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Frank Lilley, LSP Senior Consultant
Golder Associates, Inc.
Golder’s Project Experience
with Nano Scale Zero Valent
Iron
Golder’s Project Experience
with nZVI Technology
presented at
EBC Remediation Program Westborough, Massachusetts
April 10, 2012
Presented by:
Frank W. Lilley, LSP
Speaker
3
Frank W. Lilley, LSP - Senior Environmental
Engineer/Consultant 30 Years Experience –MassDEP, USEPA Region I, Private Sector
BA Biology and Chemistry, Boston University
MS Environmental Engineering, Tufts University
MGP, CERCLA, Site Assessment and Remediation, Remedial Design: Thermal
Technologies, In-Situ Soil and Groundwater Remediation, Sediment Remediation,
Risk Based Closure Strategies, Property Redevelopment, Air Pollution
Monitoring/Permitting, New England Regulatory Agency Negotiations, Multimedia
Compliance Auditing
Golder Associates Inc.
New England Operations
Boston Office
300 Friberg Parkway
Westborough, MA 01581
508-366-5366
Golder Associates Contributors
Michael J. Borda, Senior
Geochemist PhD MT. Laurel,
N.J. email:
Florin Gheorghiu, C.P.G., P.G.
MT. Laurel, N.J. email:
Phone N.J. Office: 856-793-
2005
4
Who is Golder?
7,000 Global Employees
1,300 Golder US Employees
12,000 projects each year,
both large and small
51 years in business,
founded in Toronto Canada
First Office in Boston
A global ground
engineering and
environmental services
company
100% Employee Ownership
Operations: Golder US,
Golder Canada,
Golder South America
Golder Europe
Golder Australasia
Deliver local solutions to
global issues
Recognized for and
committed to client service,
technical excellence and
sustainable solutions
5
Comprehensive Suite of Services
Ground Engineering Environmental & Social
Assessment
Natural Resources
Management
Management &
Compliance
Planning & Design Site Remediation
Geotechnical Engineering
Soil & Rock Mechanics
Rock & Mining Engineering
Tailings Management
Construction Materials
Testing/Engineering
Tunnelling
Geophysics
Environmental, Ecological, Human
Health Risk Assessment
Community Outreach
Cultural Sciences/Archaeology
Permitting & Stakeholder
Engagement
Air/Acoustics/Noise
Toxicology
Energy Management
Waste Management
Health & Safety/Industrial Hygiene
Due Diligence Consulting
Industrial Wastewater Treatment
Groundwater/Hydrogeology
Surface Water/Sediments
Geochemistry
Biological Sciences
Ore Evaluation Services
Sustainability/Climate Change Adaptation
Renewable Energy
Process Engineering
Information Management & Graphics
Project/Program Management
Contracting/Construction Services
Decommissioning/Demolition
Brownfields
Enhanced Natural Attenuation
Hydrogeologic & Reactive Barriers
Thermal Desorption
In-Situ Chemical Oxidation
Sediment Remediation
Golder’s Service Areas
6
Golder Northeast
7
Speakers Remedial Technology Experience
Former USEPA Region I Alternative Technology
Coordinator and Private Experience:
Mobile Incineration Nitrobenzene Sludge
Thermal Desorption PCBs
In-Situ Vitrification VOCs
Soil Washing and Surfactants PCBs
Sludge Stabilization nitrobenzene sludge
LNAPL Remediation-Extraction-petroleum and solvents
ISCO Soil Blending/Injections-solvents and petroleum
Lessons Learned
Is it really “proven”
Bench Scale Tests are limited
Full Scale Pilot Tests are necessary
Vendors may promise everything
Materials handling and delivery systems are key to
success
Stakeholder Acceptance
There are no silver bullets 8
nZVI Intellectual Property (IP)
Waterloo patent (1993): Applicable to any iron body
placed in the ground by any means (PRB, reactive
zone, etc.). EnviroMetal Inc (Adventus) exclusive
license.
NASA (2003): EZVI = Emulsified Zero Valent Iron.
