, NY 14260
716-645-6800 X3996
References:
Fountain, John. Project Summary: Extraction of Organic Pollutants Using Enhanced Surfactant
Flushing—Part II. NY State Center for Hazardous Waste Management, November 1993.
Fountain, J.C. and Waddell-Sheets, C. "A Pilot Field Test of Surfactant Enhanced Aquifer
Remediation: Corpus Christi, Texas." Abstract from presentation at an ACS Symposium in Atlanta,
Georgia, September 27-29, 1993.
Fountain, J.C. "A Pilot Scale Test of Surfactant Enhanced Pump and Treat." Proceedings of Air and
Waste Management Association's 86th Annual Meeting in Denver, Colorado, June 13-18, 1993.
Canadian Air Forces Base Borden, Alliston, Ontario, Canada
State University of New York (SUNY) Buffalo
Description of Demonstration: Researchers conducted a field-scale test of a surfactant flooding
system to extract organic pollutants from a sand aquifer. The test was conducted at the Canadian Air
Forces Base Borden, a field test facility operated by the University of Waterloo's Centre for Ground-
Water Research. A three-square-meter cell was built in a four-meter-thick surficial sand aquifer by
driving sheet piling walls into the underlying clay. A second sheet-piling barrier was installed one
meter beyond the first wall for secondary containment. Five injection wells were installed on one side
of the cell and five extraction wells on the other side. Multi-level monitoring wells also were installed.
PCE was introduced into the test cell. The cell was then flushed by pumping a 2% aqueous mixture of
surfactant from one side of the cell to the other. On the surface, the contaminant was air stripped and
the aqueous surfactant solution recycled.
Wastes Treated: PCE
Status: Completed.
Demonstration Results: Approximately 80% of the PCE that was spilled into the cell was recovered.
The results of analyses of the core and monitoring wells, however, suggest that the remaining PCE is
not in the cell. Probable explanations include volatilization of PCE from the surface of the cell and,
possibly, that some PCE was trapped at the edges of the cell where the zig-zag shape of the sheet
piling walls created considerable dead space. The surfactant solution was initially injected into the five
injection wells through a constant-head system on each well. The system was changed to a peristaltic
pump delivery system due to plugging of the injection wells by fine material.
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Contacts:
John Fountain
University at Buffalo
Department of Geology
772 Natural Science Complex
Buffalo, NY 14260 '
716-645-6800X3996 ;
Ralph Rumer, Executive Director
NY State Center for Hazardous Waste Management
207 Jarvis Hall
Buffalo, NY 14260-4000
716-645-3446 i
References:
Fountain, John C. and Hodge, Dennis. Project Summary: Extraction of Organic Pollutants Using
Enhanced Surfactant Flushing—Initial Field Test (Part 1). NY State Center for Hazardous Waste
Management, February 1992.
Surfactant Washing Demonstration
General Motors NAO Research & Development Center
Warren, MI
Description of Demonstration: Following laboratory evaluations of a surfactant washing technique,
researchers conducted a two-phase field test of an in situ surfactant washing method at a site
contaminated with poly chlorinated biphenyls (PCBs) and oils. Feasibility studies were also conducted
on the use of ultrafiltration to recover surfactant from aqueous waste streams generated from the in
situ surfactant washing. The field test site was used to store unused machineiy and the contamination
is confined to the upper 15 feet of the subsurface fill material. A containment wall of clay and cement
was previously installed around the five-acre site. This wall extends to a depth of 60 feet below the
surface. A surfactant solution was applied to a test plot 10 feet in diameter and five feet deep. The
leachate was collected with a recovery well installed through the center of the plot. The leachate
pumped to the surface was biotreated to degrade the oils and surfactant while the PCBs were
recovered from the leachate by an activated carbon system. Soil cores from tlhe site showed initial
concentrations of up to 6,000 ppm PCBs and 67,000 ppm oils. In separate tests, leachate from the
surfactant washing demonstration was collected in a process tank and pumped into a Romicon Model
HF-Lab-5 ultrafiltration unit equipped with either of two membranes (XM50 and PM500) to evaluate
the recovery of the surfactant from the leachate for possible reuse.
Wastes Treated: PCBs, oils
Status: Completed.
Demonstration Results: About 10% of the initial contaminants (mass) was washed from the test plot
after 5.7 pore volume washings during the phase 1 field test. During the phase 2 field test conducted
the following year at the same site, an additional 14% of the contaminants was washed from the test
plot after 2.3 pore volume washings. The results from the second phase of the field study surpassed
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the prediction of the long-term performance of this technology based on the phase 1 results and
confirmed the technical viability of this process.
