&EPA
United States
Environmental Protection
Agency
Office of Research and
Development
Washington DC 20460
EPA/600/Q-97/002
National Conference on
Management and
Contaminated Sediments
Research Programs and
Future Directions
May 14, 1997
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<£>
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Notice
The U.S. Environmental Protection Agency (|EPA) strives to provide accurate, complete, and
useful information. Neither EPA nor any person contributing to the preparation of this
document, however, makes any warranty, expressed or implied, with respect to the usefulness
or effectiveness of any information, method, jor process disclosed in this material. Nor does
EPA assume any liability for the use of, or for damages arising from the use of, any information,
methods, or process disclosed in this document.
1
Any mention of trade names or commercial products does not constitute endorsement or
recommendation for use.
Printed on Recycled Paper
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Table of Contents
Remediation Strategies and Options for Contaminated Sediment 1
Carol Ancheta
Demonstration of ADDAMS 13
Paul Schroeder
Overview of Ongoing Research and Development 15
Dennis Timberlake
U.S. Army Corps of Engineers Research Program 21
Norman Francingues
Biological Research 23
Gregory Sayles
MicrobFal Dechiorination and Bioremediation of PCBs 25
John Quensen
Phytoremediation of Sediments 33
Steven Rock and Dolloff F. Bishop
Treatment of Metal-Bearing Solids , 41
Thomas Stolzenburg
Treatment of Dredged Harbor Sediments by Thermal Desorption 49
Edward Alperin
Solvent Extraction Process Developments to Decontaminate Sediments 63
Phillip DiGasbarro '
Containment Research 77
Louis Thibodeaux
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Remediation Strategies and Options
for Contaminated Sediment
Carol! Ancheta
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
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Carol Ancheta
Carol Ancheta has her B.S. in biology from the University of Western Ontario and a certificate in
environmental management from Ryerson Polytechnic University. Ms. Ancheta currently works
for Environment Canada in the Remediation Technologies Program. Her responsibilities include
problem delineation, cost evaluation, and site management, and her project work includes the
Collingwood, Toronto, and Hamilton Harbors.
Ms. Ancheta has received many awards in her area of study, including "Best Technical Paper" at
the Western Dredging Association and Texas A & M University, and Environment Canada's Citation
of Excellence Award. Ms. Ancheta serves as an industry advisor to the University of Toronto,
Department of Engineering and Applied Chemistry, and the United States National Research
Council Committee on Contaminated Sediments. She is also the second vicepresident of Western
Dredging Association.
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Remediation Strategies and Options !
for Contaminated Sediment '
i
Presented by Carol Ancheta !
•Thunder Bay case study
•Using SEDTEC in decision-making
l\
REMEDIAL OPTIONS FOR CONTAMINATED SEDIMENT I
•Do nothing
•No immediate action
•Cap
•Contain
•In situ treatment
•Dredge
•Pre-treat
•Treat
•Dispose/re-use
WHEN IS REMEDIATION REQUIRED?
QUESTION:
Does the site pose a
threat to the ecosystem
and human health?
National Conference on Management and Treatment of Contaminated Sediments
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National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
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CONTAMINANT VARIABILITY
Lowest effect level TPAH = 4 ug/g
Severe effect level TPAH = 10,000 ug/g
Depth of Contamination
Station
1
2
0-25
2,694.21
1-40
55,940.12
40-50
14,821.62
50-60
1,553.09
57,309.02
60-80
1,004.92
60-100
10,663.61
WHEN IS REMEDIATION REQUIRED?
ANSWER:
Assess severity of chemical contamination.
Assess severity of biological contamination.
•benthic community structure
•fish community
•sediment bioassays
Uptake studies
Tissue residues
National Conference on Management and Treatment of Contaminated Sediments
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REMEDIAL OPTIONS FOR CONTAMINATED SITES
•Do nothing 'Dredge
•No immediate action »Pre-treat
•Cap 'Treat
•Contain *Dispose/re-use
•In situ treatment
J
THUNDER BAY - Remedial Action
•Contain
•Dredge
•Pre-treat
•Treat
•Dry Cap
•Re-use as industrial fill
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CONTAIN
Rubble Mound:
The core material is usually clay. The
core is surrounded by either:
1) fine granular material, increasing in
coarseness and grain size as it moves
outward away from the core
2) surrounded by a synthetic filter material
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DRY CAP
Placement of a large
volume of material over the
sediment so that the final
elevation of the cap surface
is above the water level.
TECHNOLOGY SELECTION
•cost
•productivity
•transportable
•environmental performance
•compatability with site
conditions/other technologies
•experience
SEDTEC
A Directory of Contaminated Sediment
Removal and Treatment Technologies
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SEDTEC OFFERS
«• INFORMATION - Strong reference too! for easy
access to the best technologies and information on
professionals operating in the field
•«• APPLICATION - Quick access to problem solving
and information services for clients with specialized
needs already working in the bussiness.
+ EXCHANGE - Detailed resource for vendors who
want to evaluate
SEARCH RESULTS SCREEN
DETAILS - Technology type and description
• COST - Operational performance costs and production rates
PROJECT- Case studies and projects with contacts for
technology auditos and funding agencies,
DEVELOPERS/VENDORS - Company names, locations &
contacts
PHOTO/SCHEMATIC - Diagram and picture of technology
LITERATURE - Technology literature references
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Demonstration of ADDAMS
Paul Schroeder
National Conference on Management and Treatment of Contaminated Sediments
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Paul R. Schroeder, Ph.D.
Dr. Paul R. Schroeder has a B.S. in cfvil engineering from the University of Illinois, an M.S. in
environmental and water resources engineering from Vanderbilt University, and a Ph.D. in civil
engineering from Ohio State University. He has worked as an environmental and research civil
engineer and has served as adjunct faculty for several universities. He has 18 years of research
experience in dredged material disposal obtained while working for the U.S. Army Corps of
Engineers.
