542-B-00-001
Table of Contents
EPA/ITRC/RTDF Permeable Reactive Barrier Short Course
Section
Permeable Reactive Barriers: Application and Deployment .............. -j
Introduction: Permeable Reactive Barriers (PRBs) for
Treating and Managing Contaminated Groundwater In Situ ____ ................. 2
Collection and Interpretation of Design Data I:
Site Characterization for PRBs ............................. 3
Reactive Materials I: Zero-Valent Iron ..... ........................... 4
Collection and Interpretation of Design Data II:
Laboratory and Pilot Scale Tests Design Calculations ......................... 5
Monitoring and Maintenance for PRBs
PRB Emplacement Techniques
PRB Permitting and Implementation
Reactive Materials II: Treatment of Metals by Fe° PRB Systems and
Non-Metallic Reactive Materials for Promoting PRB-Based Treatment ............ 9
PRB Cost Analysis and Comparisons ......... „ .................. 10
Bibliography ...................... ....... „ ................. ., 1
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Section 1
Permeable Reactive Barriers:
Application and Deployment
-------
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EPA/ITRC/RTDF
Permeable Reactive Barrier Short Course
Permeable Reactive Barriers:
Application and Deployment
U.S. Environmental Protection Agency (EPA)
Technology Innovation Office (TIO)
National Risk Management Research Laboratory (NRMRL)
Interstate Technology & Regulatory Cooperation Work Group (ITRC)
Remediation Technologies Development Forum (RTDF)
&EPA
Interstate Technology & Regulatory
Cooperation Work Group
The Interstate Technology & Regulatory
Cooperation Work Group (ITRC) is a state-led,
national coalition
ITRC's mission: to create tools and strategies to
reduce interstate barriers to the deployment of
innovative hazardous waste management and
remediation technologies
In Situ Permeable Reactive Barriers:
Application and Deployment
-------
What is the ITRC?
Environmental regulators working with
industry and stakeholders to:
• Support the nation's $200 billion environmental
technology industry
• Improve state permitting processes
• Speed deployment of technologies through
interstate and regulatory collaboration
Who is the ITRC?
In Situ Permeable Reactive Barriers:
Application and Deployment
-------
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What are the Products and Services
Offered by the ITRC ?
ITRC offers Trail Maps, called "Guidance Documents," to
guide regulators and users in the deployment of innovative
technologies.
These "Guidance Documents" come in three forms
• Technical / Regulatory Requirements
• Technology Overview
• Case Studies
Over 20 ITRC Guidance Documents are available for seven
different technology areas.
More details about ITRC are available at
http://www.itrcweb.org
Remediation Technologies
Development Forum
The Remediation Technologies Development Forum (RTDF),
sponsored by U.S. EPA, fosters partnerships between the
public and private sectors to undertake research,
development, demonstration, and evaluation efforts to
address mutual cleanup needs.
The RTDF consists of seven Action Teams focusing on
specific high-priority problems, such as chlorinated solvent
contamination, and innovative technologies, such as
permeable reactive barriers.
More details about RTDF are available at
.
In Situ Permeable Reactive Barriers:
Application and Deployment
-------
Course Developers
• Richard C. Landis—DuPont Company
m Robert Puls—U.S. EPA National Risk Management
Research Laboratory
• Matt Turner—New Jersey Department of
Environmental Protection
• John Vidumsky—DuPont Company
• John Vogan—EnviroMetal Technologies, Inc.
• Scott D. Warner—Geomatrix Consultants, Inc.
Acknowledgments
• Southern States Energy Board (SSEB)
• Eastern Research Group, Inc. (ERG)
• Environmental Management Support, Inc. (EMS)
• Coleman Research Corporation
• RTDF and ITRC course reviewers
• EPA course reviewers
• EPA Forums
• EPA Regions
In Situ Permeable Reactive Barriers:
Application and Deployment
-------
Goals for This Course
Provide timely and accurate information about
PRB design, construction, monitoring, and
economics
Provide practical tools for making regulatory
decisions concerning PRB design and
deployment
Course Topics
Introduction
Design Data—Site Characterization
Zero-Valent Metals
Design Data—Laboratory and Pilot-Scale Tests;
Design Calculations
Compliance Monitoring, Performance
Monitoring, and Long-Term Maintenance
In Situ Permeable Reactive Barriers:
Application and Deployment
-------
Course TopiCS (continued)
• Case Studies
• Design Exercise
• Emplacement Techniques
• Permitting and Implementation
• Non-Metallic Reactive Materials
• Economic Considerations
Why Provide This Course?
• Permeable reactive barriers may be appropriate
for more than 500 sites in the next 10 years
• The potential cost savings for using PRBs
instead of a conventional technology may
collectively range from $500 million to greater
than $1 billion
In Situ Permeable Reactive Barriers:
Application and Deployment
-------
Schedule
Day 1
.8:15-12:00
.12:00-1:00
.1:00-5:15
Day 2
.8:10-12:00
Welcome, Introduction, Site Characterization,
Zero-Valent Iron: Laboratory and Pilot Scale
Tests, Design Calculations, Compliance and
Performance Monitoring, Long-Term
Maintenance
Lunch, Case Study Presentation
Design Exercise, Emplacement, Permitting
and Implementation, Questions and Open
Discussion
Treatment of Metals, Non-Metallic Reactive
Materials, Economics, Questions and Open
Discussion, Wrap Up
Resources
• Course manual contains overheads for all course
topics
• Handouts
• Bibliography (primary references used in
development of course materials)
. RTDF, ITRC, EPA (TIO, NRMRL) Web site addresses
www.rtdf.org/barriers.htm
www.itrcweb.org
www.epa.gov/tio
www.epa.gov/ada/kerrcenter.html
clu-in.org
In Situ Permeable Reactive Barriers:
Application and Deployment
-------
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Section 2
Introduction:
PRBs for Treating and Managing
Contaminated Groundwater In Situ
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EPA/ITRC/RTDF
Permeable Reactive Barrier Short Course
Introduction
Permeable Reactive Barriers for Treating and
Managing Contaminated Groundwater In Situ
KTDF
&EPA
What?
A Permeable Reactive Barrier (PRB):
• A permeable zone containing or creating a
reactive treatment area oriented to intercept and
remediate a contaminant plume
• Removes contaminants from the groundwater
flow system by physical, chemical, or biological
processes
Introduction; Permeable Reactive Barriers for
Treating and Managing Contaminated
Groundwater In Situ
-------
Concept
Waste Area
Groundwater— . .,
Flow Direction-Aquifer
b)
Aquitard
Waste Area
-PRTZ
••^-Remediated
.•Owater
-PRTZ
Clean Water
Aquifer
Aquitard
Why Use a PRB?
• Treatment occurs in the subsurface
• Typical treatment is passive
• Lower costs than conventional methods
• Allows full economic use of a property
• Robust
• Monitoring can be focused
Introduction: Permeable Reactive Barriers for
Treating and Managing Contaminated
Groundwater In Situ
-------
Treatment Matrix
• Zone or material that promotes treatment
• Focus on zero-valent iron [Fe°]
to treat groundwater affected by
• chlorinated ethenes
• chlorinated ethanes
• chlorinated
methanes (some)
• dissolved metals
Treatment Materials;
Treatable Contaminants
Treatment Material
Target Contaminants Technology Status
Zero-valent iron
Reduced metals
Metal couples
Limestone
Sorptive agents
Reducing agents
Biologic electron
acceptors
Halocarbons,
reducible metals
Halocarbons,
reducible metals
Halocarbons
Metals, acid water
Metals, organics
Reducible metals,
organics
Petroleum
hydrocarbons
In practice
Field demonstration
Field demonstration
In practice
Field demonstration,
in practice
Field demonstration,
in practice
In practice,
field demonstration
Introduction: Permeable Reactive Barriers for
Treating and Managing Contaminated
Groundwater In Situ
-------
Hydraulic Control Systems
Controls velocity through the reactive media
Routes affected groundwater through the
treatment zone (horizontal and vertical)
Prevents migration around treatment zone
• funnel and gate, low permeability barriers
• continuous wall
Hydraulic Control Systems
Flow
Flow
Low Permeability
Barriers
Funnel & Gate
Continuous Wall
Map View
Caissons/Multiple Gates
Introduction: Permeable Reactive Barriers for
Treating and Managing Contaminated
Groundwater In Situ
-------
Current Applications
• Full-scale installations
• >20
• Pilot-scale demonstrations
• >40
• Laboratory-scale tests
. >ioo
• Feasibility assessments
. >1000 (likely)
Current and Future Research
• Expand list of treatable contaminants
• Faster reaction/treatment time
• Deeper (and more complex) emplacement
• Inexpensive reactive materials
• Less expensive emplacement
• Performance monitoring
• Longevity
Introduction: Permeable Reactive Barriers for
Treating and Managing Contaminated
Groundwater In Situ
-------
Research Organizations
• Government
. EPA, DOE, DOD
• Academia
• Waterloo, Stanford, Oregon Graduate Institute, Rice
• Industry
• DuPont, General Electric, Monsanto
• Private
• users and designers
Introduction: Permeable Reactive Barriers for
Treating and Managing Contaminated
Groundwater In Situ
-------
Section 3
Collection and Interpretation of
Design Data I:
Site Characterization for PRBs
-------
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EPA/ITRC/RTDF
Permeable Reactive Barrier Short Course
Collection and Interpretation of
Design Data I:
Site Characterization for
Permeable Reactive Barriers
KTDF
Path to PRB Design and
Emplacement
L
Site Characterization Data
Laboratory Testing | Conceptual Model
1
Pilot Test
I
Final Design '
I
Full-Scale Emplacement
Site Characterization for Permeable Reactive Barriers
-------
Purpose
To address the importance of characterizing a
site before reactive barrier installation
To identify the critical aspects of site
characterization
To discuss ways to get this information
Topics
• Goals
• Potential problems
• Site characterization issues
• Site characterization methods and tools
• Monitoring methods and approaches
Site Characterization for Permeable Reactive Barriers
-------
Goai = Passive Remediation System
The plume enters under the natural gradient
The entire plume is captured by the system
Regulatory concentration goals are achieved at
point of compliance
Potential Problems
• The plume could pass over, under, or around the barrier
• The groundwater flow direction or velocity might change
• Incomplete remediation as higher concentrations reach the barrier
• Loss of surface reactivity—precipitate coatings, etc.
• Barrier plugging, decreased permeability
Over Under Around
Side Views
Plan View
Site Characterization for Permeable Reactive Barriers
-------
Site Characterization Issues to
Address to Achieve Goal
i Hydrology
i Geology
i Contaminant distribution within the aquifer
i Geochemistry
• Microbiology
These parameters are not discrete, but highly interactive.
Hydrology
• Groundwater flow
• direction (gradient)
• velocity
• flux
• Seasonal changes in groundwater flow velocity,
direction (e.g. due to recharge events)
• Effects of nearby intermittent pumping
• Provide data for construction of groundwater
flow model
Site Characterization for Permeable Reactive Barriers
-------
CO
-e
Q.
Changes in GW Flow Direction
Time
Plume & Barrier
at Installation
Plume & Barrier
During Rainfall Event
Elizabeth City - GW Flow Direction
Site Characterization for Permeable Reactive Barriers
-------
Geologic Setting
Depositionai environment
• type, mineralogy, TOC
Stratigraphy
• depths and continuity of sand layers, clay layers,
bedrock
• keyed barrier or hanging wall
4. zones of water/contaminant movement
• degree of fracturing
Contaminant Distribution
• Identify contaminants and degradation products
• Plume location in all dimensions
• x, y, z, concentrations and time
• Is natural attenuation occurring?
• Has steady state been reached?
• Are the high concentration zones moving?
+ What concentrations will reach the wall?
Site Characterization for Permeable Reactive Barriers
-------
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Q.
Dynamic/Unstable Plume
Time
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Plume & Barrier
at Installation
, -
Plume & Barrier
,as Center of Mass
Moves Downgradient
Hydraulic Conductivity Distribution
Controls flux
May vary by several orders of magnitude
Site Characterization for Permeable Reactive Barriers
-------
Hydraulic Conductivity - MW 27
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Support Center, Elizabeth City, NC
Site Characterization for Permeable Reactive Barriers
-------
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Geochemistry Considerations
Oxygen concentration
• O2 is preferred electron acceptor
. high O2) increased Fe(OH)3 precipitation
Carbonate alkalinity
• precipitation of Fe(CO)3 (side rite)
• precipitation of Ca(CO)3 (calcite)
Sulfate concentration
• possible sulfide formation
Geochemical Models
Help in formulation of site conceptual model
Predict solubility-controlling minerals
Provide indication of what precipitates will form
in reactive zone
Site Characterization for Permeable Reactive Barriers
-------
Water Quality Parameters
. Major ions (Na, Ca, Mg, K, SO4, Cl, HCO3)
• Dissolved oxygen distribution
• Redox potential (Eh)
• Needed input parameters for geochemical
modeling
Geochemical Models used for PRBs
. MINTEQA2
. EQ3NR
.PHREEQE
. WATEQ4F
Site Characterization for Permeable Reactive Barriers
-------
CO
Q.
Eh-pH Diagram
SEM-EDS Data—Iron Sulfide
Site Characterization for Permeable Reactive Barriers
-------
SEM-EDS Data—Calcite
"particle
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* residence
^particle
^ residence
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Ethene
TCE
DCE
VC
Fe° + 1 .502 + 6H+ -> Fe(OH)3 + 1 .5H2
Rust
Fe2+ + CO32- -> FeCO3 (siderite)
Site Characterization for F'ermeable Reactive Barriers
-------
-S
.0.
Microbiology
• Upgradient natural attenuation of plume?
• Enhanced biodegradation
Microbiology Testing
Fatty acid profile (PLFA)
Dissolved H2 analyses
Site Characterization for Permeable Reactive Barriers
-------
Data Collection Prior to Implementation
of Site Characterization
• Existing monitoring well data
• water table depths
• water quality
• Historical records
• aquifer tests, maps
• statigraphy
• recharge areas
• drainage basins
Characterization Methods
Use push tool technologies where appropriate
• Geoprobe® and Hydropunch®
• cone penetrometers
Surface geophysical techniques
• ground-penetrating radar
• seismics
Map and model the results
• hydrologic
• geochemical
Site Characterization for Permeable Reactive Barriers
-------
Surface Geophysical Techniques
• Ground penetrating radar
• buried objects
• water table depth
• bedrock depth
• Seismics
• water table depth
• bedrock depth
• fractures
• strata thickness
Photo courtesy of Spectrum Environmental Services, Inc.
