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Cleaned
By Nature
Manipulation of Emulsion
Chemistry for Emulsified
Vegetable Oil Applications
Michael R. Sieczkowski, CHMMJRW Bioremediation, LLC
NDIA ENVIRONMENT, ENERGY & SUSTAINABILITY SYMPOSIUM & EXHIBITION
DENVER, CO
June 14, 2010
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BIOREMEDIATION OF CHLORINATED
SOLVENTS THROUGH ENHANCED
REDUCTIVE DECHLORINATION
• Based on attaining and maintaining
anaerobic conditions until complete
degradation is accomplished.
• Add organic substrate to establish
anaerobic conditions and provide
hydrogen from fermentation for
dechlorination.
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HOLY GRAIL OF SUBSTRATES
• Supportive of RD
• Good dispersion
• Good persistence
• Easy to store & mix
• Easy to inject
• Inexpensive.
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ORGANIC SUBSTRATES
• Readily soluble
– lactates
– alcohols
– sugars (molasses)
• Slowly soluble
– engineered polymers
– biopolymers (chitin)
– whey
– oils.
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SUPERIOR OIL SUBSTRATE
• Slowly soluble
• Non-coalescing
• Small uniform particle
size
• Minimally attracted to soil
• Easy to store, mix and
inject.
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STANDARD EMULSIONS
Mixture of two
immiscible
materials, and
surfactant
Kinetic stability –
natural state is
separate phases
Particle size can be
manipulated.
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MICROEMULSION
Mixture of two immiscible materials and surfactant
Thermodynamically stable –natural state is single phase
Inherent small particle size
Readily forms and mixes
with water
Ultralow surface tension.
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Modified from B. Paul, S. Moulik, Current Science, Vol 80, No 8, 25 April
2001
Typical Forms of a Microemulsion
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DEVELOPMENT OF A SOY
MICROEMULSION - LACTOIL™
Thermodynamically stable microemulsion
Bi-continuous phase, oleaginous material,
surfactant, ethyl lactate, water
High Zeta potential (-83 mV at pH of 8.0)
Small particle size.
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Neat LACTOIL™ after 30 days Dilute LACTOIL™ (1:9) after 30 days
EMULSION STABILITY
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LactOilTM
EVO1
EVO2
EMULSION PARTICLE SIZE
Differential Volume
Vo
lum
e (
%)
Particle Diameter (µm)
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EASE OF MIXING
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MICROEMULSION
Small particle size allows material to flow
through soil pores
High thermodynamic stability allows
material to move advectively
Ultralow interfacial tension allows
material to readily mix with water
High Zeta potential allows some material
to “stick” to soil.
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LAB EVALUATION
Biologically active lab tests
Comparative tests with other EVOs
Multiple dosages of PCE to attempt to
reach substrate exhaustion
Microcosms run for over one year.
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Lactate Production
0.00
0.20
0.40
0.60
0.80
1.00
25 127 218
Days
um
ole
s
LACTOIL™ EVO1 EVO2
EVIDENCE OF EMULSION STABILITY
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Ethene
VC
c DCE
TCE
PCE
LACTOIL™ EVO1 EVO2
100%
90%
80%
70%
60%
50%
40%
30%
20%
10%
0%
Active Laboratory Microcosms
Relative Proportion of Chlorinated Ethenes at 277 Days
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Lab Conclusions
• The material performs as well or better than standard EVO
• Minimal material preparation is required
• Microemulsion stability is in excess of 6 months.
Photo courtesy of Dr. Rachel Brennan, Penn State University
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FIELD TRIAL
1
Bedrock
Alluvium Alluvium
Conceptual Site Model
ICM
Biobarriers
Photo courtesy of Shaw E&I
Figure courtesy of Shaw E&I
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µMoles CHC MW-005
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
Historical Pre-Treatment Day 212
TCE
cis-1,2-DCE
VC
µMoles CHC MW-007
0
1
1
2
2
3
3
Historical Pre-Treatment Day 212
PCE
TCE
cis-1,2-DCE
VC
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Average ORP SCA Barrier
-300.0
-250.0
-200.0
-150.0
-100.0
-50.0
0.0
50.0
100.0
6/15 7/15 8/14 9/13 10/13 11/12 12/12
mV
FIELD RESULTS
Injection
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FIELD CONCLUSIONS
• The process has reduced TCE in shallow aquifers for extended periods of time
• The process can be implemented using basic field techniques
• The process has proven repeatable in seven areas of the site.
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RECENT FIELD RESULTS
Battelle Seventh International Conference
Remediation of Chlorinated and Recalcitrant
Compounds
May 2010
Site 24, Treasure Island Naval Station
Site 19, Vandenberg AFB
Former Fire Training Area, Myrtle Beach AFB
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