Dr. Schroeder is currently employed with the U.S. Army Engineer Waterways Experiment Station
as a research civil engineer. He is working on the development of the Automated Dredging and
Disposal Alternatives Modeling System as well as several projects involving disposal of
contaminated dredged material. He is the author of the Hydrologic Evaluation of Landfill
Performance (HELP) model and won the American Society of Civil Engineers (ASCE) Horner
Award and the ASCE Hering Medal for his papers on the HELP model. He has served as an
assistant editor of the ASCE Journal of Environmental Engineering Division.
Dr. Schroeder will present a live computer demonstration.
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Overview of Ongoing
Research arid Development
Dennis Timberlake
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May 13-14, 1997
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Dennis Timberlake
Dennis Timberlake has a B.S. in chemical engineering from the University of Arizona and an M.S.
in chemical engineering from Oregon State University. He has been with the U.S. Environmental
Protection Agency's (EPA) Office of Research and Development for the last ten years.
Mr. Timberlake provides in-house technical assistance to regional efforts to remediate
contaminated sites and serves as the program manager for EPA's contaminated sediment risk
management research program.
National Conference on Management and Treatment of Contaminated Sediments May 13-14, 1997
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OVERVIEW OF
ONGOING RESEARCH
AND DEVELOPMENT
RESEARCH AND DEVELOPMENT
Dennis L. Timberlake
EPA/ORD/NRMRL
Overview
Problem Definition
NRMRL Efforts
Is there a need for researchon the treatment
of contaminated sediments?
Why Sediments are a Problem
Why Sediments are a Problem
High percentage of Fines
High Water Content
High Volumes/Low Concentrations
Ecological Effects
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Sediments to be Managed
Maintenance Dredging
Remediation
Maintenance vs. Remediation
Dredging
Cost Constraints
Timeline .
Scale
Level of Contamination
J
Research Areas
Existing Technologies
New Technologies
J
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EPA Survey and Expert Panel
In-Situ Treatment
High Volume/Low Concentration
In-Situ Containment
Current NRMRL Focus Areas
In-Situ Treatment
Treatment Within Disposal Facilities
Fate and Transport of Contaminants
Ex-Situ Management
Technical Assistance
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U.S. Army C6rps of Engineers
Research Program
Norman
Francingues
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Norman R. Francingues, Jr.
Norman R. Francingues, Jr., received his B.S. degree in civil engineering from Mississippi State
University in 1969 and his M.S. degree in civil (environmental) engineering from Mississippi State
University in 1971. He is a charter member of the Mississippi State Chapter of Chi Epsilon, an
honorary civil engineering fraternity. He has worked as an environmental engineer in the U.S.
Army Corps of Engineers and a commissioned officer in the U.S. Army Reserves during the past
26 years. His research experience spans such topics as wastewater management, toxic and
hazardous waste treatments, environmental restoration technology development and dredging, and
remediation of contaminated sediments. He is presently chief of the Environmental Engineering
Division at the U.S. Army Engineers Waterways Experiment Station, Vicksburg, MS. He also
directs the research activities of the WES Hazardous Waste Research Center.
Mr. Francingues has served as the principal Corps technical liaison on contaminated sediment
treatment to the U.S. National Research Council's Commission on Engineering and Technical
Systems Marine Board. He currently chairs the Permanent International Association of Navigation
Congresses Ten Member Nation Working Group on "Handling and Treatment of Contaminated
Dredged Material From Ports and Inland Waterways." Mr. Francingues is a member of Chi Epsilon,
the Society of American Military Engineers (SAME), the Permanent International Association of
Navigation Congresses (PIANC), and the Western Dredging Association (WEDA). He has more
then 100 publications to his credit.
No slides were available at the time this handout was reproduced.
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Biological Research
j
I
Gregory Sayles
National Conference on Management and Treatment of Contaminated Sediments
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No slides were available at the time this handout was reproduced.
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Microbial Dechlorination
and Bioreme;diation of PCBs
John buensen
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May 13-14, 1997
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John F. Quensen, III, Ph.D.
Dr. Quensen earned his B.S. in biology from Virginia Commonwealth University, an M.A. in marine
science from the College of William and Mary, and a Ph.D. in ecology from Purdue University. As
a post-doctoral trainee in environmental toxicology at Michigan State University, he developed an
interest in biodegradation research.
Dr. Quensen is currently an assistant professor at Michigan State University. For the past several
years his research has focused primarily on the anaerobic microbial dechlorination of PCBs and
related compounds. He has published several papers on the subject in Science, Applied and
Environmental Microbiology, and Environmental Science and Technology, and co-authored a
comprehensive review on microbially mediated PCB dechlorination with Donna Bedard of General
Electric.
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Microbial Dechlorination and
Bioremediation of PCBs
John Quensen
Michigan State University
East Lansing, Michigan
Outline
• Discovery, occurrence & importance of
PCB dechlorination
• Potential Limiting Factors
• Enhancing PCB Dechlorination
• Aerobic Degradation of Dechlorination
Products
• Toxicity Reduction
Occurrence of PCB Dechlorination
Acushnet Estuary (New Bedford, MA)
Escambia Bay (FL)
Hoosic River (MA)
Industrial lagoons
River Raisin, (MI)
Sheboygan River (WI)
Silver Lake (MA)
Waukegan Harbor (IL)
Wood's Pond (MA)
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Congener Specificity
Dechloriuation Acdvity
M
Q
H
H'
P
N
Susceptible Chlorines
Flanked & unflanked ntela
Hanked & unflanked para
Flanked para
Doubly flanked meta
Flanked para
Meta of 2,3- & 2,3,4- groups
Flanked para
Flanked meta
Importance of PCB Dechlorination
• Products are more biodegradable
aerobically
• Products have less bioaccumulation
potential
• Products are less toxic
• Is an intrinsic process
• Has potential for bioremediation
Potential Limiting Factors
• Insufficient electron donors
• Competing electron acceptors
• Limited bioavailability
• Toxic or inhibitory co-contaminants
«• Oil & grease
» Metals
• Congener specificity
National Conference on Management and Treatment of Contaminated Sediments
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Enhancing PCB Dechlorination
H Carbon additions
• Priming
i FeSO4 amendment
I Mixing
i Inoculation
Structure Initial Mole % Autoclaved Live
2-
4-
2-2-/26-
2-3-
2-4-/2S-
7.9
4.6
15
2.7
9.1
5
11
3
3
3
85
82
71
83
86
Aerobic Degradation of Dechlorination Products
Aerobic Degradation of Dechlorination Products
Structure
26-2-
34-/S-4-
2S-2-/4-4-
24-2-
26-3-7236-
Initial Mole % Autoclaved Live
2 1
4 42
4 27
3 50
4 3
2.8
1.4
1.4
10.7
2.5
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Aerobic Degradation of Dechlorination Products
Structure Initial Mole % Autoclaved Live
23-2-t26-4-
25-3-
24-3-
25-4-
24-4-
5.4
1.9
2.9
3
5.8
-2
16
20
32
-1
Aerobic Degradation of Dechlorination Products
Structure
34-2-/234-/23-S-
125-26-
25-25-CB/26-35-
24-25-
24-24-
236-25-/245-2S-
/24-S4-
Initial Mole %
1
2.4
25
4.2
1.4
Autoclaved
5
4
2
2
8
Live
6
3
1
7
1
Toxicity Reduction
Dcchlorination of Congeners with AhR-Mediated Activity
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AhR Mediated Toxicity Reduction
Sample
Non-dechlorinated 1242
SLdechlorinated 1242
RR dechlorinated 1242
3.1 , 5.7
<6 X 10-2** 7.8 X 10-2
<6 X 10-2** 4.7 X 10-2
*Units are pmole TEQ/nmole of PCBs.