Push Tool Technologies
Driven rapidly and inexpensively
• more samples can be collected, allowing:
* denser coverage of the area
• evaluation of a larger area
Can collect water, soil, and soil-gas samples
Site Characterization for Permeable Reactive Barriers
-------
Push Tool Technologies
Discrete vertical delineation of aquifer
• better data on stratigraphic continuity
• depending on the tools, you can get:
• soil resistance to penetration
• soil saturation
• hydraulic conductivity
• electrical conductivity
• goechemical characterization
• NAPLs using laser-induced fluorescence, field GC
Geoprobe® Model 5400
Geoprobe® Model 4220
vl
Geoprobe® Model 540B ~ ^(
^*"mis*
Photos courtesy of Geoprobe Systems
Site Characterization for F'ermeable Reactive Barriers
-------
co
Q_
Geoprobe Cr and
TCE Data
Geoprobe vs.
Well Data
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-------
Conductivity Data vs.
Aqueous Chemistry
Hydrologic Characterization Tools
• Pumping tests
• Small-scale slug tests
• Lab permeameter tests
• Borehole f lowmeters
• Permeable flow velocity probes
• Potentiometric information
Site Characterization for Permeable Reactive Barriers
-------
Map and Model the Results
Will help to decide if data is sufficient
Aid in determining the design and location of
the reactive barrier(s)
Development of monitoring network design
Groundwater Flow Model
• Predict flow velocities under different
conditions
• Evaluate effectiveness of hanging wall
• Evaluate different funnel and gate designs
• A simple flow model usually sufficient
Site Characterization for Permeable Reactive Barriers
-------
Flow Models Used for PRB's
. MODFLOW
. FLOWPATH
•FRAC3D
Conclusions
• A thorough site characterization is needed for
the immediate and continued success of a
reactive barrier installation
• The "passive" nature of the technology makes
this critical
• Good hydrologic characterization essential to
remedial effectiveness
Site Characterization for Permeable Reactive Barriers
-------
Conclusions (continued)
Current conditions must be known and future
conditions predicted
Push technologies and surface geophysics offer
rapid, economical ways to get the needed data
Summary List of Field Design Data
• Groundwater flow, direction, velocity, temporal
and spatial variability
• Aqueous geochemistry (pH, Eh, DO, alkalinity,
sulfate, other cations-anions, TOC)
• Microbiology (natural attenuation?)
• Stratigraphy (esp. confining layers)
• Contaminant distribution, flux (3D and time)
Site Characterization for Permeable Reactive Barriers
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Section 4
Reactive Materials I
Zero-Valent Iron
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-------
EPA/ITRC/RTDF
Permeable Reactive Barrier Short Course
Reactive Materials:
Zero-Valent Metals
RTDF
&EPA
Path to PRB Design and
Emplacement
Site Characterization Data
i
Laboratory Testing
I Conceptual Model j
*| Preliminary Design
Pilot Test
I
Final Design
1
Full-Scale Emplacement
Reactive Materials I—Zero-Valent Metals
-------
Zero-Valent Metals
Promote degradation of chlorinated organic
compounds
Promote precipitation of redox sensitive trace
metals, radionuclides
Reactive Metal:
Desirable Characteristics
• Effective in removing contaminants of concern
• Compatible with subsurface environment
• Persistent over long time periods
• No adverse geochemical reactions or byproducts
• Low operating and maintenance costs
• Readily available
• Low to moderate cost
Reactive Materials I—Zero-Valent Metals
-------
I
CL
History
• Research at the University of Waterloo into in
situ VOC degradation, beginning in late 1980s
• Various metals could remove VOCs from
contaminated groundwater
• Iron is reactive, readily available and relatively
inexpensive
• Over 700 potential sites identified
Cooperative Technology
Development
• Initial research at University of Waterloo
• U.S. EPA RTDF/ITRC
• U.S. DOD-sponsored programs (VOCs)
• U.S. DOE-sponsored programs (trace metals)
• RICE Consortium (sequenced treatment)
• Industrial research groups (General Electric,
Dupont, Monsanto)
Reactive Materials I—Zero-Valent Metals
-------
Granular Iron
Typical Granular Iron Characteristics
Grain size range: 2.0 to 0.25 mm (-8 to +50 mesh)
Bulk density: 2.6 g/cm3 (160 Ib/ft3)
Specific surface area: ~ 1.0 m2/g
Hydraulic conductivity: 5 x 10~2 cm/sec (142 ft/day)
Cost: ~ $350 to $400 US/ton + shipping
Reactive Materials I—Zero-Valent Metals
-------
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Iron Specifications
• Low carbon content (typically less than 3%)
• Low level of trace metal impurities
• No surface films
Reaction Mechanism — VOCs
• Corrosion of iron drives reaction
• Iron provides electron source for reduction
(dechlorination) of organics
• Pathway is not complete stepwise
dechlorination
• More highly chlorinated compounds degrade
faster (TCE degrades faster than vinyl chloride)
Reactive Materials I—Zero-Valent Metals
-------
Thermodynamics of Iron as a Reductant
pH
Figure Courtesy P. Tratnyek, Oregon Graduate Institute
Reaction Summary — VOCs
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Reactive Materials I—Zero-Valent Metals
-------
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Q.
Reaction Location on iron Surfaces
IVktal Oxide Film Boundry Layer Bulk Soln
Figure Courtesy P. Tratnyek, Oregon Graduate Institute
Chemicai Process—VOCs
"\
-------
Observed Percent Molar
Conversions—Chlorinated Ethenes
66%»
PCE
100% Non-Chlorinated
End Products
4%a
30%a
•-pathway through(chloro)acetylene intermediates
rates will vary depending on iron type
Implications of Molar Conversions-
Chlorinated Ethenes
• Initial concentration of 10 mg/L TCE
• 920 mg/L cDCE
* 76 mg/L VC
Reactive Materials I—Zero-Valent Metals
-------
Molar Conversions-
Chlorinated Ethenes
0 5 10 IS 20 25 30 35 40 45 50 55 60
Residence Time (hr)
Observed Percent Molar
Conversions—Chlorinated Methanes
50%
50% 40%
CT > TCM >DCM . •
Non-Chlorinated
End Products
60%
Note: -Chlormethane (CM) may appear as an additional intermediate.
-DCM and CM are not degraded by Fe(0).
-will vary depending on iron type
Reactive Materials I—Zero-Valent Metals
-------
Implications of Molar Conversions-
Chlorinated Methanes
• Initial concentration of 10 mg/L CT
• 1.3mg/LTCM
• 1.1 mg/LDCM
Molar Conversions—
Chlorinated Methanes
10,000 9
CT
DCM
TCM
IS 20 25
Residence Time (hr)
30
35
40
Reactive Materials I—-Zero-Valent Metals
-------
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Q.
Common Compounds —
Concentration Ranges Treated
Compound
PCE
TCE
c/s1,2-DCE
VC
Concentration
Range
(ppb)
10 - 50,000
25 - 400,000
200 - 200,000
40 - 50,000
Compound
CT
TCM
1,1,1-TCA
Concentration
Range
(ppb)
100-25,000
50 - 20,000
45 - 600,000
Contaminants Treatable by Fe° in
PRBs
Organic Compounds
Methanes
Ethanes
Ethenes
• tetrachloromethane
• trichloromethane
• hexachloroethane
• 1,1,1-trichloroethane
• 1,1,2-trichloroethane
• 1,1-dichloroethane
• tetrachloroethene
• trichloroethene
• cis-1 ,2-dichloroethene
• trans-1 ,2-dichloroethene
• 1,1-dichloroethene
« vinyl chloride
Propanes
Other
• 1 ,2,3-trichloropropane
• 1 ,2-dichloropropane
• hexachlorobutadiene
• 1 ,2-dibromoethane (EDB)
• freon 113
• freon 1 1
e lindane
• N-nitrosodimethylamine
• nitrobenzene
Reactive Materials I—Zero-Valent Metals
-------
Contaminants With Unknown
Treatability
Organic Compounds
m chlorobenzenes
• chlorophenols
• certain pesticides
• PCBs
Common Contaminants Presently
Not Treatable by Fe°
Organic Compounds
m dichloromethane (methylene chloride)
• 1,2-dichloroethane
• BTEX compounds
• petroleum hydrocarbons
Reactive Materials I—Zero-Valent Metals
-------
•fi
Q.
Changes in Inorganic Groundwater
Chemistry
• Introduction of Fe2+ •> ferrous hydroxide
precipitates
• pH increase
• Carbonate equilibrium affected -> carbonate
precipitates
• Sulfate reduction -> sulfide precipitates
• Implications for long-term performance
Inorganic Chemistry
Downgradient
•" &~
ckgrouncf
bijffertncj desclution
capaorty
of aquifer »lEh
minor Op dmusion/dissolution
^<
s flow volocitNVaquifcrcorKliljpm,
Reactive Materials I—Zero-Valent Metals
-------
Waterloo Permeable Reactive Wall
Field Trial 1991
• CFB Borden, Ontario, Canada
• Unconfined sand aquifer
• Groundwater flow velocity: 9 cm/day
• Water table: 2.5 m bgs
• Groundwater contaminants
. TCE 253 mg/L
• PCE 43 mg/L
• Reactive wall (20 m3)
• 22% granular iron and 78% coarse sand
Waterloo Field Trial
Reactive Materials I—Zero-Valent Metals
-------
Waterloo Field Trial
Waterloo Field Trial
Reactive Materials I—Zero-Valent Metals
-------
Waterloo Permeable Reactive Wall
Field Trial 1991
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Reactive Materials I—Zero-Valent Metals
-------
Waterloo Permeable Reactive Wall
Field Trial 1991
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Distance Along Flow Path (m)
Waterloo Permeable Reactive Wall
Field Trial Results
• Almost 5 years of consistent operation
• 90% TCE and 86% PCE removal
• Breakdown products (e.g., vinyl chloride)
degraded
• Insignificant amounts of precipitates
Reactive Materials I—Zero-Valent Metals
-------
Current Status (Fall 1999)—
PRBs for VOC Removal
• 30 full-scale systems
• 20 private facilities
. 5 U.S. DOD facilities
. 3 U.S. DOE facilities
• 2 other government facilities
Field Projects
» Full-Scale
• Pilot-Scale
Australia
Belfast
Denmark (3)
' Germany (3)
Reactive Materials I—Zero-Valent Metals
-------
3
Q.
Technology Acceptance
1992 1993 1994 1995 1996 1997 1998 1999
Year
Primary Contaminants Treated
PCE
TCE
cDCE &VC
111TCA&
11DCA
Reactive Materials I—Zero-Valent Metals
-------
Long-Term Performance Data
Organic
• Consistent VOC degradation over several
years
• No evidence of microbial fouling
• No site has yet required "retrofitting" or iron
replacement due to loss of reactivity
• PRBs have been extended at some sites to
achieve "complete" plume capture
Long-Term Performance Data
Inorganic
• Most carbonate precipitates occur at
upgradient interface (coring evidence) or in
upgradient mixed iron/gravel zones
• Accumulation of precipitates over time may
cause porosity/permeability loss
• No evidence of hydraulic plugging due to
precipitates
Reactive Materials 1—Zero-Valent Metals
-------
Trends in Field Applications
• Database degradation rates in design
• Decrease in granular iron costs
• Sand-iron mixtures to accommodate
construction constraints
• Increase focus on plume characterization to
minimize installation costs
• Combined PRB/natural attenuation remedies
Technology Advancements
• Degradation/removal of other contaminants
• Enhancements to increase degradation rates
• Long-term O&M procedures (if needed)
• Innovative installation techniques
• Sequenced treatment (metal/biological)
• Source zone remediation
Reactive Materials I—Zero-Valent Metals
-------
Source Zone Remediation
Create low flux, high residence time
environment
Bentonite/kaolinite plus a low % of iron
introduced into DNAPL source zone
DNAPL residual dissolves, reacts with
iron
Laboratory and field trials (3)
Synergy with Natural Biodegradation
Processes
• Both are reductive processes
• PRB enhances reducing environment
• Understand processes and incorporate into
design
• Barrier location relative to source and
compliance point
• Relative reaction rates of parent and daughter
products
• Take advantage of available space and
residence time for natural biodegradation
Reactive Materials I—Zero-Valent Metals
-------
€
D.
Combining PRBs with Natural
Biodegradation Processes
TCE
Concentration
cd
ct
\ Perm
\ Bar
Compliance
Point
eable
rier
^ Design
^^- — Basis
^•^^^^ ' Target
^ Concentration
Distance
Cost Effective PRB Design
Not
Compliant
Compliant
Overkill ,
_
1'
i
1 ~ •>. Compliance
1 ^__^^ Point
l
Plume PRE
fl
Treated Plume in
Panels Equilibrium
Distance
Reactive Materials I—Zero-Valent Metals
-------
-------
Section 5
Collection and Interpretation of Design
Data II:
Laboratory and Pilot Scale Tests
Design Calculations
-------
-------
m
•e
Q.
EPA/ITRC/RTDF
Permeable Reactive Barrier Short Course
Collection and Interpretation of
Design Data II:
Laboratory and Pilot-Scale Tests
Design Calculations
BTDF
Path to PRB Design and
Emplacement
| Site Characterization Data
I
| Laboratory Testing | Conceptual Model
*| Preliminary Design f — '
._. J.,_ '
1 Pilot Test 1
| Final Design |
Full-Scale Emplacement
Collection and Interpretation of Design Data II
Laboratory and Pilot-Scale Tests
Design Calculations
-------
Why Perform Laboratory Testing?
• Complex ambient water chemistry
• Atypical contaminants
• additives
• complex organic compounds
• Laboratory tests can be designed to confirm
assumptions (i.e., inexpensive)
• Comprehensive laboratory testing can be
reserved for most complex cases
Types of Laboratory Tests
Batch Tests
• contaminants of
unknown
treatability
• static conditions
• relative reactivity of
different materials
Column Tests
• contaminants
known to degrade
flowing conditions
treatment rate in
candidate material
Collection and Interpretation of Design Data II
Laboratory and Pilot-Scale Tests
Design Calculations
-------
Schematic of Set-Up for Batch Tests
Aluminum Crimp Cap
Teflon-lined Septa
Simulated or Site Groundwater
Glass Vial
Reactive Granular Iron Material
Batch Reactivity Tests
Collection and Interpretation of Design Data II
Laboratory and Pilot-Scale Tests
Design Calculations
-------
Interpretation of Batch Test Data -
VOCs
• Plot VOC concentration vs. time
• Apply first-order rate equation to calculate half-
life
First Order Kinetics
C/CL = e-kt
o
In (C/C0) = -kt
C = measured or desired concentration
C0 = initial concentration
k = first order rate constant (t-1)
t = time
Collection and Interpretation of Design Data II
Laboratory and Pilot-Scale Tests
Design Calculations
-------
•e
a.