Colloidal iron in oil emulsion (DNAPL)
Zhang (2005): Production and use of NZVI for
groundwater remediation
Golder produces and implements nZVI
under license from Lehigh University
9
ENGINEERED Photo: www.nanovic.com.au/?a=news.prize&p=53&id=61
True (uniquely reactive)
INCIDENTAL Photo: www.iboro.ac.uk/departments/mm/research-
groups/thermofluids-combustion/graphics/soot.jpg
institutional defenses
NATURAL Photo: “Nanode Colony” Dr. Phillipa Uwins, University of
Queensland, Australia
natural defenses , new antibiotics
Types of Nano-Particles
10
Why go Nano/Sub-Micron?
In a given volume, smaller particles provide
larger total surface area
Surface Area = 3 m2
Sphere Radius =
1 m
Sphere Radius =
0.1 m
Total Surface Area = 30 m2
Sphere Radius = 0.1
mm
Total Surface Area = 3.07 m2
11
nZVI 2-5 μm
Bottom-up
Top-down
Atoms or
molecules
Mechanically
Grinded / Ball-Milling
Physical size
reduction
Lehigh University
2005
Chemically
Precipitated
Classical method
since 1996 (Zhang
et. al.)
Borohydride
reduction
Synthesis Approach
12
Zero Valent Iron (ZVI) and nano-Scale Zero Valent Iron (nZVI)
Zero valence oxidation state (Fe0)
Reacts with chlorinated solvents to produce non-
toxic products
nZVI allows for greater distribution in subsurface
Nanometer size/sub-micron size, but not truly
nano-material!
Does not exhibit different electronic properties from
bulk iron
Remedial applications include in-situ groundwater
remediation 13
Key Technical Issues
nZVI Reactivity Two (2) pathways, different products
• Beta-elimination (TCE->Acetylene)
• Hydrogenolysis (TCE->DCE->VC->Ethene)
Use of Bi-metallic Nano-Scale Particles
Pd coating is critical
nZVI Deliverability
Surface modifier is critical
“Fresh” is best
nZVI Treatment Longevity
Conversion from abiotic to biotic 14
What happens to Chlorinated Solvents?
Roberts, A. L., et. al, 1996 Reductive Elimination of Chlorinated Ethylene by ZV Metals. Environmental Science and Tech.
15
Permeable reactive barrier (PRB)
Specific surface ~500 m2/kg
Typical quantities needed -
Several metric tones
Installed PermeableIron Reactive Wall
GroundwaterContaining
Chlorinated
SolventsCleanGroundwater
Ground Surface
Bori ng
Boring
Bori ng
See p
ZVI Treatment
16
What does ZVI look like?
Fe0 core that shrinks over time reactivity
Iron oxide coating forms immediately in contact with water or air
Iron oxides will interact with aquifer materials
Will not travel indefinitely
Agglomeration ultimately forms Fe-oxide flocs with some continued reactivity
Fe0
Fe+2
Fe+3
50 nm
17
Why Bi-metallic?
Exploit noble metal chemistry gold, silver, palladium (Pd), platinum, tantalum,
rhenium, nickel, and copper
Highly resistant to oxidation or corrosion
Galvanic series (electro-potential series) Metals become catalytically important
Less noble metal (base metal) will experience galvanic corrosion (preferential oxidation of the base metal)
Siphoning electrons from iron because the noble metal (Pd) is resistant to donating electrons
We use Pd
as a surface
catalyst
With Pd,
nZVI is
called BMP
BMP reacts
more
closely to
freshly
precipitated
nZVI
18
Taken from: Oberdorster et al., Rapid Environmental Impact Screening for Engineered Nanomaterials: A
Case Study Using Microarray Technology June 2006
benzo[a]pyrene - LC50 < 0.1
ppm (Govers et al., 1984)
48 hour LC50 ~ 55 ppm
Same as bulk iron
• Are these truly nano?
Classified as slightly toxic
No different from PRB
Fish study show no mortality
What about toxicity?