The ultrafiltration feasibility studies showed that 46% of the surfactant (mass) was recovered during
the field test using the XM50 membrane. The membrane retained 94% and 89% of the PCBs and oils,
respectively. The second field test showed that the PM500 membrane recovered 67% of the surfactant
and retained more than 90% and 83% of the PCBs and oils, respectively.
Contacts:
Abdul S. Abdul
General Motors NAO R&D Center
Warren, MI 48090-9055
810-986-1600
Carolina C. Ang
General Motors NAO R&D Center
Warren, MI 48090-9055
810-986-1611
References:
Abdul, A.S. and Gibson, T.L. "Laboratory Studies of Surfactant-Enhanced Washing of Polychlorinated
Biphenyls from Sandy Materials." Environmental Science and Technology, 25 (4) 1991, p 665-670.
Abdul, A.S.; Gibson, T.L.; Ang, C.C.; Smith, J.C.; and Sobczynski, R.E. "In Situ Surfactant Washing
of Polychlorinated Biphenyls and Oils from a Contaminated Site." Ground Water, 30 (2) March-April
1992, p 219-231.
Abdul, A.S. and Ang, C.C. "In Situ Surfactant Washing of Polychlorinated Biphenyls and Oils from a
Contaminated Field Site: Phase II Pilot Study." Ground Water. 32 (5) September-October 1994, p 727-
734.
Ang, C.C. and Abdul, A.S. "Aqueous Surfactant Washing of Residual Oil Contamination from Sandy
Soil." Ground Water Monitoring Review, 11 (2) 1991, p 121-127.
Ang, C.C. and Abdul, A.S. "A Laboratory Study of the Biodegradation of an Alcohol Ethoxylate
Surfactant by Native Soil Microbes." Journal of Hydrology, 138, 1991, p 191-209.
Ang, C.C. and Abdul, A.S. "Evaluation of an Ultrafiltration Method for Surfactant Recovery and
Reuse During In Situ Washing of Contaminated Sites: Laboratory and Field Studies." Ground Water
Monitoring and Remediation, Summer 1994.
10
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Current Research
Surfactant Remediation of Ground Water
University of Oklahoma—Institute for Applied Surfactant Research
Description of Research: Researchers have been conducting laboratory, bench-, and pilot-scale work
in four areas: the use of food-grade additive (edible) surfactants; use of high-performance surfactants;
recovery and reuse of surfactants; and improving the hydraulic efficiency of "injected solutions. The
work on "edible" surfactants—substances that are already approved by the FDA for use as food
additives—may be helpful in expediting cleanup processes from a regulatory perspective and has been
funded by EPA's R.S. Kerr Environmental Research Laboratory (RSKERL).
Funding for three field demonstrations have been received and are in the planning stage. These
demonstrations will be supported by RSKERL, with additional field studies pending with industry, and
the Departments of Defense and Energy.
Wastes Treated: VOCs, SVOCs, BTEX, PAHs, PCBs, metals
i
i
Contact:
David A. Sabatini, Ph.D., P.E.
University of Oklahoma
School of Civil Engineering and Environmental Science
Norman, OK 73019
405-325-4273; fax: 405-325-4217; Internet: sabatini@mailhost.ecn.uoknor.edu
References:
Knox, R.C.; Sabatini, D.A.; and Canter, L.W. Subsurface Transport and Fate Processes. Boca Raton,
FL: Lewis Publishers, 1993, ISBN* 0-87371-193-9, 430p.
Rouse, J.D.; Sabatini, D.A.; and Harwell, J.H. "Minimizing Surfactant Losses Using Twin-Head
Anionic Surfactants in Subsurface Remediation." Environmental Science and Technology, 27 (10)
1993, p 2072-2078.
.
Rouse, J.D.; Sabatini, D.A.; Suflita, J.M.; and Harwell, J.H. "Influence of Surfactants on
Biodegradation of Organic Compounds." Critical Reviews in Environmental Science and Technology.
In Press (May 27, 1994).