Half-Life (t 1/2)
t1/2 = ln(2)/k = 0.693/k
Usually expressed in units of minutes, hrs, days
Literature values may show "normalized" k, t1/2 (unit
surface area of reactive metal/ml of water)
Column Studies
Site groundwater
Simulate site conditions (flow rates through
PRB)
Determine removal/degradation rates
Changes in inorganic chemistry
Collection and Interpretation of Design Data II
Laboratory and Pilot-Scale Tests
Design Calculations
-------
Possible Triggers For Column
Studies
• Nitrate levels
• Non-chlorinated organic carbon content
• Dissolved oxygen
• DCA/DCM production
• Guar-based installation methods
• High (100s mg/L) total VOC concentrations
Column Treatability Study
Plexiglas
Column
Effluent Samples
QD
Solution Reservoir
Sampling
Ports
-T Influent Pump
Sampling -
Port
Collection and Interpretation of Design Data II
Laboratory and Pilot-Scale Tests
Design Calculations
-------
Laboratory Column
Apparatus
Interpretation of Column Data-
VOCs
• Plot VOC concentration vs. distance along
column
• Convert to concentration vs. time profiles using
flow rate
• Apply first-order rate equation to calculate
half-life
Collection and Interpretation of Design Data II
Laboratory and Pilot-Scale Tests
Design Calculations
-------
TCE
60
Flow Velocity=46 cm/day (1.5 ft/day)
ft Vs. = 0.45 hr)
Flow Velocily=85 cm/day (2.8 ft/day)
0 2.5 5 10 15 20 30 40 50
Column Distance (cm)
cDCE
500 -
450 -
DJ
•== 400 •
~ 350 -
^ 300 -
0)
O otrn
e 250 -
o
O 200 •
{§ 150 -
E?
o 100 -
50 -
0 -
100% Granular Iron
\
\ \ ^
\ \TXX**\ Flow Velocity=85 cm/day (2.8 ft/day)
\ \ t /a = 2.3 hr
\ \
t V4 = 2.0 \ Y
^, \
Row Velocity= "^^^^ \ r-i
46 cm/dav (1 .5 WdayT^*^ \ X^-v-
S^L ^^^_
0 2.5 5 10 15 20 30 46 5^
Column Distance (cm)
Collection and Interpretation of Design Data II
Laboratory and Pilot-Scale Tests
Design Calculations
-------
•fi
Q.
vc
Flow Velocity=
46 cnn/day (1.5 ft/day)
Flow Velocity=
85 cm/day (2.8 ft/day)
5 10 15 20 3"0
Column Distance (cm)
Column Treatability Test Results
Compound
PCE
TCE
c/s1,2-DCE
VC
Typical
Half-Life
(hours)
0.5-2
0.5-2
2-6
2-6
Compound
CT
TCM
1,1,1-TCA
1,1 -DCA
Typical
Half-Life
(hours)
0.5-1
1-3
0.5-2
10-24
Collection and Interpretation of Design Data II
Laboratory and Pilot-Scale Tests
Design Calculations
-------
Rate Constants for Degradation by Iron
Methanes
PCM
TCM
HCA
Ethanes
1122TeCA
1112TeCA
111TCA
Ethenes
PCE
TCE
11DCE
112DCE
C12DCE
VC
O CD ODO«D
O>»> O
O »O
O O « O
O [FTfrfifc (D ®
O • O
O«E>
0»0
I0'5 10'" 10* 10'2 10°
kSA (Lm2hr-1)
Reference: Johnson, etal., 1996, EST30(8), 2634-2640
Residence Time Calculation—
VOCs
• Assume concurrent production and degradation
of each VOC in solution
• Express this concurrent production and
degradation using first-order kinetic model
• Determine total residence time required
• Adjust residence times to account for lower field
groundwater temperatures
Collection and Interpretation of Design Data II
Laboratory and Pilot-Scale Tests
Design Calculations
-------
in
-e
Q.
Residence Time Calculation
VOCs
Co.
I"
o
I
0>
o
0
o
Cor
Total Residence Time = tc > 1A > tB
Co Initial
Concentration
PC Performance
Criteria
t Residence
Time
Residence Time (hr)
Residence Time Calculation—
10mg/LTCE
10,000
•n—i—^—i—i—
0 5 10 15 20 25 30 35 40 45 50 55 60
Residence Time (hr)
• Required residence time is 48 hrs, depending on degradation of VC
Collection and Interpretation of Design Data II
Laboratory and Pilot-Scale Tests
besign Calculations
-------
Geochemicai Modeling of
Inorganic Column Data
Assess mechanism of trace metal removal
Examine potential precipitation/stability of
various mineral phases using saturation indices
Decline in carbonate species can be used to
make (very) preliminary estimate of porosity
loss over time due to carbonate precipitation
Groundwater Flow Modeling Studies
• Determine design velocity through treatment
zone
• Determine length of system required to capture
plume
• Assess potential for bypass/underflow
Collection and Interpretation of Design Data II
Laboratory and Pilot-Scale Tests
Design Calculations
-------
in
-e
Q.
Groundwater Flow Modeling Studies
• Combine aquifer characteristics and reactive
material properties
• Effects of reactive material variability
• Effects of changing material properties
over time
• Permeable barrier configuration
• Identification of monitoring well locations
Groundwater Velocity through a PRB
For a continuous wall, groundwater velocity can
be approximated using the aquifer velocity:
V= Ki/n
V = groundwater flow velocity
K = hydraulic conductivity
i = hydraulic gradient
n = porosity
Model simulations are likely necessary for a
funnel and gate configuration
Collection and Interpretation of Design Data II
Laboratory and Pilot-Scale Tests
Design Calculations
-------
Example PRB Flow Model-
Assumptions
Hydraulic conductivity:
Homogeneous Aquifer: 10ft/d
Pea gravel: 500 ft/d
Iron: 50 ft/d
Hydraulic Gradient: 0.01 ft/ft
Pathline tick mark interval: 200 days
Head contour: 0.5 ft
Model Results—Uniform Flow Field
r
s-I
*
<4o
Collection and Interpretation of Design Data II
Laboratory and Pilot-Scale Tests
Design Calculations
-------
Model Results—Non-Uniform Residence Time in Gate
Model Results—Modified Gate Design
Collection and Interpretation of Design Data II
Laboratory and Pilot-Scale Tests
Design Calculations
-------
Model Results—Funnel and Multiple Gates
Model Results—Continuous Wall
Collection and Interpretation of Design Data II
Laboratory and Pilot-Scale Tests
Design Calculations
-------
in
.p
Continuous Wall—
-Warren AFB
•»• impermeable cap\^
K=0.000283 ft/day >
(10-' cm/sec) Mf-
'/ * '
15 ft - V -
;,/ ,
K=40 ft/day
i=0.01
I 3ft
feofV':
^ \,- ^\ K=142 ft/day
'„,•:.' .'i (5xlO-2 cm/sec)
4ft
Model Results—Warren AFB
Hydruilk Head* and Smain
FtONET
(c) 1991
by WHS
*WCC«
E»i»pot
MM:
5.000E-01
Mu:
QjQUJB+QQ
be:
2.500E-02
Mia:
lOOOEtOl
Mu:
O.OOOE+O)
Inc:
1.0005-01
Unlu:
Collection and Interpretation of Design Data II
Laboratory and Pilot-Scale Tests
Design Calculations
-------
Dimensions of PRB
• Residence time requirement (bench scale
studies/database)
• Treatment zone flow velocity (model results)
• Thickness = residence time x groundwater velocity
• Determine length and depth of system required to
capture plume, prevent underflow
Field Applications
Pilot-scale testing
• at field site
• above-ground reactor
• small in situ system
• may or may not be needed depending on application
Collection and Interpretation of Design Data II
Laboratory and Pilot-Scale Tests
Design Calculations
-------
IO
•S
Q.
Pilots Demonstrating
"Proof of Concept"
• Data collection, velocity measurements, coring
• New York, 1995
• Lowry AFB, 1995
. Moffett Federal Airfield CA, 1996
. Dover AFB, DE, 1997
Pilot Installation—Moffett Field
Collection and Interpretation of Design Data II
Laboratory and Pilot-Scale Tests
Design Calculations
-------
Pilot Installation—
Moffett Field
Pilot Installation—
Lowry Air Force Base
Collection and Interpretation of Design Data II
Laboratory and Pilot-Scale Tests
Design Calculations
-------
in
•fi
Q.
Measuring Groundwater Velocity in a
PRB
• Water level measurements
• Tracer tests
• In-well, in-situ meters
• uncertainty in results must be recognized
Pilot Installation—New York
Collection and Interpretation of Design Data II
Laboratory and Pilot-Scale Tests
Design Calculations
-------
Success in Meeting Regulatory
Criteria
In Situ Installation, New York (May 1995)
Compound
Influent
Cone, (ppb)
Downgradient
Cone, (ppb)
TCE
cDCE
VC
32 - 330
98 - 550
8.1 - 79
<1 -1.6
< 1 - 7.6
Uncertainty in Measured Pilot-Scale
Degradation Rates
Detection Limit
jRepanea Cancefitmtian!
Distance
Collection and Interpretation of Design Data II
Laboratory and Pilot-Scale Tests
Design Calculations
-------
in
•S
Q.
Pilot-Scale Degradation Rates
In Situ Installation, New York (May 1995)
Compound
Predicted
Half Life3
(hr)
Observed
Half Lifeb
(hr)
TCE
cDCE
VC
0.4 to 1.1
1.5 to 4.0
2.0 to 6.0
<4.0
3.0 to 5.0
5.0 to 10.0
a from laboratory studies
b two point curves using detection limit as second point and measured
field velocity
Full-Scale Design and Implementation
• Is a pilot needed?
• Is model refinement needed?
• Hydraulic and geochemical characterization along
line of installation
• Choice of construction method vs. PRB
dimensions
• Development of monitoring plan
Collection and Interpretation of Design Data II
Laboratory and Pilot-Scale Tests
Design Calculations
-------
I
-------
Section 6
Monitoring and Maintenance for PRBs
-------
iiiflM iiiiiii n i ill ill i ill
is?:! °!h:
i"'i;'!in'll!" ,'!!tti'!', li .- '' I1
"If f ], I
.11 ii 'I
,!:, a lli'l:":
TJCI ' • ••M^list *•',;: • it
ItliSl: (fil; ,v
|<|ll|i;} ji'i;1
ii!,:':i Jiiiiiih,
iiiiiii' li<
it
•i
iiiiiii i
MliOiiW ! tl
-------
1
CD
t5
-------
Monitoring at PRB Sites
Monitoring program dependant upon objective
• Two programs applicable to PRBs
• compliance monitoring
• performance monitoring
Compliance Monitoring
Objective
• determine compliance with the applicable groundwater
standard or criteria
Regulatory requirements for monitoring
Focus is on the site and compliance point
Monitoring and Maintenance for
Permeable Reactive Barriers
-------
Procedure
• Identify groundwater standard/criteria
• Develop monitoring network based on
groundwater modeling
• Determine compliance points/wells
• Prepare monitoring plan/QAPP
• Monitor for compliance with standard
Monitoring Well
Construction Methods
• Aquifer wells
• follow state-specific requirements for installation
• Wells within or near the PRB
• small-diameter wells (1-2" wells)
• typically no sand pack or grout required
• installation
• suspended in reactive media prior to backfilling
• pushed or drilled into the reactive media
Monitoring and Maintenance for
Permeable Reactive Barriers
-------
Installation of Monitoring Wells
Pilot Permeable Reactive Barrier
Moffett Federal Airfield
Monitoring Well Placement at
Moffett Field
Monitoring and Maintenance for
Permeable Reactive Barriers
-------
Monitoring Well Placement at
Moffett Field
Sampling
Representative samples require special
procedures
Retention time within PRB cannot be
compromised
For all wells—low-flow sampling procedure
recommended
For wells within or near the PRB—low-flow
sampling and collection of smaller sample
volumes is necessary
Monitoring and Maintenance for
Permeable Reactive Barriers
-------
Low-Flow Sampling
• Benefits for PRB
• lower purge volume, slower rate
• representative samples of mobile fraction within
groundwater
• retention time within PRB unaffected
• more "passive" sampling method
Low-Flow Sampling Procedure
• Use of peristaltic, low-speed submersible or bladder pumps
• Continuous monitoring of water quality parameters
• dissolved oxygen
• specific conductance
• redox potential
• turbidity
.pH
• temperature
• Sample collected upon equilibration of parameters
• ±10 percent for DO and turbidity
• ±3 percent for conductance
• <0.3 feet groundwater drawdown
• Typical purge rate 100-500 mL/min
Monitoring and Maintenance for
Permeable Reactive Barriers
-------
CD
t5
CD
Monitoring Frequency Considerations
• Groundwater flow velocity
• Reactive media residence time
• Contaminants of concern
• Fluctuation in contaminant concentration
• Location and placement of PRB
• Seasonal fluctuations in groundwater elevation
Monitoring Frequency
• First quarter after installation
. monthly monitoring—analytical and field parameters
• weekly monitoring—groundwater levels
• Initial monitoring program (1-2 years)
• quarterly monitoring—analytical and field parameters
• monthly monitoring—groundwater levels
• Long-term monitoring
• frequency of monitoring can be reduced based on
operational stability
• Post-closure monitoring
• monitoring for teachable constituents of reactive media
or contaminants of concern
Monitoring and Maintenance for
Permeable Reactive Barriers
-------
Monitoring Frequency
Suggested Permeable Reactive Barrier Monitoring Frequency
For Inorganics and Radionuclide Contamination
Parameter
Frequency
A - First Quarter After Installation
Field Parameters
Inorganic Analytes***
Inorganic Contaminants
Radionuclides
Groundwater Levels
Monthly
Weekly (until equilibrium is reached)
B - Initial Monitoring Program
(1 - 2 years)
Field Parameters
Inorganic Analytes***
Inorganic Contaminants
Radionuclides
Groundwater Levels
Quarterly
Monthly, then to be determined
C - Long Term Monitoring
Field Parameters
Inorganic Analytes***
Inorganic Contaminants
Radionuclides
Groundwater Levels
Quarterly
(may be modified based on
performance)
D - Post-Closure Monitoring
Inorganic Contaminants of
Concern
Leachable Constituents from
Reactive Media
Radionuclides of Concern
To be determined based upon the
closure method and data collected
during operation of the PRB
-------
Suggested PRB Monitoring
Frequency For Chlorinated
Solvent Contamination
1
Parameter
Frequency
A - First Quarter After Installation
Field Parameters
Organic Analytes
Inorganic Analytes
Groundwater Levels
Monthly
Monthly
Monthly
Weekly (until equilibrium is
reached)
B - Initial Monitoring Program
(1 - 2 years)
Field Parameters
Organic Analytes
Inorganic Analytes
Groundwater Levels
Quarterly
Q u arterly
Quarterly
Monthly, then to be determined
C - Long Term Monitoring
Field Parameters
Organic Analytes Quarterly
(may be reduced based upon
Inorganic Analytes «r^ntirt|1-nr«ftnH1ity)
Groundwater Levels
D - Post-Closure Monitoring
Inorganic Parameters (Fe & To be determined based upon
other leachable constituents) data collected during operation
-------
Monitoring Parameters
Field and Laboratory Parameters
Analyte or Parameter
Field Parameters
Water Level
pH
Gtoundwater temperature
Rcdox Potential
Dissolved Oxygen
Specific Conductance
Turbidity
Salinity
Organic Analytes
Volatile Organic Compounds
(VOCsHcJ
Inorganic Analytes
Metals Id]: K,Na,Ca,Mg,
Fe,Al,Mn,Ba.V,Cr*J,Ni
Metals: Cr*
Anions; SO,, Cl, Br, F
NO,
Alkalinity
Other
TDS
TSS
TOC
DOC
Radionuclides
Reid Screening
Cross a /Gross p activities
(screening)
Specific Isotopes
(Am,Cs,Pu,Tc,U)
Analytical Method
ample Volume
[b]
ample Container
Preservation
In-hole Probe
In-hole Probe or Flow-thru
Cell
In-hole Probe
Flow-thru Cell
Flow-thru Cell [a]
Field Instrument
Field Instrument
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
USEPA SW846, Method
8240
USEPA SW846, Method
8260a or b
40 CFR, Part 136, Method
624
40 mL
40 mL
40 mL
Glass VOA vial
Glass VOA vial
Glass VOA vial
4°C, pH<2
No pH adjustment
4°C, pH<2
No pH adjustment
4°C,pH<2
No pH adjustment fi
40 CFR, Part 136, Method
200.7
40 CFR, Part 136,
or HACH method
40 CFR, Part 136, Method
300.0
40 CFR, Part 136, Method
300.0
40 CFR. Part 136, Method
310.1
lOOmL
200ml
lOOmL
lOOmL
lOOmL
Polyethylene
Glass, Plastic
Polyethylene
Polyethylene
Polyethylene
4°C, pH<2,
(HN03)
4°C
4°C
4°C
4°C
40 CFR, Part 136,
Method 160.2
40 CFR, Part 136,
Method 160.1
40 CFR, Part 136,
Method 415.1
40 CFR, Part 136,
Method 415.1
100 mL
100 mL
40 mL
40 mL
Glass, Plastic
Glass, Plastic
Glass
Glass
4°C
4°C
4°C,pH<2(H2SO4)
4°C,pH<2(H2SO<)
HPGe gamma spectroscopy
FBDLER
Gas Proportional Counting
Alpha Spectroscopy
Gamma Spectroscopy
None
[e]
125ml
M
4L
None
[e]
polyethylene
W
polyethylene
None
[e]
pH<2, (HNO3)
W
pH<2, (HNO3)
Sample Holding Time
None
None
None
None
None
None
None
None
14 Days
7 Days
14 Days
7 Days
14 Days
7 Days
180 days
24 hours
28 days
48 hours
14 days
7 days .