19
FACT FICTION WHY? 60 – 80%
dechlorination in one
(1) year
100% dechlorination in
hours
bench scale, thorough
mixing, good contact
Estimated zones of
influence
nZVI travels indefinitely
with groundwater
Flocculation, settling,
interaction of oxide with
aquifer
nZVI is a nano size
material at production,
not in subsurface
nZVI is a nano-material
no change in electronic
properties, flocculation
occurs rapidly in
subsurface
Expectations
20
Field-scale Implementation
20 pilot- and full-scale implementations
worldwide!!
Site Information Site Location Geology Contaminants
Treated Contact Information
Pharmaceutical Facility Research Triangle Park, NC Fractured bedrock PCE, TCE, DCE, VC Florin Gheorghiu, Golder Associates +1 856-793-2005 [email protected]
Manufacturing/Research
Facility Research Triangle Park, NC Fractured bedrock PCE, TCE, DCE, VC
Michael Borda, Ph.D. ([email protected] and Florin Gheorghiu
([email protected]), Golder Associates +1 856-793-2005
Nease Chemical Salem, OH Fractured bedrock PCE, TCE, DCE, VC Michael Borda, Ph.D. ([email protected]) and Florin Gheorghiu
([email protected]), Golder Associates +1 856-793-2005
Brownfield Rochester, NY Fractured bedrock TCE Allen Kane, Golder Associates +1 610-941-8173 [email protected]
Industrial Plant Rochester, NY Fractured bedrock
Methylene chloride,
1,2-dichloropropane,
1,2-dichlorethane Allen Kane, Golder Associates +1 610-941-8173 [email protected]
Industrial Plant Sheffield, AL Unconsolidated sediments PCBs, PCE, TCE,
DCE, VC Jeff Paul, Golder Associates +1 770-492-8150 [email protected]
Brownfield North Alabama Unconsolidated sediments PCE, TCE, DCE,
PCBs Chris Paul, Golder Associates +1 770-496-1893 [email protected]
Former Chemical Storage
Facility Winslow Township, NJ Unconsolidated sediments PCE, TCE, DCE Heather Lin, Golder Associates +1 856-793-2005 [email protected]
Industrial Plant Rock Hill, SC Unconsolidated sediments TCE, DCE David Ley Golder Associates +1 770-496-1893 [email protected]
Lake Lucina Cleaners Florida Unconsolidated sediments PCE, TCE, DCE Kelly Baltz, Golder Associates +1 904-363-3430 [email protected]
Adams Cleaners Florida Unconsolidated sediments PCE, TCE, DCE Kelly Baltz, Golder Associates +1 904-363-3430 [email protected]
Town-N-Country Cleaners Florida Unconsolidated sediments PCE, TCE, DCE Kelly Baltz, Golder Associates +1 904-363-3430 [email protected]
Touch of Quality Cleaners Florida Unconsolidated sediments PCE, TCE, DCE Kelly Baltz, Golder Associates +1 904-363-3430 [email protected]
Malnove / Potlatch Florida Unconsolidated sediments PCE, TCE, DCE Kelly Baltz, Golder Associates +1 904-363-3430 [email protected]
Valcartier Garrison Quebec, Canada Unconsolidated sediments TCE, DCE, VC Sylvain Hains, Golder Associates +1 418-781-0285 [email protected]
Industrial Plant Ontario, Canada Unconsolidated sediments PCE, TCE Florin Gheorghiu, Golder Associates +1 856-793-2005 [email protected]
Solvent Manufacturing