Sabatini, D.A.; Knox, R.C.; and Harwell, J.H. Surfactant Enhanced Subsurface Remediation: Emerging
Technologies. ACS Symposium Series, American Chemical Society, Washington, DC, 1994 (to be
published)
i
Sabatini, D.A. and Knox, R.C., eds. Transport and Remediation of Subsurface Contaminants:
Colloidal, Interfacial and Surfactant Phenomena. ACS Symposium Series 491. American Chemical
Society, Washington, DC, 1992. ;
Shiau, B.J.; Sabatini, D.A; and Harwell, J.H. "Solubilization and Mobilization of Chlorinated Solvents
Using Direct Food Additive (Edible) Surfactants." Ground Water, 32 (4) July/August 1994, p 561-569.
11
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Surfactant Enhanced Aquifer Remediation
The University of Michigan
Description of Research: Dr. Abriola's research group has been conducting laboratory and numerical
modeling studies to evaluate the use of surfactants for remediating aquifers contaminated by
nonaqueous phase liquids (NAPLs). This work has been funded by the EPA's R.S. Kerr Environmental
Research Laboratory and Great Lakes Mid-Atlantic Hazardous Substance Research Center (HSRC).
The specific objectives of this research are to: screen and select surfactants that will enhance the
solubility of NAPLs in water; measure the solubilization of representative NAPLs (e.g., dodecane,
PCE, o-DCB) in aqueous surfactant solutions; quantify the ability of selected surfactants to recover
entrapped NAPLs from soil columns; and develop and evaluate numerical models capable of predicting
surfactant-enhanced solubilization and mobilization of NAPLs in ground-water systems.
Soil column experiments were conducted to test the ability of a nonionic surfactant, polyoxyethylene
(20) sorbitan monooleate (trade name Witconol 2722 or Tween 80), to recover entrapped dodecane.
After injecting a 4% surfactant solution, the concentration of dodecane exiting the column increased by
approximately 100,000 times. Removal of 10% of the residual dodecane required 0.7 liters of
surfactant solution, while comparable recovery without surfactant would have required 130,000 L of
water. Numerical models were developed to explore the optimal surfactant flushing strategies based on
the flow rate, flushing time, and volume of surfactant required to remove NAPLs from soil columns.
Additional studies are underway to investigate the effects of rate-limited solubilization, NAPL
mobilization and sorption on surfactant-based remediation technologies. No field demonstrations have
been conducted to date, but we anticipate that these studied will provide the basis for such work.
Wastes Treated: VOCs, dodecane
Contacts:
Dr. Linda Abriola
Dept. of Civil & Environmental Engineering
119 EWRE Building
The University of Michigan
Ann Arbor, MI 48109-2125
313-763-9406
Dr. Kurt Pennell
Dept. of Civil & Environmental Engineering
109 EWRE Building
The University of Michigan
Ann Arbor, MI 48109-2125
313-764-6487
References:
"Surfactant Flushing Research to Remove Organic Liquids from Aquifers," Ground Water Currents,
March 1994. EPA 542-N-92-002.
"Surfactants Can Trap, Untrap Contaminants" Centerpoint, 1 (2) 1993. (A publication of the HSRCs).
"Surfactant-Enhanced Solubilization of Residual Dodecane From Soil Columns 1. Experimental
Investigation, 2. Modeling Investigation" Environmental Science & Technology, 27, 1993, p 2332-
2351.
"Surfactant-Enhanced Remediation of Soil Columns Contaminated by Residual Tetrachloroethylene,"
Journal of Contaminant Hydrology, 16, 1994, p 35-53.
12
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Recycle/Reuse of Surfactant Used in Flushing
Eckenfelder, Inc.
Description of Research: Researchers from Eckenfelder, Inc., and Vanderbilt University have
successfully tested a pilot-scale system for recycle and reuse of spent surfactant solution from
organics-contaminated soil washing. The research involved testing of the integrated pilot-scale unit on
the removal of biphenyl from a soil test bed (152 pounds) spiked with biphenyl as a representative
nonvolatile contaminant and the continued treatment of the soil with the recycled surfactant solution.
Not only was 99% of the biphenyl removed from the soil, but there was no decrease in the
effectiveness of the recycled surfactant solution in removing the biphenyl compared to the virgin
solution.
This work was conducted under a U.S. EPA Small Business Innovative Research Phase II (SBIR-II)
research grant. Since it had been determined in earlier Phase I research that the surfactant can remove
high levels of biphenyl (1000 mg/kg) from soil, the Phase II research simulates the polishing of the
removal of biphenyl. Soil with an initial biphenyl concentration of 92 mg/kg was cleaned to
approximately 1 mg/kg using 7.7 pore volumes of a 2.5% surfactant solution, A conservative estimate
of 20 to 40 pore volumes of water would be required to reach the same degree of biphenyl removal.