**TEQlssay was less than the MDL.
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Phytoremediation of Sediments
Steven Rock and Dolloff F. Bishop
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May 13-14, 1997
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Phytoremediation of Sediments
Dolloff F. Bishop
Steven A. Rock
National Risk Management Research Laboratory
U.S. Environmental Protection Agency
Possible Applications of Plants to
Sediment Remediation
dewatering of dredged sediments
enzyme exudation
root zone oxygenation
containment and erosion control
r\
Dewatering sediments
Willows, poplars, and cottonwoods (family
Salicaceae) are phreatophytes:
— grow from cuttings
— roots thrive in saturated soils
— growth up to 4 m per year
National Conference on Management and Treatment of Contaminated Sediments
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Niagara Mohawk, New York Utility,
has planted dredged sediments
with willow trees
5 year old trees can use up to 100
gallons of water per tree per day
Enzyme Exudation
In the presence of contaminants certain plants exude
certain enzymes
— Duckweed (a wetland plant) produces
nitroreductase which reduces TNT
— Poplar trees produce dehalogenase which cleaves
chlorine fromTCE
EPA Athens Lab has conducted
wetland pilot scale tests with
duckweed on soil from Milan Army
Ammunition Plant, with up to 80%
decrease in TNT concentration
National Conference on Management and Treatment of Contaminated Sediments
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Oxygenation
Common reeds (Phragmites australis) have been
shown to release oxygen from roots
— small quantities, very close to roots
Containment and erosion control
Reeds, wild celery (Vallisnera americana), and other
aquatic and wetland plants hold soils through
spreading root structures
National Conference on Management and Treatment of Contaminated Sediments
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Mechanisms foi
Phyto
Physical Effect*
•Transptratlon of
• HydnMiHcContrtjfof
lion
i within the plant
of the dehalogenaae
/genase enzymes, which
helpc tatyze degradation
, ^r$yrK*£.
Enhanc»d RhtzocpJMn Blodagradatlon
^ , » Supplyc^^ftB^«^*'-L*"**
ed to shoots and
c ^
Mechanisms fo
Accumulatic
+ In Rot
+ Trans
shoot
n
ts •
ocatedto W
; and leaves j •'.'. ':.'. ... .,.'.'. ...^
;tals
Rhizofiltration
Intracellular
Sequestration
v J
Mechanisms fo
Physical Effi
PoplarTree
can use 25 •
of water pei
Transpiration
^ Cotton
0200 gal
tree per
DfVolatil
c Control
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
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T\
Mechanisms foi
Phytodegradatfi
+ Metaboli
+ Product! 3i
enzymes
degra* lation.
oxygenase
Photosynth ssis
IN
iy
Phytoremediation
(Phyte = plant, remedy = correct evil)
A set of processes which use plants to clean contamination in soil,
groundwater, surface water, sediment, and air.
Processes may include contaminant destruction, contaminant,
extraction, or a combination of techniques.
T\
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
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Treatment of M
rtal-Bearing Solids
Thomas
Stolzenburg
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
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Thomas Stolzenburg, Ph.D.
Thomas Stolzenburg has B.S. degrees in biology and natural resource management from the
University of Wisconsin-Stevens Point, and a Ph.D. in water chemistry from the University of
Wisconsin-Madison. He has worked as an environmental consultant with RMT, Inc., in Madison,
Wisconsin, for 14 years. Prior to that he conducted research on polychlorinated biphenyls (PCBs)
for Sea Grant on the Fox River in Wisconsin.
Dr. Stolzenburg is currently employed by RMT, Inc., as a senior consulting applied chemist and
national delivery manager. He is responsible for overseeing the proprietary in-house research on
waste treatment, which has resulted in numerous patents for RMT. The chemical treatment
processes developed in the Applied Chemistry Department at RMT, Inc., have led to the treatment
of over 1 million cubic yards of hazardous waste^ mostly for lead leaching.
National Conference on Management and Treatment of Contaminated Sediments May 13-14, 1997
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INC.
Treatment of
Metal-Bearing Solids
Using a Buffered Phosphate Stabilization System
Tom Stolzenburg, Ph.D.
Senior Applied Chemist
RMT, Inc.
'hemistry of Metals Fixation
Remedial Technologies for Metals
Solubility of Lead, Cadmium, Zinc
TCLP Test Results
Solubility After Treatment
'etal Treatment Alternatives
Solidification
Stabilization
- pH Control
— Chemical Fixation
Vitrification
Physical Separation
Thermal Extraction
Chemical Extraction
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
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tabittzation Alternatives
pH Control
-Lime
— Carbonates: limestone & dolomite
— Magnesium Oxide
Chemical Fixation
— Iron Hydroxides
— Phosphates
— SuHIdes: Dithioearbamates
Chemical Reduction
- Metallic Iron
'olubility of Lead, Cadmium and
Zinc is Dependent Upon:
• pH
• Concentration of Anions in the Solution
• Nature of Anions in the Solution
• Ionic Strength
'olubility of Lead Species as a
Function ofpH
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— -Srrg*.