7 days
28 days
28 days
[e]
N/A
[e]
6 months
[a] - If <1.0 mg/L use photometric field kit for analysis.
{b] - See Section 7.4 (Sampling) of this report for variances in sample volumes.
(c] - GC methods may be substituted once identity of compounds and breakdown products are verified.
[d] - Other metals analytes which are characteristic of the media should be included.
[c] - General guidelines, the parameter is a laboratory specific parameter.
-------
CD
o '
o
Monitoring Frequency
Dependent on groundwater velocity and
groundwater modeling
After installation an equilibrium period may
occur during which data may not represent the
steady state monitoring conditions of the PRB
Periodic evaluation and adjustment of
monitoring program should be conducted
Compliance Monitoring Parameters
• Field parameters—pH, temperature, redox
potential, dissolved oxygen, conductance,
turbidity, salinity, groundwater level
• Organic analytes (as necessary)
e contaminants of concern and by-products
• Inorganic analytes (as necessary)
• Radionuclides (as necessary)
Monitoring and Maintenance for
Permeable Reactive Barriers
-------
Monitoring Well Placement
• Groundwater modeling will determine the
placement and the number of monitoring wells
required
• Wells may need to be installed in different
water-bearing units or at multiple levels within
the same water-bearing zone
• Dependent on configuration of PRB
(i.e., funnel and gate vs. continuous wall)
• Negotiations between involved parties
General Guidelines for
Well Placement
• Upgradient of PRB
• Downgradient of PRB
• Sidegradient of PRB
• Possible within PRB (if PRB installed within a
plume)
Monitoring and Maintenance for
Permeable Reactive Barriers
-------
i
CD
Hypothetical Example of Monitoring Well Placement
Figure 2 Funnel and Gate
Groundwater Flow
Hypothetical Example of Monitoring Well Placement (cont.)
Figures Continuous Wall
Permeable Reactive Barrier
^\
D •
D_^
~T*~"
• F
•
C
-
C
C
•
Note: For reference only. Site specific
conditions must dictate placement
• B
— -—Reactive Media
^B
*B
•
Not to Scale
Groundwater Flow
F
1 Plan View
KEY: FlowUnej
0 Potential Monitoring
Monitoring and Maintenance for
Permeable Reactive Barriers
-------
Performance Monitoring
Objective
• verification of performance of wall as designed
• also an element of QA for installation/emplacement
» verification of achievement of intended
hydrogeochemistry
Not typically considered regulatory monitoring
requirements
Focus is on the wall itself, not the site or
compliance points or boundaries
• early warning for decrease in wall performance
Performance Monitoring-
Extent/Scope
Duration and extent of monitoring
determined by:
• site-specific hydrogeochemistry
• performance sampling objectives
• negotiations among involved parties
• current status of specific barrier technology
development, maturity
Monitoring and Maintenance for
Permeable Reactive Barriers
-------
1
Performance Monitoring—What
Changes in system reactivity
Changes in site and reactive wail hydraulics
over time
Changes in contaminant residence time
Short circuiting
Performance Monitoring
System reactivity
• collection of core samples of the reactive media
• analysis of emplaced iron over time
• surface precipitates
• Geochemical indicator parameters
+ pH, redox potential, DO, ferrous iron, sulfide, alkalinity
• inexpensive field tests
Monitoring and Maintenance for
Permeable Reactive Barriers
-------
SEM Photo-Iron Surface
Precipitation of Oxides on Iron
Figure Courtesy P. Tratnyek, Oregon Graduate Institute
Monitoring and Maintenance for
Permeable Reactive Barriers
-------
1
Performance Monitoring
Site and reactive wall hydraulics
• head measurements
• pumping tests
• slug tests
• tracer tests (research)
• in situ flow meters
Performance Monitoring
Contaminant residence time or short circuiting
e contaminant degradation/transformation
• analysis of contaminants of concern and by-products
«• monitoring within or in close proximity to the reactive
media
Monitoring and Maintenance for
Permeable Reactive Barriers
-------
Performance Monitoring—
Multi-Level Sampling
• High resolution of vertical distribution of
contaminants and other water quality data
• "Passive" sampling of groundwater necessary
• Identify short circuiting or changes in residence
time affecting contaminant removal
• Effective for tracer testing
Design Plan for the Permeable Barrier Installed
at the Somersworth Sanitary Landfill, NH
Cross-Sectional
View (ETI, 1996)
3/4"
diameter
Vertical
4/ Depth
I of
I Backfill
Vertical
Depth of
Reactive
Material
] coarse sand
1 reactive gate material
Thickness of
Reactive Material —>
(4ft)
| clay backfill U monitoring well
I bedrock
Monitoring and Maintenance for
Permeable Reactive Barriers
-------
1
Performance Monitoring
Scope and extent of performance monitoring
expected to decrease as
• longevity of reactive media can be accurately
predicted
• increasing acceptance of technologies
Long-Term Maintenance
Operation and maintenance plan
• contingency sampling plan
Closure plan
Monitoring and Maintenance for
Permeable Reactive Barriers
-------
Long-Term Maintenance
Operation and Maintenance Plan
• Contingency sampling plan necessary in the event the
PRB fails to meet performance or compliance criteria
• porosity/permeability reduction
• carbonate precipitates occur at upgradient interface
» iron (oxy) hydroxides form on iron surface
• microbial fouling
• Hydraulic considerations
• contaminant bypass
• incomplete plume capture
Long-Term Maintenance
Operations and Maintenance Plan
Reactive media restoration or replacement - WHY?
• loss of permeability through the reactive media
• potential for PRB to be a future contaminant source
• spent reactive material
• contaminant desorption from reactive media
• concentrations of contaminants (metals or
radionuclides) in reactive media affect disposal
options
• reaching reactive capacity of the media
Monitoring and Maintenance for
Permeable Reactive Barriers
-------
Long-Term Maintenance
Operations and Maintenance Plan
Reactive media restoration or replacement - HOW?
• may consist of mechanical restoration or replacement
of affected section
• rejuvenation technology is in development stage
• ultrasound techniques
• a lump sum cost could be budgeted into O&M once
every 5-10 years
Passive Collection with
Reactor Cells
Collection Trench w/,
Impermeable Barrier
Remediated
Groundwater
Reactor Cells w/
Reactive Medi
Direction
USDOE Rocky Flats Mound Site Plume, Tetra Tech EM, Inc. 1398
Monitoring and Maintenance for
Permeable Reactive Barriers
-------
Long-Term Maintenance
Closure Plan Considerations
• Future use of property and the need for
institutional controls
• Cost of removal vs. long-term operation and
maintenance
• Regulatory requirements for closure
• Changes in hydraulics and non-contaminant
downgradient water quality
Long-Term Maintenance
Long-term maintenance requirements current
subject of intensive research
• issues to be addressed
• longevity
• hydraulic capture
Monitoring and Maintenance for
Permeable Reactive Barriers
-------
Section 7
PRB Emplacement Techniques
-------
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-------
•e
Q_
EPA/ITRC/RTDF
Permeable Reactive Barrier Short Course
PRB Emplacement Techniques
RTDF
SEPA
Path to PRB Design and
Emplacement
Site Characterization Data
. Laboratory Testing
Conceptual Model
Preliminary Design
T
'•Pilot Test'-.
I
Final
Design I
I Full-Scale Emplacement I
PRB Emplacement Techniques
-------
Overview
• Current emplacement methods
• Recent emplacement advances
Permeable Barrier Configurations
• Continuous reactive wall
• Funnel and gate
• Alternative designs
• in situ reactor
• GeoSiphon cell (WSRC)
PRB Emplacement Techniques
-------
CO
Q.
Continuous Reactive WaSSs
Wall of reactive material extends across entire
plume
• continuous zone of reactive material
• no impermeable sections
• little disturbance of groundwater flow
PRB Emplacement Techniques
-------
f
Funnel and Gate
• Low permeability funnel
• potential for flow around and beneath system
• Permeable treatment gate
• higher velocity created in treatment zones
• well-defined treatment zone facilitates monitoring
Conceptual Funnel and Gate
Low Permeability Wall
Pea • Gravel
Granular
Iron
_ Pea • Gravel _
• • •
Permeable Gate
Low Permeability Wall
Groundwater Flow
Monitoring Well*
PRB Emplacement Techniques
-------
1
0.
Comparison of Treatment Systems
Continuous
Wall
Volume reactive material Large
Residence time Greater
Flow system disturbance Small
Monitoring zone Large
Full-Scale Systems
• >20 continuous reactive walls
• cofferdam (6)
• trenching machine (8)
• hydrofracturing (1)
• 5 funnel and gate systems
• slurry wall (3)
• sheet piling (1)
. HOPE (1)
• 3 in situ reaction vessel systems
Funnel
and Gate
Large
Less
Large
Small
PRB Emplacement Techniques
-------
I
Full-Scale Treatment Systems
Continuous Wall
• Sunnyvale, CA
• Sunnyvale, CA
• Elizabeth City, NC
> South Carolina
• New York
• Superfund Site, NJ
»Kansas City, MO
• Denmark (2)
> Fairfield, NJ
• Watervliet, NY
• Sumter, SC
• Louisiana
• Seneca, NY
• Germany
Funnel & Gate
• Coffeyville, KS
• Lakewood, CO
• Colorado
• Oregon
• Vermont
Other
• Northern Ireland
• RFETS, CO
•Savannah River
Example Site
100 ft. long, 30 ft. deep, 1.8 ft.f low-through thickness
Construction Mobilization Construction Iron
Method
(unit cost)
1993 Funnel and Gate $50,000 $175,000 $312,000
(sheet pile funnels)
Continuous Trencher $75,000 $50,000 $189,000
(SSOO/linear feet)
Vibrated Beam/Mandrel $75,000 $120,000 $189,000
($10/sqtt)
Jetting $50,000 $110,000 $189,000
($40 /sat sq ft)
Bioslurry Trench $50,000 $30,000 $189,000
($10/sqft)
Note*; Unit costs are based on discussions with contractors (trencher, mandrel) or reported literature values (letting Bioslurry trench)
Total
$537,000
$314,000
$384,000
$349,000
$269,000
PRB Emplacement Techniques
-------
•e
D.
Case Studies Illustrating
Design/Emplacement Issues
1) Funnel and gate, sheetpiling
2) Continuous wall, trencher
3) Continuous wall, hydrofracturing
4) Continuous wall, jetting
Denver Federal Center
PRB Emplacement Techniques
-------
I
Site Design Summary
In-situ System, FHA Facility, CO (Oct/96)
Impermeable Zone
-1,040 ft total length
Treatment Zone:
- 4 treatment zones
- 40 ft wide (each), 20 ft depth
- 5 to 10 ft saturated thickness
Influent Groundwater
- TCE and DCE isomers
- (< 700 ppb), VC (< 15 ppb)
Cost
Construction $675,000
Granular Iron $225,000
Total
$900,000
Site Design Summary
In-situ System, FHA Facility, Co (Oct/96)
Construction
• Lateral variation in concentration and velocity
used to minimize iron costs
• Sheet pile "funnel" installation difficult due to
complex, difficult, iithology
• "Fast track" implementation schedule
PRB Emplacement Techniques
-------
•2
•6
. Q.
Permeable Reactive Barrier Configuration
FHA Facility, Colorado
COA-at 4
(tow
1
QATE4
South-North X-Section
PRB Emplacement Techniques
-------
Primary Groundwater Contaminants
atPRB
1,1,1-TCA
1,1-DCE
TCE
cis-DCE
vinyl chloride
200 n,g/L
230
600
170 [ig/L
Boundary of Denver Federal Center
Looking to the West
PRB Emplacement Techniques
-------
Denver Federal Center-Ground Water Contours
Denver Federal Center-TCE Contours
PRB Emplacement Techniques
-------
f
Denver Federal Center-Sheet Pile Installation
Vibratory Hammer Driving Sheet Pile
PRB Emplacement Techniques
-------
-s
Q.
Denver Federal Center-Gate Construction
Denver Federal Center-Placing Fe° in Cell 1
PRB Emplacement Techniques
-------
I
Template for Reaction cell
Denver Federal Center-Wall Construction
PRB Emplacement Techniques
-------
Denver Federal Center-Wall Completion
Multi-Level Piezometers, Cell 2
PRB Emplacement Techniques
-------
I
Denver Federal Center-Gate 2
Denver Federal Center-Water Levels
PRB Emplacement Techniques
-------
15
•e
Q.