The process achieved a 90% volume reduction of waste even without optimization of the system.
Researchers also have developed a mathematical model to assess relative cleanup times as a function
of the location of the recovery and injection wells, surfactant concentration, solution flow rates, and
soil particle size. The model also has been used to estimate preliminary full-scale costs for PCB
removal.
The surfactant selected by Eckenfelder, Inc. for testing is sodium dodecyl sulfate (SDS). It is
biodegradable, relatively nontoxic, and commercially available. The anionic character of SDS permits
its recovery and reuse by solvent extraction and also reduces its tendency to sorb to negatively charged
soils, such as clays.
Researchers have proposals in to DOE and DOD for further tests of both in situ and ex situ systems.
Wastes Treated: PCB-contaminated soil
Contacts:
Ann Clarke
Eckenfelder, Inc.
227 French Landing Rd.
Nashville, TN 37228
615-255-2288
i
Ken Oma
Eckenfelder, Inc.
227 French Landing Rd.
Nashville, TN 37228
615-255-2288
13
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References:
Oma, K.H.; Clarke, A.N.; Megehee, M.M.; Mutch, R.D.; and Wilson, D.J. "Pilot-Scale Surfactant
Flushing Test Results with PCB-Contaminated Soil." Proceedings of an ACS Conference on Emerging
Technologies for Hazardous Waste Management, Atlanta, Georgia, September 21-23, 1992.
Clarke, Ann N.; Oma, Kenton H.; Megehee, Maria M.; and Wilson, David J. "Soil Cleanup by
Surfactant Recycle Washing. II." Separation Science and Technology. 28 (13-14) October 1993, p
2103-2135.
Oma, Kenton H.; Clarke, Ann N.; Megehee, Maria M.; and Wilson, David J. "Soil Cleanup by
Surfactant Washing. HI." Separation Science and Technology. 28 (15-16) November 1993, p 2319-
2349.
Underwood, Julie L.; Debelak, Kenneth A.; and Wilson, David J. "Soil Cleanup by Surfactant
Washing. VI." Separation Science and Technology. 28 (9) July 1993, p 1647-1669.
Underwood, Julie L.; Debelak, Kenneth A.; Wilson, David J.; and Means, Jennifer M. "Soil Cleanup
by In-Situ Surfactant Flushing. V." Separation Science and Technology. 28 (8) May 1993, p 1527-
1537.
Soil-Surfactant Interactions in In Situ Soil Washing
Howard University
Description of Research: Researchers currently are conducting tests on treatment of PCBs with
surfactants with the support of the Great Lakes/Mid-Atlantic Hazardous Substance Research Center.
Wastes Treated: PCBs
Contact:
Jim Johnson
Department of Civil Engineering
Howard University
2400 6th Street, NW
Washington, DC 20059
202-806-6570
References:
Chawla, R.C.; Cannon, J.N.; Johnson, J.H.; and Porzucek, C. "Importance of
Soil-Contaminant-Surfactant Interactions in In-Situ Soil Washing." ACS Symposium on Emerging
Technologies for Hazardous Waste Treatment. Atlantic City, New Jersey, June 4-7, 1990, p 23.
Porzucek, C. Surfactant Flooding Technology for In Situ Cleanup of Contaminated Soils and Aquifers
—A Feasibility Study. Los Alamos National Laboratory, UD-702.LA-11541-MS, November 1989.
14
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Use of Cationic Surfactants to Reduce Mobility of Contaminants
University of Michigan
Description of Research: Researchers with the Great Lakes/Mid-Atlantic Hazardous Substance
Research Centers are conducting basic research to determine the partitioning characteristics of PAHs
such as phenanthrene. This information applies to the use of cationic surfactants to reduce the mobility
of contaminants such as PAHs. Such treatment may be used in conjunction with bioremediation to
keep the contaminants from migrating over the relatively long period for complete biodegradation to
occur.
Wastes Treated: PAHs
Contact: \
Dr. Kim F. Hayes (on sabbatical until 1995)
Environmental and Water Resources Engineering
Department of Civil and Environmental Engineering
Room 181 EWRE Building
University of Michigan
Ann Arbor, MI 48109-2125
References:
"Surfactants Can Trap, Untrap Contaminants" Centerpoint, 1 (2) 1993. (A publication of the
Hazardous Substances Research Center).
Surfactant Enhancement of Biodegradation of Aromatic Hydrocarbons
Cornell University
•
Description of Research: A study was conducted to determine whether a non-ionic surfactant added
to the surface of Lima silt loam would enhance the biodegradation of phenamthrene and biphenyl.