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National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
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olubility of Cadmium Species as
'a Function ofpH
•7.BMT.K. /
^Zinc-Contaminated Site Soils
Zinc Solubility Curve
0.65 •
0.065 .
10 11
\
Foundry Waste
- i
7 9 11 13
PH
J
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
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^^Stabilization Approach
Convert ths Metals to a Form That Do Not
Leach in the Various Standard Leaching
Tests or In the Environment
Verify Stabilization Effectiveness With Both
Acid and Water Leaching Tests (E.G. TCLP,
SPLP, ASTM Water Leach, ANS 16.1, MEP)
"••L*
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whability of Smelter Waste
IJ— 4
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National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
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lydraulic Dredging and In-line
Treatment of Hazardous Sediment
• Achieved Clean Closure of a 17-Acre Lagoon
• Continuous Hydraulic Dredging With In-Line
Treatment; Rendered 370,000 Yd3 Of Sediment
Nonhazardous
• Constructed An On-Site Disposal Facility to Cost-
Effectively Dewater Sediment
• Achieved Waste Minimization by Applying an In-
Line Treatment Process to the Wastewater
System
J
'nderwater Treatment of
Hazardous Sediment
• Stabilized Lead and Rendered the Material
Nonhazardous to Significantly Reduce
Permitting and Disposal Costs
• Used Treatment Chemicals/Dosages to
Effectively Address Water Quality Concerns
• Controlled Dispersion of Hazardous
Sediment and Treatment Chemicals in a
Flowing Environment
• Achieved Adequate Mixing and Treatment
Underwater
. \J
^^\
tplicability of Buffered
Phosphate Chemistry
Iron Foundry Wastes
Steel Mills Wastes
Brass Foundry Wastes
Smelter Wastes
Battery Recyclers
Leaded Paint
Shooting Range Wastes
Mining Wastes
Lead Arsenate Pesticides
Ashes
Sludges
Sediment
Soils
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
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Treatment of Dredged Harbor
Sediments by Thermal Desorption
Edward Alperin
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
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Edward S. Alperin
Edward Alperin has a B.S. in chemical engineering from Lowell Technological Institute and received
his Qualified Environmental Professional registration in 1995. He has worked for IT Corporation
for the last 22 years and currently serves as director of the Technology Applications Laboratories,
which includes three laboratories in Knoxville and Oak Ridge, Tennessee, and the U.S.
Environmental Protection Agency (EPA) Test and Evaluation Facility in Cincinnati, Ohio.
Mr. Alperin is an IT senior technical associate. As the program manager for IT's Thermal
Desorption program, he was responsible for the development, design, construction, and
demonstration of the process including the treatment of sediments contaminated with compounds
such as polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), dioxins, and
mercury. He has published over 20 articles on thermal desorption and has recently served on a
task group for the American Academy of Environmental Engineers to prepare the second edition
of the Monograph on Thermal Desorption.
National Conference on Management and Treatment of Contaminated Sediments May 13-14, 1997
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Treatment of Dredged Harbor Sediments
by Thermal Desorption
By
Ed Alperin, Mary Hall, Stuart Shealy - IT Corporation
Keith Jones- Brooknaven National Laboratory
Presented at
National Conference on Management and Treatment of
Contaminated Sediments, May 13-14, Cincinnati, Ohio
Overview
•MM
• Harbor Sediment Problem
• Treatability Study Objectives
* Bench-Scale Testing and Results
— Dewatering
— Thermal Desorption
— Stabilization
— Biotoxicity Testing
* Conceptual Design and Cost
Contaminated Harbor Sediments
• Generated by routine dredging of shipping channels and
berthing areas
• Can contain heavy metals as well as toxic organics
• Frequently do not meet biotoxicity requirements for open
ocean disposal
* Estimated 500,000 cubic yards per year generated in COE New
York District
J
National Conference on Management and Treatment of Contaminated Sediments
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Disposition of Treated Sediments
• Unrestricted ocean disposal
* Burialln trenches excavated on ocean floor near current
disposal areas (with no treatment)
* Land disposal as non-hazardous material
* Beneficial use as construction fill or road base
• Beneficial use of monolithic waste form for construction of
artificial reefs (fish aggregation areas)
3 Stage Treatment Process
Treatability Study Objectives
• Identify dewatering characteristics and conditions
• Identifythermattreatmentcondttionsneededforremovalof
organlcs and secondary waste generation
• Develop stabilization formulations to reduce teachability of
toxic metals
* Demonstrate that treatment reduces blotoxicity of sediments
* Develop mass balance data for conceptual design and cost
estimate
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
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Newtown Creek Harbor Sediments
• Obtained by New York District of COE, using barge mounted
clamshell dredge
• Fine-grained, high organic content sludge, 34.6% solids
• Organo-chlorine pesticides were 462 ug/kg.
• PCB's were 2997 ug/kg.
• PAHs were 52^40 ug/kg.
• Dioxins/furans (as 2,3,7,8-TCDD TTEs) were 0.3 ug/kg.