Denver Federal Center-Water Levels
WATER LEVELS ACROSS 3HEET PILE
-
^1^^
Denver Federal Center—
Contaminants
PRB Emplacement Techniques
-------
Denver Federal Center-
Geochemistry
Denver Federal Center-
Microbiology
PRB Emplacement Techniques
-------
1
•s
•8
Q.
Summary
High microbial activity in iron and sediments
Low permeability upgradient sediments near
cell 2
Problems with flow
PRB Emplacement Techniques
-------
-------
I
Q.
PRB Emplacement Case Study
Continuous Wall
Case Study - New York Site
• Site located in Syracuse area
• 100s of ppb TCE, cDCE, TCA requiring
treatment
• Water table at 3 ft bgl, clay zone at 15 to
17 bgl
PRB Emplacement Techniques—prbSacasestud
-------
Rationale For PRB Implementation-
New York Site
• PRP no longer active at site
• Savings of at least S0.6M relative to pump and
treat
• Shallow plume
• Contaminants amenable to treatment
Site Design Summary
Pilot-Scale In Situ System, New York (May 1995)
• Impermeable zone:
• 15 ft of scalable joint sheet pile on either side of
treatment zone
. 15 ft depth
• Treatment zone:
. 10 ft length
• 31/a ft flow-through thickness
• Influent groundwater:
• 100s of ppb TCE, cisDCE, TCA
PRB Emplacement Techniques—prbSacasestud
-------
-9
Q.
Pilot-Scale PRB
Construction, May 1995
Pilot-Scale PRB
Construction, May 1995
PRB Emplacement Techniques—prbSacasestud
-------
Pilot Scale Installation—New York
Pilot-Scale Installation—New York
PRB Emplacement Techniques—prbSacasestud
-------
•8
a.
Permeable Reactive Barrier Configuration
New York, Pilot-Scale
*D4 -D5 «D6
t
5ft
15ft
P1
P3
Pea Grayelv , , ( | (
^ Iron Filingsy- ;•" Direction of GW flow
Monitoring Well
'
New York
Observed VOC Concentrations Along the
Center Transect — New York
Weil Location
Upgradient Pea Gravel
Midpoint of Iron Zone
Downgradient Pea Gravel
Concentration Along Center Transect (mg/L)
TCE
Oct.
1995
160
<1.0
1.5
June
1997
189
2.0
<1.7
cDCE
Oct.
1995
450
2.0
7.5
June
1997
98
<7.8
15
VC
Oct.
1995
79
<1.0
1.2
June
1997
53
<0.7
<0.7
PRB Emplacement Techniques—prbSacasestud
-------
Changes in Inorganic Chemistry Along
Center Transect — New York
Chemical Parameter (unit)
Ca (mg/L)
Fe (mg/L)
Mg (mg/L)
HC03 (mg/L)
CI (mg/L)
S04 (mg/L)
pH
Eh (mV)
Monitoring Well Location
U2
90.6
<0.1
12.7
291
47.4
17.2
7.39
261
FE2
9.6
0.158
7.33
47.8
49.2
<5.0
9.46
-459
D2
15.4
<0.1
4.23
56.5
42.8
<5.0
8.56
-156
D5
33.6
0.159
5.95
Na
Na
--
7.06
-16.5
Groundwater Velocity Through the
Pilot PRB
• Model prediction -1 ft/day
• Head measurements < 0.66 to 1.3 ft/day
• Tracer test 1.3 to 1.6 ft/day
• Velocity meter (Sept. 1996) 0.66 ft/day
• Velocity meter (June 1997) 1 to 2.3 ft/day
PRB Emplacement Techniques—prbSacasestud
-------
.a
.a
a.
Coring of Pilot PRB—New York Site
• 2 years after installation
• Angle cores to examine upgradient
interface
• Total carbonate, SEM, microbial analyses
Coring of PRB—
New York
PRB Emplacement Techniques—prbSacasestud
-------
Cross Section of Core Sample
Locations, NY
New York-
Content
•Core Analysis, Carbonate
12 18 24
Flow-Through Distance (in)
30
36
PRB Emplacement Techniques—prbSacasestud
-------
.a
£
a.
New York—Core Analysis,
Microbiai Populations
2.5E+06
2.0E+06 - -
1.5E+06 ••
l.OE+06 -•
S
5.0E+05 - •
O.OE+00
12 18 - 24
Flow-Trough Distance (in)
30
36
Core Results—New York Site
• Carbonate precipitates predominate and occur
only within a few inches of the upgradient
interface
• Porosity decline from 0.55 to 0.5 postulated (?)
• Reactivity maintained after 2 years
• No evidence of microbial fouling
PRB Emplacement Techniques—prbSacasestud
-------
Site Design Summary
Full-Scale System, New York (1997)
• Two parallel continuous treatment walls (100%
iron):
. 120 ft length Wall A
• 370 ft length Wall B
• 1 ft flow-through thickness on each wall
. 18 ft depth (T 3')
• Cost (including design, materials, site
preparation/restoration) = $797,000
Continuous Wall vs. Funnel and Gate
• Less hydraulic uncertainty with
continuous wall relative to funnel and gate
• Continuous wall less expensive than
funnel and gate system
PRB Emplacement Techniques—prbSacasestud
-------
_Q
s
Q.
Design of Continuous Wall
Industrial Facility, New York
Monitoring,'WeMs
Flow Direction
PRB Installation Using Continuous
Trencher
• "one pass" PRB installation
• Most trenchers have a depth limitation of
25 feet
• Rapid installation
• QA/QC issues with respect to volume of
iron emplaced
PRB Emplacement Techniques—prbSacasestud
-------
I
Permeable Reactive Barriers
Zero-Valent
Iron Permeable
Reactive Barrier
Reductive Dechlorination
EUiene
Courtesy of GeoSyntec
PRB Emplacement Techniques—prbSacasestud
-------
Funnel and Gate
Permeable Reactive
Material
Groundwater Flow
Low-Permeability
Funnel
Courtesy of GeoSyntec
Continuous Wall
Permeable Reactive Material
Groundwater Flow
Courtesy of GeoSyntec
PRB Emplacement Techniques—prbsacasestud
-------
Elizabeth City, NC
Continuous Trenching
Continuous Trenching for
PRB Installation
PRB Emplacement Techniques—prbSacasestud
-------
Continuous Trenching for
PRB Installation (com.)
n
Continuous Trenching for
PRB Installation (com.)
PRB Emplacement Techniques—prbSacasestud
-------
Continuous Trenching for
PRB Installation (com.)
Continuous Trenching for
PRB Installation
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PRB Emplacement Techniques—prbSacasestud
-------
.a
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PRB Installation (com.)
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PRB Installation (com.)
Granular
Iron
PRB Emplacement Techniques—prbSacasestud
-------
Continuous Trenching for
PRB Installation (com.)
Granular
Iron
Continuous Trenching for
PRB Installation (cont.)
Granular
Iron
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PRB Emplacement Techniques—prbSacasestud
-------
Continuous Trenching for
PRB Installation (com.)
Granular
Iron
Continuous Trencher
PRB Emplacement Techniques—prbsacasestud
-------
Continuous Trencher
Full-Scale Monitoring—New York
• Quarterly monitoring program
• Consistent flow through system observed
• With thin PRBs, vertical alignment of wells is
very important
• Wells in iron show VOCs below detection limits
• VOCs in aquifer downgradient of wall make
treatment efficiency difficult to determine along
entire length of wall
PRB Emplacement Techniques—prbSacasestud
-------
1
Recent Advancements in PRB
Emplacement
Alternatives to Excavation and
Trenching
Incentives for Emplacement
Advancement
• PRB depth
• need to go deeper
• emplacement across selected depth
intervals
• Construction issues
• obstructions (overhead and
underground)
• unstable soils
• worker safety and exposure
PRB Emplacement Techniques
-------
Incentives for Emplacement
Advancement
PRB thickness
• many applications require only a few inches of
iron
Cost
• construction costs
• disposal of spoils
• reduce excessive iron usage
Half-Life Discussion
TCE has a half life of about 1 hour for
treatment with zero valent iron
If GW velocity is 1 foot per day
• 12 inches/day
• 2 hours of residence time per inch
• 2 half lives for each inch of iron thickness
• 12 half lives requires 6 inches of iron
PRB Emplacement Techniques
-------
Half-Lives (continued)
TCE (ppb) Half lives
« 10,000
» 5,000
- 2,500
• 625
• 160
• 40
- 10
- 2.5
• 0
• 1
• 2
• 4
. 6
• 8
• 10.
. 12
Recent Emplacement
Advancements
Vertically oriented hydraulic fracturing
Jetting
Tremie tube
PRB Emplacement Techniques
-------
I
Vertical Hydraulic Fracturing
• Iron suspended in guar-based slurry
• Fractures initiated using proprietary down-hole tool
• Iron slurry injected at high pressure/low velocity
• Fractures propagate along vertical orientation
• Adjacent fractures coalesce to form continuous
wall
• Slurry breaks down leaving permeable iron barrier
Overlapping Fractures
Injection Casing
Vertical Orientated
Fractures
PRB Emplacement Techniques
-------
K
•
Vertical Fracture Thickness
Thin continuous frac Thick continuous frac
Caldwell Trucking Superfund
Site
Permeable Reactive Barrier
Emplacement Using Hydraulic
Fracturing
PRB Emplacement Techniques
-------
Project Highlights
• TCE in groundwater at 6,000 ppb
• Contaminated ground water discharges
through spring, impacting surface water
• Goal of PRB is to restore surface water
quality
• PRB installed upgradient of spring
• Vertical hydraulic fracturing technology
used for PRB emplacement
Groundwater Flow from
Source to Spring Area
Passaic River
React!
Wall in
Spring Area
Groundwatej
Flow
Direction
Caldwell
Trucking Company
Super-fund Site
PRB Emplacement Techniques
-------
Subsurface Iron Reactive Barrier
G rou nd Suit*
Initiation Of Fracture
Ground Surface
Azimuth
Initiated Frac
PRB Emplacement Techniques
-------
Geological Cross-Section
Along Reactive Wall
Design Overview
• Designed to achieve 10 half-lives for TCE
(6,000 ppb => 6 ppb)
• Spans 40-foot depth interval from 25 to 65
feet below ground
• 3.5-inch fracture thickness in
unconsolidated zone
• Two walls in series: 150-foot and 100-foot
• Total PRB thickness of 7 inches
PRB Emplacement Techniques
-------
Iron Reactive Barrier at
Caldwell Superfund Site
Construction
• Hydraulic fracturing of
unconsolidated zone
• 250 feet of barrier (150 + 100)
• Hydrofrac wells at 15-foot spacing
• 140 tons of Iron injected
• Permeation infilling of upper bedrock
zone
• 116 tons of iron injected along a barrier
width of 150 feet
PRB Emplacement Techniques
-------
Construction (continued)
• Construction QA
• electrical resistivity
• hydraulic pulse testing
• 10,000 square feet of barrier installed
• Construction completed March 1998
Construction QA - Active
Resistivity Measurement
•Surface Pins
Low Voltage n n n p
Excitation u u u
Record In Phase
Induced Voltage
Down Hole
Receivers
Conductive
Frac Fluid
PRB Emplacement Techniques
-------
J
HydroFrac Injection in B1 & B2
Black and while version of graphic not available for printing.
Real Time Instrumentation
Display
Real Time Data
Acquisition &
Recording
Display of Resistivity
& Injection Time Histories
Display of Frac
Geometry
PRB Emplacement Techniques
-------
Mixing and Pumping System
Mixing equipment
Hoppers loading
iron into equipment
Control/pumping unit
Status of Project
• Spring water concentrations reduced from
6,000 ppb to 200 ppb but variable
• PRB extension and upgrade completed 6/99
• panels extended 90 feet (60 + 30) in
unconsolidated zone
• additional iron injected into existing panels
• bedrock zone extended 30 feet
• Performance monitoring ongoing
PRB Emplacement Techniques
-------
I
Monitoring
i Performance monitoring: 12 month
shakedown and performance monitoring
period using up- and down-gradient
monitoring wells
• basis for contractor's warranty
Compliance monitoring: surface water in
the seep and creek (quarterly - VOCs only)
• basis for regulatory acceptance
Why We Chose Fracturing for
Iron Emplacement
• Depth to 65 feet
• Desire to maintain integrity of clay layer
• Small iron thickness required (7 inches)
• Complex upper bedrock zone
• Minimize site disruption
• Ability to "tweak" after installation
PRB Emplacement Techniques
-------
Emplacement by Jetting
Iron suspended in guar (jetting fluid)
A high velocity stream of fluid erodes a
cavity in the soil matrix
A portion of the soil matrix is mixed with the
reactive media (iron filings)
Jetting creates either columnar or panel type
structures in the sub-surface
A PRB Emplacement Challenge
Permeable Reactive Barrier
Emplacement Using Jetting at an
Active Manufacturing Facility
PRB Emplacement Techniques
-------
I
Area Of Concern
TCE Plume
PRB Emplacement Techniques
-------
Existing P&T System
pr
•!.i" V5894
1 f f
Project Highlights
• A PRB of 2 to 4 inches is required
« PRB will be 485 feet long by 15 feet deep
emplaced by jetting
• Twelve utility & 2 road crossings
• Working near or underneath a water tower
• Construction completed 9/99
• Performance monitoring initiated
PRB Emplacement Techniques
-------
Site Characteristics
• Groundwater velocity of 0.09 feet / day
• Depth to groundwater is roughly 5 feet
• Mudstone confining unit at roughly 15 feet
PRB Design
• One 2-inch wall for most of the plume
width
• Two 2-inch walls in series for the 100 ppb
portion of the plume
• Wall depth is roughly 15 feet
PRB Emplacement Techniques
-------
I
PRB Emplacement Challenge
Jetting Process
PRB Emplacement Techniques
-------
Jetting Energy
Columnar Emplacement
PRB Emplacement Techniques
-------
I
Panel Emplacement
Panel Emplacement
PRB Emplacement Techniques
-------
Interconnecting Panels
Panel Type PRB
PRB Emplacement Techniques
-------
I
Columnar Type PRB
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Why Jetting Was Selected
• Ability to emplace a PRB 2 to 4 inches
thick
• Ability to work around utilities
.12 utilities
• Minimize disruption of plant operations
• 2 road crossings
• Ability to work near or underneath a water
tower
PRB l-mplacement Techniques
-------
u
h-
*
Tremie Tube Emplacement
• Tremie tube technology is the use of a
driven tubular structure that transfers
material into the ground without mixing
with the soil
• tube driven to desired depth
. tube filled with ZVI
• tube withdrawn from ground
• ZVI barrier left behind
DOE'S
Paducah Gaseous Diffusion Plant
Permeable Reactive Barrier
Emplacement Using Tremie Tube
PRB Emplacement Techniques
-------
Project Highlights
• Thin (2-inch) reactive zones were
emplaced as part of a technology
demonstration project at a DOE site.