Plant Czech Republic Unconsolidated sediments PCE, TCE, DCE
Michael Pupeza (Golder Associates) +39 (348) 450 0375
[email protected]; Miroslav Černík (AQUATEST a.s., Czech Republic),
Industrial Plant Czech Republic Fractured bedrock PCE, TCE, DCE
Michael Pupeza (Golder Associates) +39 (348) 450 0375
[email protected]; Miroslav Černík (AQUATEST a.s., Czech Republic),
Industrial Plant Germany Unconsolidated sediments TCE, DCE, Cr, Ni Johannes Bruns, Golder Associates +49 5141 989614 [email protected]
Industrial Plant Biella, Italy Unconsolidated sediments TCE, DCE Michael Pupeza (Golder Associates) +39 (348) 450 0375
Brownfield Slovakia Unconsolidated sediments TCE, DCE
Michael Pupeza (Golder Associates) +39 (348) 450 0375
[email protected]; Miroslav Černík (AQUATEST a.s., Czech Republic),
SUMMARY OF GOLDER PROJECTS
By the numbers…
23 Locations World-Wide
14 in US (61%)
6 in Europe (26%)
2 in Canada (9%)
1 in Caribbean (4%)
19 Chlorinated ethene Sites (83%)
2 PCB Sites (9%)
1 Chlorinated Methane and Ethane Site (4%)
1 Chromium Site (4%)
nZVI Materials
Mechanically crushed (78%)
Well-head precipitated nZVI (18%)
Laboratory precipitated (4%)
22
0.00
0.20
0.40
0.60
0.80
1.00
1.20
0.0 0.5 1.0 1.5 2.0
Elapsed Time (Hrs)
C/C
0 TCE
C2H6
C2H4
Sum
Results
Plume
Characteristics
2.5 miles long
0.5 miles wide
130 ft deep
TCE
Multiple Source Areas
Valcartier Garrison, Canada
24
P I - 0 6 - 5 P I - 0 6 - 6
P O - 0 6 - 3 P O - 0 6 - 4 P O - 0 6 - 5 P O - 0 6 - 6
P O - 0 6 - 8 P O - 0 6 - 1 0 P O - 0 6 - 1 1 P O - 0 6 - 1 2
P O - 0 6 - 1 5
P O - 0 6 - 9
P F D - 1
P F D - 2
P F D - 3
P F D - 4 P F D - 5
P F D - 6 P F D - 7
P F D - 8
P F D - 9
P F D - 1 0
P F D - 1 2
P F D - 1 1
P F D - 1 4
P F D - 1 3
P F D - 1 5 P F D - 1 6
P F D - 1 7
P F D - 1 8
P F D - 1 9
P F D - 2 0
P I - 0 6 - 7 P I - 0 6 - 4 P I - 0 6 - 3
P O - 0 6 - 1 4
P O - 0 6 - 1 3
P O - 0 6 - 1 6 C P T - 5
C P T - 4
C P T - 8 C P T - 9
C P T - 7
C P T - 6
P I - 0 6 - 8
P F D - 2 1
P F D - 2 2
P F D - 2 3
P F D - 2 4
C P T - 1 1
C P T - 1 0
P O - 0 6 - 2 P O - 0 6 - 1 C P T - 1
P I - 0 6 - 2 P I - 0 6 - 1
P O - 0 6 - 7
Treatment
zone
5 m
40 m
4,500 kg of Golder nZVI
0.1% Pd
Slurry density of 10 g/l to 40 g/l
80,000 L soy protein dispersant
Groundwater flow
Injection Layout
26
Results
After nZVI injection, ORP values drop <-400 mV, microbiologic diversity shifts
TCE reduced by 50 – 60 % in 1 month
TCE reduced by >80% after 10 months, no build-up of daughter products
After 10 months, DCE concentrations increasing, correlated to biological re-diversification
Golder retained for full-scale implementation
In excess of 100,000 kg BNP proposed for treatment
nZVI
Treatment,
Design and
Implementation
Pilot-scale (100
x 100 x 40 m)
Injection of
4,000 kg of
BNP (nZVI-
palladium) and
soy powder
dispersant
Microbiological
screening
performed to
assess
bioremediation
26
Quebec, Canada - Concentration Data
27
RCRA CA Site: North Carolina Bedrock nZVI Injection using Hydraulic
Fracturing,
North Carolina
Ohio
28
Results
0
500