• Leachable cadmium, copper, lead, nickel and zinc
Dewatering Tests and Results
••••••^••BranM
0 Release of free draining water in drainage beds
0 Filtration on a 4 inch pressure leaf filter
• Lime and filter aid added to improve filtration
0 Unable to significantly dewater sediments
• 36% of solids below 2u particle size
• 15 to 20% of solids were organic material
Thermal Desorption Testing
• All tests conducted in the Rotary Thermal Apparatus (RTA)
• Treatment matrix tests to identify effective treatment conditions
• Series of 26 RTA batches at selected treatment conditions used
to generate 14 kg of thermally treated material for stabilization
testing
• Condensate and offgas treatment residuals from production
run collected for analysis and mass balance data
National Conference on Management and Treatmenf.of Contaminated Sediments
May 13-14, 1997
53
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Rotary Thermal Apparatus (RTA)
• Bench-sole, batch charged rotary kiln (6"D X16")
• Indirectly heated byan electric furnace
• Can treat >pproxim»tely1 kg of sediment
• Purged with nitrogen
• Offgas is condensed in chilled spray column or in a series of
Impinger scrubbers
• Non-candensabte gas goes through carbon column
RTA Flow Sheet
IT'S Rotary Thermal Apparatus (RTA)
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
54
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RTA Off-gas Sampling System
Thermal Treatment Matrix Tests
• Four runs to identify effective treatment conditions
• Treatment conditions:
— 350°C for 5 minutes (at temperature)
— 450°C for 0 minutes
— 450°C for 5 minutes
— SSO'CforS minutes
• Treated soil analyzed for PAHs, PCBs and OCPs
• Treated soil analyzed for biotoxicity using screening tests
Thermal Treatment Matrix Test Results
• Treatment lowered PCBs, OCPs and PAHs to non-dectable
concentrations for all conditions
• Thermal treatment lowered biotoxicity of sediments
• Sediments treated at 550°C for 5 minutes had lowest biotoxicity
• 550°C with 5 minutes at temperature selected for production
runs
National Conference on Management and Treatments Contaminated Sediments
May 13-14, 1997
55
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Biotoxicity Screening Tests
• Treated and untreated sediments crushed to 3/8" and extracted
with "Instant CKcirtST solution
* Acute mortality for:
— Silverside Minnow (Menidia berylina)
— Mysid Shrimp (Mysidopsis bahia)
— Mussel Larvae (Mytilusedulis)
* Short-term chronic "observed effect" toxicity for mussel larvae
• Data normalized as Toxicity Units (toxicity relative to blank)
Thermal Matrix Biotoxicity Results
RTA Production Runs
Treated 25.0 kg of air dried sediments (43% solids) in 26 RTA
runs
RTA purge gas treated in series of 4 scrubber impingers and
small carbon bed
Collected condensate (aqueous and oil phases), carbon and
other residuals
Analyzed treated sediments and residuals for PCBs and
Dioxirts
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
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PCB and Dioxin/Furan Results
• PCBs in sediments lowered from 6969 u/kg to 1.8 u/kg (dry basis)
• Dioxins (2,3,7,8-TCDD TTF) in Sediments lowered from 695 to 154
ng/kg (dry basis)
• Thermal desorption produced 15.8 Ib condensate oil per 1000 Ib of
untreated sediment (dry basis)
* Condensate oil contained 452 mg/kg PCBs
and 28 ug/kg dioxin TTE
•• PCB and dioxin recoveries were 110 and 122%, respectively
• 93% of the PCBs and 52 % of dioxins were in the condensate oil
• Activated carbon contained 2 pg/kg dioxin TTE
Conclusions - Thermal Desorption Tests
• Thermal desorption is effective in removing toxic organics
(OCPs, PAHs, PCBs and dioxins) from sediments.
• Thermal desorption reduces biotoxictty of sediments.
• Thermal desorption produces significant quantities of
treatment residuals that contain PCBs and dioxin/furans.
Stabilization Testing Performance
Criteria
' Monolithic Waste Form
— UCS greater than 290 psi
— Leachable metals below TCLP limits
— Meet ocean disposal biotoxicity requirements
• Fill Material
— No free liquids
— Leachable metals below TCLP limits
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
57
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Stabilization Testing
1 Portland cement, class C fly ash, blast furnace slag and silica
fume used to stabilize the thermally treated sediments
' Formulations developed for monolithic waste form for artificial
reef construction and for soIWike material to be used as fill.
' 10 formulations were screened for physical characteristics and
metals teachability.
' 5 formulations screened for biotoxictty
1 5 kg of monolithic waste form sent to BNL for testing
GROUT MOLDS
Stabilization Results
' Thermally treated sediments contained significant levels of
teachable (TCLP) cadmium, copper, lead, nickel and zinc.
' M stabilization formulas resulted in effective fixation of metals.
(all metals but zinc were ND in TCLP leachate)
> Leachabto(TClP)zincwasreducedfrom2€.1 mg/L
to 0.115-0.076 mg/L.
' UCSofmonclith formulas ranged from 240 to 550 psi
' 5 formulations selected for biotoxicity screening
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
58
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Selected Formulations for Biotoxicity
Screening
Run*
PC
(grams)
FA
(grams)
BFS
[grams)
Water
(grams)
Monolithic Waste Formulations
3R 20
4 20
5 50
Formulations For Fill Material
9 5
10 5 (Lime)
d on 109s*
14
30
4
40
50
50
87
100
102
60
61
Biotoxicity Results
0 Stabilization did not improve biotoxicityas measured by
screening tests.
• Soil-like final waste forms had higher biotoxicity than thermally
treated sediments.
0 Increased toxicity of soiHike waste forms was probably due to
higher pH of extracts (caused by leachable lime).
Biotoxicity of Stabilized Sediments
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
59
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Conceptual Treatment Process
mammmm^mmmmmw
* Thermal drying to reduce water content to 30%
* Carbon treatment of dryer condensate and offgas
• Thermal desorpflon in rotary calciner
• Calcineroffgas treated In flameless oxidizer
• Treted sediments stabilized in batch mix plant
Conceptual Treatment Process
Cost Estimate
• Based on 100,000 cubic yards per year, 12 month-24 hr
operation
• C«piUICostJ23,650,OOOorS23.65pcrytf>ofs«iiment
• Utilit!es(pow«randfueOS21.48pery(P
• Ubor 519.99 ptrycP
* Maintenance, supplies and analytical 53.48 per yd3
• Stabilization reagents for soil-like waste form, S4.05 per yd3
• Total cost S72.M per ytP
• Add S16 per yard for m onolithic waste form ($8&64/yd*)
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
60
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National Conference on Management and Treatment of Contaminated Sediments May 13-14, 1997
61
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Solvent Extraction Process Developments to
Decontaminate Sediments
Phillip DiGasbarro
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
63
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Phillip DiGasbarro
Phillip DiGasbarro has a B.S. and an M.S. in chemical engineering from Tufts University and an
M.B.A. from New York University. He has worked as a chemical engineer and project manager for
both operating and engineering service organizations, including Stauffer Chemical Company,
RhonePoulenc, Inc., and Metcalf & Eddy, Inc. He has 25 years of experience in process design
and managing engineering and construction projects for the chemical, pharmaceutical,
biotechnology, and environmental industries.
