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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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