• Emplaced 100 linear feet of reactive media
to a depth of 45 feet
• Spoils generation were minimal
• Tremie tube emplacement proved to be
cost-effective
PGDP's
Tremie Tube
PRB Emplacement Techniques
-------
Overall View
Bottom Edge
PRB Emplacement Techniques
-------
f
Driveshoe
Emplacement System
PRB Emplacement Techniques
-------
J
Tremie Tube at Depth
Placement of Materials
PRB Emplacement Techniques
-------
I
Emplaced PRB
Emplacement Sequence
Forming a continuous wall using the tremie tube method with
sequential emplacements
PRB Emplacement Techniques
-------
r*>
•
Summary
• Why was tremie tube technology
selected?
• emplace thin (2") treatment zones
• reduce emplacement costs
• reduce spoils generation & disposal
costs
Key Learnings from Case
Studies
Hydraulic fracturing, jetting, and tremie
tubes are viable and cost effective
emplacement technologies for PRBs
Thin and thick PRBs can be emplaced
Ability to work in complex surface and
subsurface environments
Importance of understanding stratigraphy
and groundwater flow
PRB technology is robust and flexible
PRB Emplacement Techniques
-------
I
Emplacement Advances
Summary
• PRBs can be placed accurately and cost-effectively
to depths > 100 ft
• PRBs can be emplaced across selected depth
intervals
• The required amount of iron can be emplaced
without excess iron usage
• Recent advancements allow PRB emplacement
where trenching and excavation would be
problematic
PRB Emplacement Techniques
-------
Section 8
PRB Permitting and Implementation
-------
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-------
CO
-8
Q.
EPA/ITRC/RTDF
Permeable Reactive Barrier Short Course
PRB Permitting and Implementation
RTDF
&EPA
Considerations
Permitting
Legal
Planning
• scheduling, access, health and safety
• spoils management
Construction QA/QC
Verification
Post-construction
Considerations for PRB Implementation and'Construction
-------
Regulatory Oversight Framework
• CERCLA program
• permit equivalency
• RCRA program
• State regulatory programs
Permitting Issues
National Pollution Discharge Elimination System
(NPDES)
Underground Injection Control (UIC)
Air quality
Local permits
Site-specific permits (i.e., wetlands)
PRB technology-specific permit does not exist
Considerations for PRB Implementation and Construction
-------
co
€
Q.
Other Regulatory Issues
Spoils management
Public involvement/comment periods
Deed restrictions-notifications
Health and safety issues
Legal Considerations
• Landowner issues
• Long-term maintenance agreements
• Access agreements
• during installation
• for ongoing monitoring
• Disruption
Considerations for PRB Implementation and Construction
-------
Constructability
High Land Use Density - Urban Setting
jiMiVt* •*•;•-.•.-'.,»-XsSjOas^^Vii.M-F'
South San Francisco Bay Area
Constructability
Moderate Density
• Low Density-Remote Area
USCG-Elizabeth City, NC
Near Durango, Colorado
Courtesy DDE-Grand Junction, CO
Considerations for PRB Implementation and Construction
-------
CO
•e
Q.
Constructabiiity
Building, legal, nearby remediation, utilities
Adjacent site
remediation
Construction
underbuilding
Deed
restriction
Future
construction
Permeable . ' ' ., '*' /
subsurface treatment . ,, North; • "
: . wall composed of "Gemenl-soil-bentonite -*^ -,---•'
t granular iron slurry wall
-.•<•.- 1 i
40ft.
I
-j._
*£ •> , ' BBxmdwatef floV^
.. „ , . *•" * .1
* »ft J* » ( Htstonqai range in '
* 5- "Jur^y* BrotmdiMMrflBwjnwaioft
EXPLANATION
• Monitoring well
® Piezometer
Constructabiiity
Heavy Equipment, Access, Mobility
Considerations for PRB Implementation and Construction
-------
Constructability
Building, Utility, Site Constraints
I
Constructability—
Geotechnical and Structural
Cone penetrometer
soundings
Soil property testing
Geotechnical design
Pre-/post-construction
building survey
Dewatering design
Designing for the unknown
Considerations for PRB Implementation and Construction
-------
1
CO
-P
Considerations—
Construction QA/QC
Material consistency and amount
• treatment zone material (reactive and inert)
• hydraulic barrier material
. batch sampling and testing—visual and laboratory
Survey alignment
Well installation
Placement of Reactive Material
• Ability to emplace reactive media:
• without crushing or damaging the media
• with respect to transportation to the site
• with mixing and staging
areas designated
Considerations for PRB Implementation and Construction
-------
Emplacement Verification
• Hydraulic and field geochemical analysis
• water level monitoring
• hydraulic pulse testing
• tracer testing (tracers depend on medium)
• examples—bromide, deuterium, dyes
• field geochemical parameters
* pH, redox, specific conductivity
Emplacement Verification-
Field Geochemical Analysis
Example: Use of pH and Redox for Fe(0) PRB
Plan Vlans
Zone of
Concern
pH
Redox
pH Redox
GWFlow
Direction
Fe(0)
9
Wells
Fe(0)
PRB Construction Incomplete?
PRB Construction Successful
Considerations for PRB Implementation and Construction
-------
CO
•6
Q.
Emplacement Verification
Geophysical methods
• natural gamma
• conductivity
• electrical resistivity
• surface radar
Plan
View
I ,,5 VoltegiKmV)
Cross-
Section
Considerations—Post-Construction
Surface completion
Landscaping Before
Post-construction
building/utility survey
Reporting
Monitoring
After
Considerations for PRB Implementation and Construction
-------
-------
Section 9
Reactive Materials II:
Treatment of Metals by FE° PRB Systems
and
Non-Metallic Reactive Materials
for Promoting PRB-Based Treatment
-------
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-------
.a
a.
Permeable Reactive Barrier Short Course
A. Treatment of Metals by Fe° PRB Systems
B. Non-Metallic Reactive Materials for
Promoting PRB-Based Treatment
KTDF
,ISTEHStATE i
&EPA
Treatment Mechanisms
• Chemical dehaiogenation
• pH control (acid neutralization)
B Chemical precipitation (oxidation and reduction)
• Coprecipitation on mineral surfaces
• Sorption reactions
• Biological enhancement
• Sequential treatment
Reactive Materials II: Non-Metallic Reactive
Materials for Promoting PRB-Based Treatment
-------
II' .inn I
Treatment Materials;
Treatable Contaminants
Treatment Material
Target Contaminants Technology Status
Zero-valent iron
Reduced metals
Metal couples
Limestone
Sorptive agents
Reducing agents
Biologic electron
acceptors
Halocarbons,
reducible metals
Halocarbons,
reducible metals
Halocarbons
Metals, acid water
Metals, organics,
nitrates
Reducible metals,
organics
Petroleum
hydrocarbons,
halocarbons,
nitrates
In practice
Field demonstration
Field demonstration
In practice
Field demonstration,
in practice
Field demonstration,
in practice
In practice,
field demonstration
Non-Metallic Treatment Materials
• Limestone
• Precipitation agents
• gypsum, hydroxyapatite, organic compost
• Sorptive agents
• granular activated carbon, bone char, phosphatics,
zeolites, coal, peat, synthetic resins
Reactive Materials II: Non-Metallic Reactive
Materials for Promoting PRB-Based Treatment
-------
•e
Q.
Non-Metallic Treatment Materials
• Reducing agents
• organic compost, dithionite, hydrogen sulfide,
bacteria, acetate, corn syrup, molasses, organic
compost
• Biological enhancements
• oxygen source, hydrogen source, carbon source
nitrate
Chemical Precipitation
The creation of an insoluble phase from
combining the target contaminant with a slightly
soluble anionic material
Example materials:
• limestone, hydrated lime, hydroxyapatite
pb-water + hydroxyapatite (CaPO4)= > Pb-phosphate(s)
Reactive Materials II: Non-Metallic Reactive
Materials for Promoting PRB-Based Treatment
-------
pH Control
• The use of a PRB to either raise or lower the
aqueous system pH
• Indirect pH control through biological activity
• Example materials include:
• lime, crushed limestone, organic compost
• pyrite, carbonic acid
Chemical Precipitation—pH Control
Metal solubility as a function of pH
Solublo Metals Cone.
mg/L
100
10
0.1 -
Cd
Fe
123456789 10 11 12
pH
Reactive Materials II: Non-Metallic Reactive
Materials for Promoting PRB-Based Treatment
-------
1
Oxidation-Reduction
Geochemical modification of the aqueous
environment through manipulation of
oxidation-reduction potential
Example materials:
. sodium dithionite (Na2S2O4) to reduce Fe(III) to Fe(ll)
• organic compost to reduce sulfate, generate HS, and
indirectly form metal precipitates
Oxidation-Reduction Example
Geochemically manipulated PRB from injection
Of SOdium dithionite (Fruchteo-, etal., Pacific Northwest Lab)
Reductant emplaced through
injection/extraction flushing
Fe3+ sediments
Groundwater flow direction
Structural Fe Reduced zone
and area of treatment
Reactive Materials II: Non-Metallic Reactive
Materials for Promoting PRB-Based Treatment
-------
Acid Rock Drainage Example
4FeS2($) + 1502(g) + 14H20(I) -> 4Fe(OH)3(s) + 8SO4%,q) + 16H+(aq)
Pyrite oxidation
Water flow direction
SO42' + 2CH2O => H2S + 2HCO3-
[Sulfate reduction]
CH2O + Fe(OH)3(s) + 7H+ => 4Fe2+ + HCO3- + 10 H20
[Iron III reduction]
'Permeable reactive barrier
Compost / Crushed Limestone PRB
Vancouver, BC
Reactive Materials II: Non-Metallic Reactive
Materials for Promoting PRB-Based Treatment
-------
1
(0
CD
.g
a.
Coprecipitation on Mineral Surfaces
Definition: removing a soluble metal from solution
through precipitation of another (carrier) component
Allows metals to be removed beyond the limits
predicted by equilibrium values
Example: removal of arsenic from a flow system
• FeCI3 + 3H2O + [As] ==> [As]Fe(OH)3 + 3H+ + 3CI"
As is trapped within and adsorbed to Fe(OH)3
• In contact with Fe(0), As may be immobilized within the corrosion layer
Sorption Reactions
• A general term to define processes of how
chemicals sorb (attach) to and desorb (detach)
from solid particles
• Divided into three types of reactions:
• hydrophobic
• hydrophilic
• ion exchange
Reactive Materials II: Non-Metallic Reactive
Materials for Promoting PRB-Based Treatment
-------
Sorption Reactions
Chemicals sorb by:
• diffusing into soil matrix
• adhering onto organic matter on soil
• attracted by electrical charge
Chemicals desorb by:
• diffusion along a concentration gradient
• displacement by a molecule with higher affinity for
the site
Sorption of Organics
• Good for compounds with
• low water solubility
• hydrophobic character
• not easily biodegraded
• Example materials include:
• GAC, peat, coal, organic-rich shale, zeolite
Reactive Materials II: Non-Metallic Reactive
Materials for Promoting PRB-Based Treatment
-------
s
-e
D.
Sorption Materials - Zeolites
Example:
Clinoptilolite
(Na, K, Ca)2.3AI3(AI, Si)2Si13O36-12H2O
Sorption of Inorganics
Good for compounds such as metals
• affinity on carbon: Pb>Cu>Ni>Zn=Mn=Cd=Co
Well-suited to hydrophilic and ion exchange
sorption reactions
Examples include:
• organic carbon, zeolites, clays, oxyhydroxides
Reactive Materials II: Non-Metallic Reactive
Materials for Promoting PRB-Based Treatment
-------
Enhanced Sorption
Surface modified zeolite PRB to sorb metals
(e.g., Cr, U, Sr, As)
Chromatc
Zeolite Surface
Source: New Mexico Tech and Oregon Graduate institute
Biological Enhancement
• Addition of nutrients to stimulate microbial
activity necessary for chemical degradation
• Example materials
• oxygen-releasing compound or oxygen source to
stimulate aerobic microbes (treat BTEX)
• nitrate to stimulate anaerobic microbes
• sugar (carbon source) to stimulate anaerobic microbes
(treat chlorinated VOCs)
• sulfate-reducing bacteria
Reactive Materials II: Non-Metallic Reactive
Materials for Promoting PRB-Based Treatment
-------
PRB as Biologically Enhanced Area
Oxygen release
ORC-wells
GW flow
direction
(map view)
Aerobic zone
_—
increased biological
activity
Area of
increased
degradation
Sucrose addition
cVOC plume
biologically
enhanced
dehalogenation
zone
Redox
Anaerobic zone
low degradation rate
Low redox
«•
Low O2
Sucrose
injection
well
ORC and HRC Barriers
Oxygen Release
Compound
. MgO2 + H20 -> 1/2 O2 + Wig (OH)2
Hydrogen Release
Compound
• Polyacetate ester that releases
lactic acid when hydrated
• Lactic acid is metabolized
anaerobically releasing H
Diagram Courtesy Regenesis Bioremediation Products
Reactive Materials II: Non-Metallic Reactive
Materials for Promoting PRB-Based Treatment
-------
Considerations for Using Reactants
• Understanding ambient hydro/geochemistry
• hydrochemical type (major inorganics)
• redox
• organic content
• Understanding physical flow system
• dispersion, heterogeneity, groundwater velocity
• Longevity of treatment
• active life, need to re-apply
Sequential Treatment Design
• Use of two or more processes in series to treat a
mixed plume - advantages:
• increase effectiveness of principal treatment
• polish treatment
• increase the longevity of the remedy
Treatment A Treatment B
Reactive Materials II: Non-Metallic Reactive
Materials for Promoting PRB-Based Treatment
-------
03
O>
•e
Q.
Sequential Design System (continued)
Example: Sorption - Dehalogenation
groundwater <^Mef+cVpC pkfrjj?)
Groundwater flow direction
Result:
Reduces tendency
for plugging in B
Treatment A - Zeolite for sorplion of metals and
carbonate - high porosity
Treatment B - Zero-valent metal to dehalogenate cVOC
Sequential Treatment—Issues
Treatment process considerations
• oxidizing vs. reducing conditions
• pH affects
• interfering mineralization/blinding
• electron consumption
Implementation
Hydraulics
Reactive Materials II: Non-Metallic Reactive
Materials for Promoting PRB-Based Treatment
-------
(.(. ',! : I b (•' Ifl'Si" ' "''." " WV '"Mill
"'!'- ,1," V ] '""IH"' 'I""'/
Case Study
Reactive Materials II: Non-Metallic Reactive
Materials for Promoting PRB-Based Treatment
-------
EPA/ITRC/RTDF
Permeable Reactive Barrier Short Course
Permeable Reactive Barriers for Cr(VI)
Groundwater Remediation
KTDF
SEPA
Permeable Reactive Barriers
Remediation of metals—issues
• immobilization mechanisms & reversibility
• adsorption-desorption
• precipitation-dissolution
• radioactivity
• toxicity (transformations?)