Phillip DiGasbarro is currently employed by Metcalf & Eddy, Inc., as a senior project manager. He
is working on the M&E Integrated Sediment Decontamination System pilot plant project. This
decontamination project that treats sediment from the New York and New Jersey Harbor by soil
washing, solvent extraction, and solidification/stabilization to produce material that can be used for
landfill cover, construction fill, landscaping, or composting. He is a member of the American
Institute of Chemical Engineers (AlChE) and the American Maritime Association (AMA) and has
authored several reports.
National Conference on Management and Treatment of Contaminated Sediments May 13-14, 1997
64
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Solvent Extraction
Process Developments
to Decontaminate
Sediments
NATIONAL CONFERENCE ON
MANAGEMENT AND TREATMENT
OF CONTAMINATED SEDIMENTS
MAY 14,1997
Introduction
• Maintaining Navigational Access Will
Generate Significant Amounts of
Contaminated Sediments that Must be
Disposed or Treated Economically
• Regulated Contaminants in Sediment:
Heavy Metals
Polychlorinated Biphenyls (PCB's)
Oioxins/Furans
Introduction (continued)
• The Type and Level of Treatment Depend on
Variety and Concentration of Contaminants and
Proposed Disposal or Use of Sediments
• The Solvent Extraction Process can be used to
Remove Organics and be Part of Overall
Treatment Plant to Produce Usable Products
• Another Process Needed to Extract/Fix Heavy
Metals
J
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
65
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General Sediment Characteristics
and Issues
• A Black, Sticky, and Mayonaise-Like Muck
• High Water Content (As-ls at 60-70%)
• Salinity
• High % Fine Grain with Some Debris/Oversize
• Variety of Organic and Inorganic Containments
• Undefined Standards for Re-Use
Newtown Creek (NY Harbor)
Sediment Features
Physical Characteristics
Solids (%)
Gravel (% of solids)
Sand (% of solids)
Silt (% of solids)
Clay (% of solids)
30 - 40%
0.1 - 34%
35 - 47%
8-43%
10-65%
Newtown Creek (NY Harbor)
Sediment Features
Contaminants
Wotils
Arconle
Cadlutn
Chromium
Copper
Lead
Mercury
Nickel
Sliver
ZJno
Level (ppm)
5-33
1-20
100-400
61 -770
68-554
1-3
12-140
2-3
104-1260
TCLP(mg/I)
<0.1
<0.1
0.03
<0.05
-------
Newtown Creek (NY Harbor)
Sediment Features
Contaminants
Organ ICE
PAHs
Pesticides
Dloxlns/Furans (total)
PCBc (total)
Total Organic Carbon
Level
1-50 ppm
ND-177ppb
0.01 -15ppb
60-400ppb
2-8%
TCLP
< 0.01 mg/l
< 0.01- 0.0005 mg/l
<0.001 - 0.01 ng/l
0.0001 - 0.02 ug/I
Goals/Objectives of Solvent
Extraction Process
• Accept Variety/Levels of Organic Contaminants
• Accept Sediment As-ls for Pre-Treatment
• Remove the Organic Contaminants (One to
Several Orders of Magnitude)
• Produce Sediment at Optimal Moisture Content
for Next Operation
y
y
Solvent Extraction Alternatives
SttMTMd
FlxrStdinwitt
(AH-Ou.Slupp,}
This Is the Focus
of M&E's Process
Development
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
67
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Many Common Industrial Solvents
• Chlorinated Hydrocarbons (CHCI2, CHCI3,
PERC)
• Ketones (Acetone, MEK, MIBK...)
a Acetates (Methyl Acetate, Ethyl Acetate...)
H Alcohols (Methanol, Ethanol, Propanol...)
• Aromatics (Benzene, Toluene, Xylene...)
• Aliphatics (Propane, Butane, Hexane...)
NOTE; REGULATION OF HAZARD AND TOXIC COMPOUNDS
HAS REDUCED® ANNED USE OF SOME OF THESE SOLVENTS
1*1
Solvent Extraction Processes
Vmfor
AJTT
KCOtMntM
Cn/U-K
*»«_
lUfi
SettM*
^Bs.
(HowHaardoM)
00t.pn>pvi»,
•chtra
Ub(Ur»efupfc>
A«*t*!»*,Alcohota
fcrBr«
»jT»4mt
OAtm
OAbn
v-Tlow
er.
*
ioe»c
OAtm
Sotv«nU
SoU^nttyh
2nd:v*iylew
High at low T
Low *1 high T
V«ryH)gh«tTe.
Po and viry low
'
y^nu
M%
Analytic Methods for
Organics Use Solvent Extraction
• Method #8290 for Dioxin/Furans Uses Mostly
Non-Polar Solvents:
Toluene Acetone
Hexane Cyclohexane
Nonane Methanol
Methylene Chloride
• Method for PCB's
• Recovery of Organics is Very High!