Researchers concluded that surfactants at low concentrations may be useful for in situ bioremediation
of sites contaminated with hydrophobic pollutants without causing movement of the parent compounds
to ground water. Dr. Alexander will continue with this work but has no plans to conduct field studies.
Wastes Treated: PAHs
i
Contact:
Martin Alexander
Cornell University
708 Bradfield Hall
Ithaca, NY 14853
607-255-2000
15
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npfAnppc*
Aronstein, B.N. and Alexander, M. "Effect of a Non-Ionic Surfactant Added to the Soil Surface on the
Biodegradation of Aromatic Hydrocarbons within the Soil." Applied Microbiology and Biotechnology,
39, 1993, p 386-390.
Aronstein B.N. and Alexander, M. "Surfactants at Low Level Concentrations Stimulate
Biodegradation of Sorbed Hydrocarbons in Samples of Aquifer Sand and Soil Slurries." Environmental
Toxicology and Chemistry, 11, 1992, p 1227-12331.
Surfactant Enhanced Soil Treatment
Michigan State University
Description of Research: Dr. Boyd is working on three research projects involving surfactants:
Surfactant treatment of soils and sediments
Dr Boyd is conducting basic research to study the effects of different classes of surfactants on the
partitioning of contaminants between the water and solid phases of sediments and sandy soils. Tests
have been conducted on DDT, PCBs, and PAHs such as naphthalene and phenanthrene.
Modification of soils with cationic surfactants
Boyd is treating clayey soils with cationic surfactants to make the soil more sorptive to common
organic contaminants. Though his work is basic research, a projected use of the technique would be to
infect the cationic surfactant into the ground in a location through which a contaminant plume would
flow Theoretically, contaminant concentrations in the water downgradient from the treated (sorptive)
zone would be substantially reduced. The contaminants immobilized within the zone could then be
treated with enhanced bioremediation to provide a comprehensive in-situ remediation technology. In a
related application, the cationic organo-clays could be used as components of barrier walls. They
would not only seal an area, but sorb any contaminants threatening to seep through.
Effects of low levels of surfactants on bioremediation
Through a cooperative agreement with ERL-Athens, Boyd has just begun laboratory work to study
how the biological dechlorination of PCBs in sediments can be enhanced by treating the sediments
with low levels of surfactants.
Wastes Treated: PCBs, PAHs
Contact:
Dr. Stephen Boyd
Department of Crop and Soil Science
Michigan State University
East Lansing, MI 48823-1325
517-353-3993
16
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General References
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Laboratory Hazardous Waste Research Symposium Cincinnati, Ohio, 13-15 April 1993, p 173-176.
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Ang, C.C. and Abdul, A.S. "Aqueous Surfactant Washing of Residual Oil Contamination from Sandy
Soil." Ground Water Monitoring Review, 11 (2) Spring 1991, p 121-127
i
Aronstein, B.N. and Alexander, M. "Effect of a Non-Ionic Surfactant Added to the Soil Surface on the
Biodegradation of Aromatic Hydrocarbons within the Soil." Applied Microbiology and Biotechnology,
39, 1993, p 386-390. Sponsored by the Army Research Office, Research Triangle Park, North
Carolina, Report Number ARO-26750.11 -LS.
Aronstein, Boris N. and Alexander, Martin. "Surfactants at Low Concentrations Stimulate
Biodegradation of Sorbed Hydrocarbons in Samples of Aquifer Sands and Soil Slurries."
Environmental Toxicology and Chemistry, 11 (9) September 1992, p 1227-1233.
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No.90-11,642.
17
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Brickell, J.L. and Keinath, T.M. "The Effect of Surfactants on the Sorption Partition Coefficients of
Naphthalene on Aquifer Soils." Water Science and Technology, 23, 1991, p 455.
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to Enhance Retardation of Organic Contaminants." Journal of Contaminant Hydrology, 10 (4)
September 1992, p 325-337.
Chawla, R.C.; Cannon, J.N.; Johnson, J.H.; and Porzucek, C. "Importance of
Soil-Contaminant-Surfactant Interactions in In-Situ Soil Washing." American Chemical Society (ACS)
Symposium on Emerging Technologies for Hazardous Waste Treatment, Atlantic City, New Jersey,
4-7 June 1990 p 23.
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Contaminated with Hazardous Organic Wastes Using Surfactants: A Critical Analysis." Solid/Liquid
Separation: Waste Management and Productivity Enhancement. Columbus, Ohio: Battelle Press, 1990,
p 355-367.