Permeable Reactive Barriers for
Cr(VI) Groundwater Remediation
-------
Cr Eh-pH Diagram
Solubility of Cr(lll) and
Dominant Aqueous Species
Permeable Reactive Barriers for
Cr(VI) Groundwater Remediation
-------
£
-9
o.
Chromate Reduction By
Zero-Valent iron
2Fe° + O2 +2H2O •» 2FE2+ + 4OH-
Fe2+ + CrO42- + 4H2O •* (FeXJ Cr^J (OH)3 + 5OH-
Elizabeth City PRB Site
Permeable Reactive Barriers for
Cr(VI) Groundwater Remediation
-------
USCG Support Center
TCE/Ctirnmium
Rumc.Sitc
Ptaqaotu* River
ToBlabcACVr
-' •-
Cr Plating Shop Plume
Permeable Reactive Barriers for
Cr(VI) <3roundwater Remediation
-------
Cr 2-D Concentration Contour:
Geoprobe
Hydraulic Conductivity with Depth
Permeable Reactive Barriers for
Cr(VI) Groundwater Remediation
-------
Elizabeth City Site - Pilot Test
Elizabeth City
Pilot Test Site
Permeable Reactive Barriers for
Cr(VI) Groundwater Remediation
-------
O)
-s
Q.
Pilot Test Reactive Mixture
*, *«
Geochemistry Data—PRB Pilot Test
Permeable Reactive Barriers for
Cr(VI) Groundwater Remediation
-------
Full-Scale Wall Installation
Trencher for
Wall Installation
Permeable Reactive Barriers for
Cr(VI) Groundwater Remediation
-------
.0
en
Site Design Summary
USCG Elizabeth City, NC (June 1996)
Cost
Continuous Wall Dimensions
-150 ft length, 2 ft flow-through
thickness
- 24 ft total depth
-18 ft saturated depth
Groundwater Flow Rate
- 0.5 ft/day
Influent Groundwater
- 10 ppm TCE, 10 ppm Cr(VI)
Construction
General Contractor $150,000
Trenching Contractor $150,000
Granular Iron $200,000
Total $500,000
Est. Annual Monitoring $50,000
Elizabeth City Site - Full-Scale PRB
Permeable Reactive Barriers for
Cr(VI) Groundwater Remediation
-------
Iron Wall—USCG Site Upgradient
Geoprobe Data, April, 1996
Wall Location in Aquifer
MUMS uw-ii MW-W
Permeable Reactive Barriers for
Cr(Vl) Groundwater Remediation
-------
•e
o.
Mufti-Level Samplers
Multi-Level Samplers
Permeable Reactive Barriers for
• Cr(VI) Groundwater Remediation
-------
Monitoring
Verification monitoring
• to assess effectiveness of emplacement (construction
QA)
Performance monitoring
• to evaluate total system performance (early warning
system)
Compliance monitoring
• to meet regulatory requirements
Performance Monitoring
Geochemical indicator parameters:
pH, Eh, DO, ferrous iron, sulfide, alkalinity
Permeable Reactive Barriers for
Cr(VI) Groundwater Remediation
;... I,.;;,::.,
-------
.a
1
a.
Iron Corrosion in Subsurface Systems
Fe° + 2H2O •* 2FE2+ + H2 + 2OH-
Fe° + O2 + 2H2O •» 2FE2+ + 4OH-
pH Fe2+
pH-2D
Cross-Section
EEh
Permeable Reactive Barriers for
Cr(VI) Groundwater Remediation
-------
Eh-2D
Cross-Section
Fe(ll)-2D
Cross-Section
Permeable Reactive Barriers for
Cr(VI) Groundwater Remediation
-------
JD
CO
-e
Q.
Cr-2D
Cross-Section
Cr-2D
Cross-Section
Permeable Reactive Barriers for
Cr(VI) Groundwater Remediation
-------
Geochemical Monitoring Results for
Iron "Fence" and Iron Wall
Cr(VO
Sulfkfet
SO,
Alkalinity
Continuous
Iron Wall
<0.01 mg/L
<0.2mg/L
-300 to-5 50 mV
9.1-9.8
<0.1 mg/L
abwHit
decrease
decrease
Iran Fence
<0.01 mg/L.
2-20 mg/L
100 to +200 mV
6.6-9.0
< 0.1 mg/L
decrease
variable
Wall Emplacement Verification
Conductivity probe
• differences in conductivity between native aquifer
materials and iron over 2 orders of magnitude
• can also use to confirm "cleanup"
Permeable Reactive Barriers for
Cr(VI) Groundwater Remediation
-------
-Q
cn
•B
Q.
Conductivity Probe—Controller
Conductivity Data
Conductivity Log - Upgradient Conductivity Log - Downgradient
__^
3520
•J2 7- .-.,..,.
|10
&8
o 10 f-
•o I
§ 5kfr-
nSt
10 15
Depth (ft)
20
-jy—r
25
0 '•—
10 15 20 25
Depth (ft)
Permeable Reactive Barriers for
Cr(VI) Groundwater Remediation
-------
Conductivity Data
Iron Wall
•T"T
» J »_SU_.« L
yi»a^rfs™= r.l, 4.-* > «"*~
»/ i » • « •«•
*• » "1 • I 1-1 i 1-
10 15 20
Depth (ft)
25
J
30
Conductivity Data - Angle Core
.
O
4000
3500
3000
2500
2000
1500
1000
500
0
,
1
J
i
*
•Ai
»
s_
ramsBW*— ^ —
«ft
* **
* .
*
,
• "»'
••Ju.1
' '-1'' ;; , '•''
,:
M. ' -
10
15
Depth (ft)
20
25
Permeable Reactive Barriers for
Cr(VI) Groundwater Remediation
-------
1
.a
a>
-e
Q-
Long-Term Performance of Permeable
Reactive Barriers Using Zero-Valent Iron
Hydrology
• evaluate changes in flow field and permeability
through the reaction zone over time
Water Levels
Permeable Reactive Barriers for
Cr(VI) Groundwater Remediation
-------
Long-term Performance Monitoring
• Potential decrease in reactivity, permeability
• analysis of emplaced iron over time
• surface precipitates
• biomass accumulation
Angle Coring
Permeable Reactive Barriers for
Cr(VI) Groundwater Remediat'on
-------
1
-e
Q.
Typical Angle
Core
Upgradient Angle Core
Permeable Reactive Barriers for
Cr(VI) Groundwater Remediation
-------
"in I'" i1 =r i' * •' f II"1 •''; ' ii'Ti r.' i i't! ' '•• • i1::1!1 '• SB"' win H: "i-' 'w: T: ar-:: • • r: ;
Angle Core Data
SEM-EDS Data—Iron Sulfide
Permeable Reactive Barriers for
Cr(VI) Groundwater Remediation
-------
o>
Q.
XPS Angle Core Results - EC90903
2.5-
1.5-
0.5-
2.5 5 15
cm from upgradient sediment-iron interface
% CO3 ' -: .
% S
nmol PLFA/g dry wt
n oxide coating thickness (x 10-8 m)
SEM-EDS Data—Green Rust
Permeable Reactive Barriers for
Cr(VI) Groundwater Remediation
-------
Corrosion Layer
Corrosion Layer
Permeable Reactive Barriers for
Cr(VI) Groundwater Remediation
-------
o>
€
Q.
Estimation of Porosity Decrease
• Assumptions
• iron filings, avg 1 mm dia, spherical
• growth of corrosion layer, a linear function
• samples to date are representative
• initial porosity = 0.5
• 25 um thickness increase over 27 months
• decrease of initial porosity of 16% (27 mo)
• porosity decline to about 33% in 7 yrs
Long-Term Performance of Permeable
Reactive Barriers Using Zero-Valent Iron
Lead Organization
Cooperators
Sites
USEPA - NRMRL
USCG, USGS, GE
Elizabeth City, NC
Denver Federal
Center, CO
Somersworth
Landfill, NH
DOE - ORNL
Y12ORNL,TN
Rocky Flats, CO
Kansas City
Plant, MO
DoD
Navy, Air Force, ACE
Moffett Field MAS, CA
Cape Canaveral, FL
Lowry AFB, CO
Dover AFB, DE
Permeable Reactive Barriers for
Cr(VI) Groundwater Remediation
-------
t;«^
I iiij jfcii^jSjj^BBHnBSujiHiatlBS ).,«,iS^^»»,,,-,>,,-Kiiii&*E«i
i/1", "i..:'''•-«, '' •-' ,1' ., :» • i> ,• if' ' ' ' .•-' v, '' ' '•: -'•?. n -••',:•'' ' -~--»--'«"-:v:.;, '',V2£>
Barrier
r
Additional Information
www.rtdf.org
www.epa.gov/ada/research .html
http://clu-in.org
Permeable Reactive Barriers for
Cr(VI) Groundwater Remediation
-------
EPA/ITRC/RTDF
Permeable Reactive Barrier Short Course
Application of an Organic-Based
Sulfate-Reducing Permeable Reactive Wall for
Treatment of Acid Rock Drainage
Ralph Ludwig, Ph.D. (U.S. EPA, Ada, Oklahoma)
David Blowes, Ph.D., (University of Waterloo, Waterloo, Canada)
Rick McGregor, M. Sc. (Conor Pacific Environmental Technologies)
KfDf
©EPA
Pacific Environmentai Center Site-
Vancouver, Canada
Application of an Organic-Based Sulfate-Reducing Permeable
Reactive Wall for Treatment of Acid Rock Drainage
-------
I "
Pacific Environmental Center Site-
Low Tide
Environmental Setting
• Sand to gravel coastal aquifer
• K ranging from 10-2 to 10'3 cm/sec
• Tidally influenced
• Groundwater impacted with Cu, Cd, Zn, Ni, and
low pH
• Groundwater discharge highly toxic to fish
Application of an Organic-Based Sulfate-Reducing Permeable
Reactive Wall for Treatment of Acid Rock Drainage
-------
o
s
Remedial Options
Pump and treat
Permeable reactive wall
• limestone-based
• zero-valent iron-based
• compost-based
Acid Mine Drainage and
Sulfate Reduction
Application of an Organic-Based Sulfate-Reducing Permeable
Reactive Wall for Treatment of Acid Rock Drainage
-------
Wall Reactions of Interest
SO2- + 2CHO •» HS + 2HCO-
Me2+ + HS
MeS(s) + 2H
Test Wall Installation
• 30 ft long, 20 ft deep, 7.5 ft wide
• Backhoe excavation with guar gum slurry trench
support
• Reactive media—mature leaf compost (15%)
• Clam shell media emplacement
Application of an Organic-Based Sulfate-Reducing Permeable
Reactive Wall for Treatment of Acid Rock Drainage
-------
O5
O
CD
Initiation of Test Wall Construction
? & tLi# *^«i~Sr!***'"fc»«*' j^
^w
Guar Gum Slurry Preparation
Application of an Organic-Based Sulfate-Reducing Permeable
Reactive Wall for Treatment of Acid Rock Drainage
-------
Guar Gum Slurry Mixing
Final Guar Gum Slurry Product
Used in Construction
Application of an Organic-Based Sulfate-Reducing Permeable
Reactive Wall for Treatment of Acid Rock Drainage
-------
Measurement of Trench Depth
Reactive Media Preparation
Application of an Organic-Based Sulfate-Reducing Permeable
Reactive Wall for Treatment of Acid Rock Drainage
-------
Reactive Media Mixing
Reactive Media—Final Product
Application of an Organic-Based Sulfate-Reducing Permeable
Reactive Wall for Treatment of Acid Rock Drainage
-------
Reactive Media—Close-Up
Completion of Trench Construction
Application of an Organic-Based Sulfate-Reducing Permeable
Reactive Wall for Treatment of Acid Rock Drainage
-------
Initiation of Reactive Media
Emplacement
.•/'«•*• «^f!|S. "
IBliltHliliti
- *!a| pi
Emplacement of Reactive Media
Using Clamshell
Application of an Organic-Based Sulfate-Reducing Permeable
Reactive Wall for Treatment of Acid Rock Drainage
-------
I
Reactive Media Emplacement in Lifts
First Half of Test Wall Completed
Application of an Organic-Based Sulfate-Reducing Permeable
Reactive Wall for Treatment of Acid Rock Drainage
-------
Completed Test Wall
Copper Concentration Profile
After 21 Months
Application of an Organic-Based Sulfate-Reducing Permeable
Reactive Wall for Treatment of Acid Rock Drainage
-------
o
0)
Zinc Concentration Profile
After 21 Months
Cadmium Concentration Profile
After 21 Months
Reactive WaH
v GroundwMrrflow
'"
Cadmium - Alt onitji j
-------
Nickel Concentration Profile
After 21 Months
Alkalinity Profile
After 21 Months
Application of an brganic-Base^d Sulfate-Reducing Permeable
Reactive Waif for Treatment of Acid Rock Drainage
-------
Positive Features
Low cost
• pea gravel $25 cy
• limestone $52 cy
• compost $0-10 cy
Metals concentration/recovery?
Nickel Rim Site
Application of an Organic-Based Suifate-Reducing Permeable
Reactive Wall for Treatment of Acid Rock Drainage
-------
-------
Section 10
PRB Cost Analysis and Comparisons
-------
I:;:, .;,!,,„ .„,, ,, ., '
'-tf-H-Mi .'.:-" 1115 li'llli'.* L i .i: ' liili'' iiliililili
-------
•e
a.
EPA/ITRC/RTDF
Permeable Reactive Barrier Short Course
PRB Cost Analysis and
Comparisons
RTDF
v>EPA
Cost Elements
• Site characterization
• Design (includes laboratory and field
pilot, if necessary)
• Construction
• reactive material
• installation method
• disposal of excess soil and materials
• Monitoring
• Operation and maintenance
• Licensing Fees
Economic Considerations for PRB Deployment
-------
1
Factors Affecting Treatment
Cost
• Groundwater velocity
• Influent VOC concentrations
• Degradation rates
• Treatment goals
• Depth, width, saturated thickness of
plume
• Reactive material
Present Cost Definition
PV=
i=o
Where:
i = 0 Capital investment year
i = 1-->n Operation and maintenance years
r = Discount rate
Y = Dollars expended in year 'i'
n = Number of years
Economic Considerations for PRB Deployment
-------
l_J
•
General Economic Assumptions
• Inflation is constant at 4%
• Cost of capital is constant at 12% for
industry
• Analysis is done on a before-tax basis
• Remedial time frame is 30 years
• Monitoring cost per well per year is $2500
• Monitoring wells cost $2400 each
Conceptual Site Model
Methodology
Economic Considerations for PRB Deployment
-------
o
I
Plume Description
Contaminant Assumptions
Initial plume concentrations:
• TCE = 10,000 ppb,
• cDCE = 1,000 ppb, and
. VC = 100 ppb.