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
68
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Solvents Selection Guidelines/Criteria
I Solvent(s) Should be Non-Toxic and If Possible Non-
Hazardous (non Flammable). If Flammable Process
Sholud be Inerted
I Solvent(s) are Easily Biodegradable (Important If Trace
Quantities Remain in Treated Sediment)
I Heterogeneous Solvents /Water Azeotropes Boil
Between Ambieute -100% and
I Reduces Fouling of Equipment Systems
I The Commercial Solvents are Inexpensive
I Solvent is Thermally Stable
I Solvents are Partially Polarwith Moderate Solubility in
Water
a
Single Contact Stage of Contaminated
Sediment and Solvents at Equilibrium
Water (A)
Solid Parttotof (&)
with Adsorbed
Organic Contaminants
+
SoV*nt
-------
Effect of Sediment Moisture
on Solvent Penetration
Solvent Recovery, %
Mo 8 fe 8 8 I
J
J
A
1
^*
=="
AOAUltfAlCOtld
Aztoeooo Blond
S 32 36 40 44
StxSmenl Solid Contont, %
NOTE: Initial Wet Sediment <9 42% Solids to Solvent Ratio = 1
Goals for Solvent Extraction Bench-Scale and Pilot Plant
Tests Recently Completed for NY/NJ Harbor Sediments
• Demonstrate Solvent Extraction
Technology with 5 -10 cy
• Generate Process Operating Information
• Generate Process Data for Full-Scale
Design
• Produce Useful, Recyclable End-Products
Pilot Plant Test Program Data
I Treated 5 cy of Screened Raw Sediment Directly by
Stabilization/Solidification
I Treated 5 cy of Screened Raw Sediment by Solvent
Extraction and Stabilization/Solification
I Solvent Extraction Test Run Conditions:
•3,5and7Extractionswrth Fresh Recycle Solvents)
•Two Solvents: Alcohol & Acetate
• Warm Temperature Extractions (120-140=0
• Mix Sediment and Solvent Moderately for 15 Min. &
SettleforlO min.Priorto Decanting Organic Layer
I
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
70
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National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
71
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Removal of Organic (ORG-X) and
Stabilization/Solidification (SOLFIX)
™£Ki
:SK: -, *
-Jt
Stabilization/Solidification
of Raw Sediment
Stabilization/Solidification
Test Run Conditions
Direct Stablllzatton^oIIdincatlon
Solvwit Extractlon/St^lllzatlon/SoIldHlcaUon
0.1 parts cement
02 parts cement
OA parts cement
0.15 parts cement
0.30 parts cement
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
72
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Solvent Extraction Variables
I Solvents Type (Hydrophobia
or Hydrophilic?)
I Solvent to Sediment Ratio
I Extractions Stages
I Solubility of Solvents) in
Aqueous Sediment Mixture
I Mixing Contact Time
I Intensity of Mixing
I Settling Time
! Extraction Temperature
Parameters / Constituents Analyzed by M&E
Light Hydrocarbons
Medium-Weight Hydrocarbons
Total Hydrocarbons
Heavy Hydrocarbons
Residual Carbon
Total Organic Carbon
% Removal
99.9%
86%
91%
92%
37%
30%
Constltuants Analyzed by BNL
PCBs
Pesticides
Chlorinated H eric ides
Dioxlns/Furans
% Removal
79-92%
94-98%
**
* Significant Amount Found in Solvent
** Solvent Contained 81 - 84% of Initial Dioxin
ITCLP Metals
ITCLPOrganics
Below MDL
Reduced up to 99%
\
Bench-Scale Chemical Results
Using 3-Stages and Acetate Solvent
Bench-Scale Chemical Results Using
3-Stages and Acetate Solvent (continued)
\
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
73
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Pilot Test
Dioxin, Furan and PCB Removal
Contvntunt/CtM*
Note: All analyses are on a dry basis
ORO-X&SOLFDC
Pilot Scife
aportHwrark
Physical Test Results
of Stabilized/Solidified Sediment
• Portlant Cement is a Practical Additive to
Solidify Product
• The Product is a Soft Concrete Material with Low
UCS of 10 -1000 psi for 10 - 40% Parts Cement.
Physical Characterization Data for
Stabilized/Solidified Sediment
CTAM./»Ot_
-------
Possible Uses for Stabilized/Solidified
Organic-Contaminant-Free Sediment
I Operational Daily Cover in Landfills
I Common Fill in Depressions, Sink Holes and Stripmine
• Interim Landfill Cover Prior to Top Soil Layer
• Interim Landfill Cover by Mixing Roam Soil
• Landscaping Soil by Mixing Other Materia
• Not acceptable for Road Subbase
T\
Guidelines for High Contaminant Removal
• Do Solvent Extraction of Contaminants in
Sediment in Aqueous Media to Have Low Energy
Cost
• Use Combination of Solvents to Attain Moderate
Sulibility in Water to Increase Diffusion of
Contaminant from Interior of Sediment Particle
Guidelines for High Contaminant Removal
(continued)
• Extract at a High Temperature, Which is Safe
Level Below Azeotropic Boiling Point of
Solvent(s)
• Use Intense Mixing to Improve Contaminant
Transfer from Particle to Organic Phase
• Use Sufficient Equilibrium Extractions with
Multistage Mixer-Settlers or Other Agitated
Contactors
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
75
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Containment Research
Louis Thibodeaux
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
77
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Louis J. Thibodeaux, Ph.D.
Dr. Louis Thibodeaux received his B.S. in petroleum-chemical engineering, and his M.S. and Ph.D.
in chemical engineering from Louisiana State University. Dr. Thibodeaux, American Institute of
Chemical Engineering (AlChE) Fellow, is the Jesse Coates Professor in the Department of
Chemical Engineering and Emeritus Director of the U.S. Environmental Protection Agency (EPA)-
sponsored Hazardous Substance Research Center South/Southwest at Louisiana State University.
His current areas of study include mass transfer in nature, transport processes in aquatic bed
sediment, and organic chemicals associated with aerosols. Dr. Thibodeaux worked at Dupont for
over two years, and then went to graduate school on a fellowship from the National Council for Air
and Stream Improvement before serving on the chemical engineering faculty at the University of
Arkansas for 16 years. '
Dr. Thibodeaux is the author of the widely-used university textbook, Environmental
Chemodynamics - Environmental Movement of Chemicals in Air, Water, and Soil, now in the
second edition. He has published over 100 journal articles and serves as a consultant to a number
of companies and government agencies. In 1991, Dr. Thibodeaux was a visiting professor at the
Ecole Nationale Superieure des Mines de Paris.; In 1992, he received AlChE's Environmental
Division Lawrence K. Cecil Award.
National Conference on Management and Treatment of Contaminated Sediments May 13-14, 1997
78
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Containment Research
Contaminated Sediment and
DrcdgedMaterials
by:
Louis J. Thibodeaux, Jesse Coates
Professor of Chemical Engineering
Hazardous S ubstance Research Center
South & Southwest
College of Engineering, Louisiana State University,
Baton Rouge, LA 70803
Presentation at National Conference on Management and
Treatment of Contaminated Sediments.