Clarke, A.N.; Mutch, R.D., Jr.; Wilson, D.J.; Oma, K.H.; Sukuzi, M.; et al (eds). "Design and
Implementation of Pilot Scale Surfactant Washing/Flushing Technologies Including Surfactant Reuse."
16th Biennial Conference of the International Association on Water Pollution Research and Control,
Washington, DC, 24-30 May 1992, p 127-135. Water Science and Technology, 26 (1-12), Part 1.
Clarke, A.N.; Plumb, P.D.; Subramanyan; and Wilson D.J. "Soil Clean-Up by Surfactant Washing. I.
Laboratory Results and Mathematical Modeling." Separation Science and Technology, 26 (3) 1991, p
301-343.
Clarke, Ann N.; Oma, Kenton H.; Maria, Megehee M.; and Wilson, David J. "Soil Clean-Up by
Surfactant Washing. EL Design and Evaluation of the Components of the Pilot-Scale Surfactant
Recycle System." Separation Science and Technology, 28 (13-14) October 1993, p 2103-2135.
Downey, D.C. and Elliott, M.G. "Performance of Selected In Situ Soil Decontamination Technologies:
An Air Force Perspective." Environmental Progress, 9 (3) August 1990, p 169-173.
Dworkin, D.; Messinger, D.J.; and Shapot, R.M. "In Situ Flushing and Bioreclamation Technologies at
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Edwards, D.A.; Laha, S.; Liu, Z.; and Luthy, R.G. "Solubilization and Biodegradation of Hydrophobic
Organic Compounds in Soil/Aqueous Systems with Nonionic Surfactants." 203rd American Chemical
Society National Meeting, San Francisco, California, 5-10 April 1992, p 726, Paper ENVR 262.
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Ellis, W.D.; Payne, J.R.; and McNabb, G.D. Treatment of Contaminated Soils with Aqueous
Surfactants (Interim Report May 1982-August 1985). Sponsored by the Environmental Protection
18
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Agency, Hazardous Waste Engineering Research Laboratory, Report Number EPA/600/2-85/129
PB86-122561, November 1985, 96p. ,
i
Falatko, D.M. and Novak, J.T. "Effects of Biologically Produced Surfactants on the Mobility and
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p 163-169. '
Fountain, J.C. and Waddell-Sheets, C. "Pilot Field Test of Surfactant Enhanced Aquifer Remediation-
Corpus Chnsti, Texas." Emerging Technologies in Hazardous Waste Management V. 27-29 September
1993, American Chemical Society (ACS); American Institute of Chemical Engineers; National
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Implications of Lab and Field Tests." Emerging Technologies for Hazardous Waste Management '
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Fountain, John C.; Klimek, Andrew; Beikirch, Michael G.; and Middleton, Thomas M "Use of
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I
Gotlieb, Itzhak; Bozzelli, Joseph W.; and Gotlieb, Erez. "Soil and Water Decontamination by
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793-804. 7th Symposium on Separation Science and Technology for Energy Applications, Knoxville
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Harwell, Jeffrey H. "Factors Affecting Surfactant Performance in Groundwater Remediation
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Hatfield, K.; Burris, D.; Stauffer, T. B.; and Ziegler, J. 'Theory and Experiments on Subsurface
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Holsen, T.M.; Taylor, E.R.; Yong-Chan Seo; and Anderson, P.R. "Removal of Sparingly Soluble
Organic Chemicals from Aqueous Solutions with Surfactant-Coated Ferrihydrite," Environmental
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"In-Situ Biosurfactant Production: An Aid to the Biodegradation of Organic Ground Water
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19
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Chemicals in Ground Water, Houston, Texas, 13 November 1985. National Water Well Association,
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Josselyn, L.P.; Dawson, H. "Surfactant Enhanced Removal of Dense Nonaqueous Phase Liquids
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Sandy Aquifer Material by Surfactant and Cosolvent Flush." 203rd American Chemical Society
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Laha S and Luthy, R.G. "Effects of Nonionic Surfactants on Microbial Mineralization of
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I
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'~
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21
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Underwood, J.L, Debelak, K.A, Wilson, D.J, and Means, J.M. "Soil Clean Up by In-Situ Surfactant
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wiADense Nonaqueous Phase Liquids by Chemically Enhanced Solubihzation." Journal of Sod
Contamination, 1 (4) 1992, p 361-378.
22
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