Remedial goals at compliance point:
. TCE = 5 ppb,
• cDCE = 70 ppb, and
. VC = 2 ppb.
Economic Considerations for PRB Deployment
:!! Kill!
-------
Cost Analysis of PRBs
• Cost analysis of continuous PRB
• Cost analysis of continuous PRB coupled
with natural attenuation
• Comparison to pump and treat
• Comparison to natural attenuation
PRB
Conceptual Model
nPRB = 50%
Economic Considerations for PRB Deployment
-------
•li
o
1
PRB Scenario
• Compliance point at down gradient edge of PRB
• PRB thickness is 12 inches
. PRB emplacement cost: $20/ft2
• Granular cast iron costs $400/ton @ 165 Ibs/ft3
• Licensing fee: 15% of capital
• Up front engineering cost: $200,000
• Number of monitoring wells: 10
Half-Life Assumptions
Typical t1/2 values:
. ZVI:
• TCE = 2 hour
• cisDCE = 3.5 hours
• VC = 6.4 hours
Economic Considerations for PRB Deployment
-------
o
i
Residence Time Model
Concentration |ig/L)
Jr* ®
1-1 O O
s g g g
1 -
\ TCE
^-A
V\cDCE
VC \ N.
Vv
- \ x^\
1
. .
« 5 10 15 20 25 30 35 40 45 50 55 60
Residence Time (hr)
PRB Requirements
Assuming GW velocity of 1 foot / day:
• ZVI:
. (1foot/day)(0.25/0.50) = 0.5 feet of groundwater
travel in PRB per day
* 12 inch PRB equals 48 hr groundwater
residence time in the PRB
• residence time required:
* TCE = 21 hrs (10,000ppb to 5ppb)
* cisDCE » 22 hrs (1000ppb to 70ppb)
* VC « 48 hrs (100ppb to 2ppb)
Economic Considerations for PRB Deployment
-------
1
PRB Summary
Replacement Cycle
Cost Item
Engineering
Emplacement
Iron
Wells
Licensing Fee
O&M
Monitoring
Total
5 Year
$263K
$1,072K
$1,770K
$24K
$194K
$0
$279K
$3,603K
10 Year
$221 K
$684K
$1,129K
S24K
$194K
$0
$279K
$2,531 K
15 Year
$209K
$568K
$937K
$24K
$194K
$0
$279K
$2,21 1K
30 Year
$200K
$480K
$792K
S24K
$194K
$0
$279K
$1,969K
PRB Summary
$10,000,000 •
$9,000,000 •
•55
Q $8,000,000 •
•£
$5,000,000 •
'•i
3 $4,000,000 •
£
Q $3,000,000 •
$2,000,000 -
$1,000,000
$0
'
(5 vear life cvcle)
„ .,
, ix"" "~
_ /(15 vear life cycle) ^ (19 ypaj f;fe cvclel
(30 year life cycle)
3 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
Time (Years)
Ecohomic Considerations for PRB Deployment
-------
o
i
PRB Summary
(10-Year Replacement Cycle - $2,532K)
$684,000
(Emplacement)
$1,129,000 (Iron)
$221,000
(Engineering)
$279,000
(Monitoring)
$194,000
(Licensing Fee)
$24,000
(Wells)
PRB With Natural Attenuation
Conceptual Model
Economic Considerations for PRB Deployment
-------
o
f
PRB With Natural Attenuation
Conceptual Model
C0
cd
ct
V Perm
N. Bar
Compliance
Point
sable
rier
^^. Design
^ — Basis
^s^^ I Target
_. Concentration
:
„ , , 1, ,
PRB With Natural Attenuation
Scenario
Assumptions are the same as for the continuous
PRB example except:
• Natural attenuation is on-going at site
• Retardation factor for natural attenuation is 1.5
• Compliance point is down gradient from PRB
• Number of monitoring wells: 20
• Barrier thickness is 6 inches
Economic Considerations for PRB Deployment
-------
<_J
•
ZVI Half-lives Revisited
ZVI:
(1foot/day)(0.25/0.50) = 0.5 feet of groundwater
travel in PRB per day
• 6 inch PRB equals 24 hr groundwater residence
time in the PRB
Half lives required:
* TCE » 21 hrs (10,000ppb to 5ppb)
* cisDCE « 22 hrs (1 OOOppb to 70ppb)
»VC^48hrs (lOOppb to 2ppb)
Residence Time Model
10,000
~ 1,000
100
10
1
, TCE
cDCE
VC
0 5 10 15 20 25 30 35 40 45 50 55 60
Residence Time (hr)
Economic Considerations for PRB Deployment
-------
I
Mass Removal Model
100,000 3
10
20 30 40
Residence Time (Hrs)
PRB / Natural Attentuation
Treatment Train
24 hr residence time in PRB degrades
. TCE from 10,000 ppb to
-------
o
Jj
Natural Attenuation
Requirements
Natural attenuation half-life for VC:
• t1/2= 1.0 year
• aquifer distance required:
* VC = (4 half lives)(365 ft/half life)(1/1.5) = 1000 feet
Comparison of PRB and Natural
Attenuation Half Lives For TCE
• 12 half lives needed to reduce TCE from 10,000
ppb to 5 ppb regardless of treatment method
• t1/2 for TCE = 1.0 year
• 6 inches of ZVI is equivalent to 3,000 feet of
natural attenuation of TCE
• (12 half lives)(365 ft/half life)(1/1.5) = 3000'
Economic Considerations for PRB Deployment
-------
o
1
PRB With Natural Attenuation
Cost Summary
Cost Item
Engineering
Emplacement
Iron
Wells
Licensing Fee
O&M
Monitoring
Total
5 Year
$262K
$1,072K
$885K
$48K
$139K
$0
$557K
$2,963K
Replacement Cycle
10 Year 15 Year
$221 K
$684K
$565K
$48K
$139K
$0
$557K
$2,21 4K
$209K
$568K
$468K
$48K
S139K
$0
$557K
$1,989K
30 Year
$200K
$480K
$396K
$48K
$139K
$0
$557K
$1,820K
*", -f- . .
PRB / Natural Attenuation Summary
t>
+*
CO
o
73
£
$2,000,000
/.' ' _ t
• ••'.'•.<<;„• :
(5 year life cycle)
~
^^e i!t]TL..»i-\^ (10 year life cycle)
..o-o-o-^1-0-0-0"""*^^ ^»-A_«— ^. ^ ^^ ^ cycle)
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
Time (Years)
Economic Considerations for PRB Deployment
-------
o
ki
PRB /Natural Attenuation Summary
(10-Year Replacement Cycle - $2,214K)
$221,000
(Engineering)
$557,000
(Monitoring) $! 39,000
(Licensing Fee)
$684,000
(Emplacement)
$48,000
(Wells)
$565,000
(Iron)
Natural Attenuation Cost
Scenario
Compliance point is down gradient from
the source
Number of monitoring wells: 20
Up front engineering: $250,000
Economic Considerations for PRB Deployment
-------
o
I
Natural Attenuation
Summary
Yearl
NPV
Engineering $25 OK $25 OK
Wells $48M $48K
O&M $OK $QK
Monitoring $50 K $557 K
Total $348K $85 5 K
Natural Attenuation
Summary
$5,000,000 i
$4,500,000 •
•g $4,000,000 •
2 $3,500,000 •
w $3,000,000 •
£
°- $2,500,000 •
>
2
3 $1,500,000 •
$0 •
(
n - -] n n
n^—o— 0— °—t>-'>- °— "*-"
) 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
Time (Years)
Economic Considerations for PRB Deployment
-------
Pump and Treat Scenario
• In situ flux = 47 gpm
• P&T rate = 70 gpm
• Capital investment: $15K per installed
gpm
• O&M cost: $20 per 1000 gallons treated
Pump and Treat Summary
Present
Year 1 Cost
Capital $1,050K $1,050K
O&M S736K $8,202K
Total $1,786K $95252K
Economic Considerations for PRB Deployment
-------
Pump and Treat Summary
$10,000,000
$9,000,000
$8,000,000 -
0 $7,000,000 •
C $6,000,000
to
£ $5,000,000 -
a.
g $4,000,000 •
*5
2 $3 000 000 •
3 $2,000,000
$1,000,000 .
^"^^
^^^ •
^x^
/
/*
S
s
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
Time (Years)
Overall Cost Comparison
$10,000,000 -
$9,000,000 -
1o $8,000,000 -
o
;! $7,000,000 •
0)
«g $6,000,000 •
°" $5,000,000 •
•g $4 000 000 •
"5
£ $3 000 000 •
o
$2,000,000 •
$1,000 000 '
to •
m j_ • J
^^~~^
Pump And Treat ^^-*^*^
^
S
s
/
'F2£^_4-i-^-*-*-^-jr^ PRB with NA (1 0 yr life cycle)
-»-•—-— -*^~^ ' ' ' Natural Attenuation
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
Time (Years)
Economic Considerations for PRB Deployment
-------
Conclusions
• Permeable reactive barriers are cost-effective
compared to P&T systems
• Zero O&M is the major advantage for PRBs
• Emplacement and media drive costs for PRBs
• Capital costs for P&T systems and PRBs are
similar
• PRB payback is quick whereas O&M for P&T
continues to add up
• Synergy with natural biodegradation processes
should be considered during PRB design stage
Conclusions
1995 1996 1997 1998
YTD
Economic Considerations for PRB Deployment
-------
-------
Section 11
Bibliography
-------
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-------
FIELD APPLICATIONS OF
PERMEABLE BARRIER TECHNOLOGY
Appleton, E.L. 1996. "A Nickel-Iron Wall Against Contaminated Groundwater." Environmental
Science & Technology, 30:12, 536A-539A.
Bain, J.G.; D.W. Blowes; S.G. Benner. 1998. "Treatment of Acidic, Mine-Associated Discharge
to a Lake Using a Permeable Reactive Barrier." 1998 American Geophysical Union Spring
Meeting, 26-29 May, Boston, MA.
Baker, M.J.; D.W. Blowes; C.J. Ptacek. 1997. "Phosphorous Adsorption and Precipitation in a
Permeable Reactive Wall: Applications for Wastewater Disposal Systems." 1997 International
Containment Technology Conference and Exhibition, 9-12 February, St. Petersburg, FL. 697-
703. CONF-970208-Proc. DE98001967.
Barton, W.D.; P.M. Craig; W.C. Stone. 1997. "Two Passive Groundwater Treatment Installations
at DOE Facilities." 1997 International Containment Technology Conference and Exhibition, 9-
12 February, St. Petersburg, FL. 827-834. CONF-970208-Proc. DE98001967.
Benner, S.G.; D.W. Blowes; CJ. Ptacek. 1997. "A Full-Scale Porous Reactive Wall for
Prevention of Acid Mine Drainage." Ground Water Monitoring and Remediation. 17:4 (Fall)-
99-107.
Benner, S.G.; D.W. Blowes; C.J. Ptacek. 1997. "Porous Reactive Wall for Prevention of Acid
Mine Drainage: Results of a Full-Scale Field Demonstration." 1997 International Containment
Technology Conference and Exhibition, 9-12 February, St. Petersburg, FL. 83 5-843 { CONF-
970208-Proc. DE98001967.
Benner, S.G.; D.W. Blowes; C.J. Ptacek. 1997. "Sulfate Reduction in a Permeable Reactive Wall
for Prevention of Acid Mine Drainage." The 213th National Meeting of the American Chemical
Society, San Francisco, CA. Preprint Extended Abstracts, Division of Environmental Chemistry.
37:1,140-141.
Bennett, T.A.; D.W. Blowes; R.W. Puls; R.W. Gillham; C.J. Hanton-Fong; C.J. Ptacek; S.F.
O'Hannesin; J.L. Vogan. 1997. "Design and Installation of an In Situ Porous Reactive Wall for
Treatment of Cr(VI) and Trichloroethylene in Groundwater." The 213th National Meeting of the
American Chemical Society, San Francisco, CA. Preprint Extended Abstracts, Division of
Environmental Chemistry. 37:1, 243-245.
Bennett, T.A.; D.W. Blowes; R.W. Puls; R.W. Gillham; C.J. Hanton-Fong; CJ. Ptacek; S.F.
O'Hannesin; J.L. Vogan. 1998. "An In-Situ Permeable Iron-Filings Wall to Remediate Cr(VI)
and TCE Contaminated Groundwater." Subsurface Barrier Technologies Conference:
Engineering Advancements and Application Considerations for Innovative Barrier Technologies,
26-27 January 1998, Tucson, AZ. Internatiorial Business Communications, Southborough, MA.
-------
Betts, K.S. 1998. "Novel Barrier Remediates Chlorinated Solvents." Environmental Science &
Technology, 1 November 1998,495A.
Blowes, D.W.; C.J. Ptacek; K.R. Waybrant; J.D. Bain; W.D. Robertson. 1994. k'In Situ
Treatment of Mine Drainage Water Using Porous Reactive Walls." The "New Economy": Green
Needs and Opportunities. Environment and Energy Conference of Ontario, November 15 & 16,
1994, Toronto, Ontario.
Blowes, D.W.; C.J. Ptacek; J.A. Cherry; R.W. Gillham; W.D. Robertson. 1995. "Passive
Remediation of Groundwater Using In Situ Treatment Curtains." Geoenvironment 2000:
Characterization, Containment, Remediation, and Performance in Environmental Geotechnics.
American Society of Civil Engineers, Reston, VA. Geotechnical special publication 46 (v.2),
1581-1607. ;; ; ^ " i ' i "; ;'
Blowes, D.W.; C.J. Ptacek; C.J. Hanton-Fong; J.L. Jambor. 1995. "In Situ Remediation of
Cbjcomium Contaminated Groundwater Using Zero-Valent Iron." The 209th American Chemical
Society Motional Meeting, Division of Environmental Chemistry, 2-7 April 1995, Anaheim, CA.
Preprint Extended Abstracts. 35:1, 780-783.
Blowes, D.W.; C.J. Ptacek; K.R. Waybrant; J.G. Bain. 1995. "In Situ Treatment of Mine
Drainage Water Using Porous Reactive Walls." Proceedings, Biominet Annual General Meeting
on Biotechnology and the Mining Environment, 26 January 1995, Ottawa, Ontario. 119-128.
]
I
Blowes, D.W.; C.J. Ptacek; J.G. Bain; K.R. Waybrant; W.D. Robertson. 1995. "Treatment of
Mine Drainage Water Using In Situ Permeable Reactive Walls." Proceedings, Sudbury '95
Symposium on Mining and the Environment, 28 May-1 June 1995, Sudbury, Ontario. V.3,
979-987.
J ,
,i;.'»i , •• :„ ••',;, i
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-------
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• • • i
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•US. Government PtMng Office: 2000 — 517-372/94609
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