May 13-14,1997
Omni Nelherland. Cincinnati, OH
Objective
* A review of selected research which
addresses the science/engineering of
chemical containment in in situ and ex situ
CS and DM disposal options.
Introduction
«• Overview of research projects at Hazardous
Substance Research Center S/SW
» Dr. Danny D. Reible, Director
• Drs. M. Saunders and H. Ward, Co-Directors
Louisiana State University, Baton Rouge
» Georgia Institute of Technology, Atlanta
» Rice University, Houston
List of research projects and focus of Center efforts
National Conference on Management and Treatment
of Contaminated Sediments
79
May 13-14, 1997
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Overview of Containment
Technologies
•*• Natural Recovery
•*• In situ Capping
*• Confined Aquatic Contaminent
*• Confined Disposal Facility
*• Landfill
Natural Recovery
•*• in bed and boundary layer processes
•*• burial by clean sediment
4- biotransformation
•*• solid-porewater equilibrium(?) thermodynamics
•*• transport kinetics
•» much on-going activities but overall
understanding is poor
In situ Capping
* theory is highly developed and verified in
the laboratory for thick caps
*• thin layer caps; need theory and supporting
data for effectiveness
*• bed consolidation driven contaminant
release is unknown
•»• a pilot-scale testing site is needed
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
80
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Chemical Release
During Dredging
* field-scale measurements, New Bedford
Harbor demonstration
Confined Aquatic Disposal (CAD)
*• research emphasis is on containment loss
from CAD facilities
* mentoring on and around units
Confined Disposal Facility
(CDF)
* research emphasis is on losses from
containment facility
•* systematic ranking of locales performed
* through dike releases, wave pumping
*• release to air from drying beds of
dredged material
* redox changes
Landfill (?)
+ not unlike CDF..., but
••• research on potential for groundwater
contamination
J
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
81
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Conclusion
•» a limited amount of containment research related
to CS & DM is on-going (in comparison to
groundwater surface water and air)
* contaminant release research in the area has been
particles>water>air
* thermodynamic, chemical equilibrium (i.e. kj
type investigators have dominated over kinetic-
type transport ones in assessing chemical
"mobility" from containment facilities
Conceptual Illustration -
Containment, Dlapota! and Natural Recovery
TtehnologlM for Contaminated Bed Sediments
(A&p*tllmm ma ft. Pthumo, USAE, \ndabura, UlsshslppO
Uptutd . Eitmiyormrfaor
UpUndSoM
ContfiwnM DMpOOMn
Shall , &rtn
Confined... ContHrad
Natural Aqunjc
R»cov«ry
DetpOcunBuki
DtopoulfAbyual
: Plain)
e MEIWCNIISN"
MimCLC DCWKTKW"
BCBTMK3LOC4TIOH*
US fUBBUC AOVtCTtM
COLLOlO TRAHSWRT*
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
82
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(E) Untapped ContanlHUd £
BOU»0»RY^
"^'•-•TSg|
ii
"z«TeV*6
,,. •/ifSSSKSBSEpllI
tei^i^i^s^^
a> Cippti With ClBIB S.dintnt
FIGURE 1. IK-SITU CONTAINMENT OF COHTAMJMATED
8ED SEDIMENT
TaWe i • SeAmeni and CJwntoal Charaaeristes
Water S^otafcy
S. myl.
Organic-MFbcn
paditjon coetfieitfn:
H«rV/*Law
Constant
H, atnfjmVmol
WaiBfDifluswiiy
D^wrfftc^
RetafdwiDn Factor
R.
Loading. &cp 1
W^inykB
Uwtfmg, £jp 2
W^mjiftg
PyreM
C13
48
Ixl 0*
S&tlO4
1170
90
S2.i*ax
Pficnanttrene
Dibenzofuran
10
'
4.2 J 3.7
6x10 *
5.8x10* '
350 "
60
29.7i2.7
7.9x10*
6.0x10*
97
!S1i21
Bayou Manehac Scdimem
O»o»nic CarOan Cooient. f_ -OC2!
BuUt Otfwly, Pt- g'on' ' * 0
Porosity, c • O.S9
Sand. S -29
Silt. %- 37
Clay. W -3*
FIGURE 2. STRUCTURAL DIAGRAM OF CAPPING SIMULATOR CELL
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
83
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MEASURING S-S FLUX
F, = AV.CA /At.A
AV - volume collacted, cm3
CA - concentration, g/cra3
At - time of collection, sec
A - surface area of CSCi cm2
F - flux, a/cm2.sec
Laboratory Test to Field-Scale Design
Chemical Steady-State Flux vs. Cap Thickness
a s 10 >s so 2s so
;ircd
i,
NH4-N Steady-State Flux
vs Cap Thickness
* Data
Theory
0 S K> IS W »" 30
Cap Thickness (cm)
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
-------
SO 100 150 2(10 250
Tiinr{(lays)
Fi(jltre I Uncapped Hnx nf DUicnmfunin and Pftcnaoifirtne - urn 2
50 100 150 -200 250
Time-(flays)
TABLE 2. TCP BREAKTHROUGH TIME AND THE TIME
NEEDED TO APPROACH STEADY STATE
Sediment
. Calculated
Breakthrough Value j,
Tine (hrt t
Value
Tims for Calculated
Approach to Value
Steady State ut*8ni
(tirt Value
Balsam
7.1
5
49
48
Quartz Sand
9.3
6
7O
63
Tao River
(China)
11.7
1 1
77
80
University
Lake
68.8
48
467
650
1 Tht depth of cappfo} liyir for quartz tand wai O.6cn. The rest were O.7cm
b C&lculttKl from Eq.9
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
85
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BREAKTHROUGH TtUE (7*ers)
PC* MCUCTMIOUCH TWZ VS. IMftEjt OETTH
National Conference on Management and Treatment of Contaminated Sediments
May 13-14, 1997
86
U.S. GOVERNMENT PRINTING OFFICE PRINT ORDER # 61009
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