1000
1500
2000
2500
3000
-200
-150
-100
-50
0
50
8/12/08 12:00 8/13/08 0:00 8/13/08 12:00 8/14/08 0:00 8/14/08 12:00 8/15/08 0:00 8/15/08 12:00
Turb
idit
y [F
NU
], D
O [
ug/
L],
Co
nd
uct
ivit
y [u
S/cm
]
Pre
ssu
re [F
ee
t o
f W
ate
r], O
RP
[m
V]
Date and Time
P-5 Multi-Parameter Monitoring During Hydrofracking and nZVI Injection
P-5 Hydraulic Head Changes P-5 ORP BNP-4 Hydraulic Head Changes P-5 Turbidity P-5 DO P-5 Conductivity
Hydrofracking
nZVI Injection Day 1 nZVI Injection Day 2
TURBIDITY
P-5 Pressure
BNP-4 Pressure
29
0
50
100
150
200
250
300
350
02-juil-06 21-août-06 10-oct-06 29-nov-06 18-janv-07 09-mars-07 28-avr-07 17-juin-07 06-août-07 25-sept-07 14-nov-07 03-janv-08
Date (JJ-MM-AA)
Co
nc
en
tra
tio
n T
CE
(u
g/L
)
PI-06-1 PI-06-2 PI-06-3 PI-06-4 PI-06-5 PI-06-6 PI-06-7 PI-06-8
Injection #1 Injection #2 Injection #3
Performance criteria
nZVI Treatment Longevity
Pilot-Scale Study showing prolonged treatment of TCE over 18 months
Short-term treatment with abiotic nZVI reactions
Long-term treatment with abiotic and enhanced bioremediation
30
nZVI Treatment Longevity
0
20
40
60
80
100
120
140
160
180
200
02-juil-06 21-août-06 10-oct-06 29-nov-06 18-janv-07 09-mars-07 28-avr-07 17-juin-07 06-août-07 25-sept-07 14-nov-07 03-janv-08
Date (JJ-MM-AA)
Co
nc
en
tra
tio
n D
CE
(u
g/L
)
PI-06-1 PI-06-2 PI-06-3 PI-06-4 PI-06-5 PI-06-6 PI-06-7 PI-06-8
Injection #1 Injection #2 Injection #3
Performance criteria
31
ORP (-100 mV) ORP (200 mV)
TOC
(1,5 mg/l)
pH (6.3)
BOD (<4 mg/l)
O2 (9.5 mg/l)
Before nZVI
injection
ORP (-450 mV)
TOC
(250 mg/l)
pH (6.1)
O2 (0.7 mg/l)
TOC
(25 mg/l)
pH (7.0)
BOD (15 mg/l)
O2 (2.0 mg/l)
1 month
after
11 month
after
Mean Geochemical Values Across a Treatment Area
Values measured in the treatment area
Values measured at the injection wells
Intro - Long-term Geochemical Changes
32
North Carolina Test Summary
First bedrock fracturing for remediation in NC
Total nZVI injected was 90 kg mixed in 2,500
gallons of water
Average nZVI concentration was 9.5 grams
per liter (g/L)
Injection rate initially 6 gpm with back
pressure of 60 psi
Increased to12 gpm with decrease in back
pressure to 50 psi
33
EXPECTED FUTURE
DEVELOPMENTS
Further Development of Dispersing/Stabilizing Agents
Further Development of Micro-ZVI
Further Development of Composite Powders
34
Further Development of Micro-ZVI
Golder Research
35
KEYS TO SUCCESS
Well-developed Conceptual Site Model
ZVI Material and Additive Selection
Full Scale Pilot Tests
Regulatory Acceptance
Reactivity
Deliverability
Treatment Longevity
36
WHAT’S ON THE HORIZON FOR nZVI
Advances in “green” dispersants
Continuing research on toxicity
Enhancing deliverability with injection
technologies, Electro-Kinetics
New iron materials, particle sizes, mixtures
of iron
37
CLOSING
Challenges exist to duplicate bench scale results in the field
nZVI is not a remedial panacea
nZVI research and implementation community must help to alleviate
regulatory concerns based on sound science
