L

By cr^atin^a hydrophil^
substrate ffom Regenesis is reducing the cos
chlorinated solvent cleanup and getting t f ^
hydrogefl in the right place at the right Wri

By SCOTT B. WILSON, president and CEO of Regenesis

It has been well over two decades that contaminated

groundwater has been successfully treated by stiniuhitinj^
natural biological processes wiihin polluted oquifcrs. This
process, coined "in-situ bioremediation," caught on in ilif
iy9()s and has since become a commonly (.-mployed sirat-
egy for cleaning pollution within groundwater systems and
soils onsite.
The particular process of employing bioremediiition to chlorinat-
ed solvent contamination is rather complex, often involving inject inn
of organic chemical substrates into the contaminated subsurface. In
turn, these substrates stimulate v.irious biochemical processes that
ultimately result in contaminant degradatit)n or dcslniction.
The cost etlectiveness of applying in-situ bioremediation to chlo-
rinated stilvent contamination hinges directly on the chemical and
physical characteristics of the .substrate applied and the ability to
successfully distribute the material in the subsurface. Recent develop
nients in substrate chemistry now allow for remaliation engineers to
distribute advanced substrates over signitkanl sul)surfate volunie.s
with lower capital costs.
 Cli^^
H
H El " H

H-C =C-H H-C =C-H

Perchloroethylene (PCE) Trichlofoethylene (TCE) Dichloroethylene (DEC) Vinyl Chloride (VC) Ethene

Figure 1: The reductive dechlorination process.

Anaerobic bioremediation
of chlorinated solvents
The most commonly encountered chlori-
nated solvent poliutants in groundwater
and soil are chlorinated ethenes, com-
monly used as dry cieaning solvents and
degreasers. These include perchioroethene
(PCE), trichloroethene (TCE) and trichlo-
roethane (TCA).
Bioremediation of these compounds takes
piace in the suhsurface through a biological
process known as "reductive dechtorination."
To stimulate this process, the environmental
engineer must apply a substrate directly to
the contaminated subsurface zone, usually
thougli borings or wells. Tlie substrate is
then attacked by naturally occurring soil
microbes in what is techjiically a fermenta-
tion reaction to produce small amounts of
dissolved hydrogen. In turn the liydrogen is
used as an energy source by another set of
subsurface microbes known as dechlorinat-
ing microbes.
In the final step of the process, the
dechlorinating microbe donates an elec-
tron to the chlorinated solvent pollutant
removing a chlorine atom in the process.
This dechlorination proceeds stepwise,
removing multiple chlorine atoms until
achieving complete dechlorination. Once
the chlorine atoms are removed from a
contaminant like PCE, the remaining por-
tion is rapidly degraded in the subsurface
by a numiier of processes (Figure I).
Soluble substrates
Much has changed since the first reductive
dechlorination projects were undertaken.
Initially, experiments were performed
in the field with the direct injection ol
gaseous hydrogen. This approach, while
successful, was not readily adopted com-

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Figure 2: Treatment design and cost summary comparison.
HRC Advanced 3-D Emulsified Oil
Product Cost Per Pound Microemulsion Substrote
Cost per pound of standard emulsion
$0.37 32,95
(includes est, shipping)'
% Carbon 0,1 0,6^
Equivalent cost of pure carbon S/lb. $3,70 $4,92
Total Product Costs
Appiication Area (100' x 100' x 10')
Corbon Required (pounds) 10,000 10,000
Std, Emulsion Required (pounds) 100,000 16,667

Dilution Water required for 1:20 (gailons) 13,226 23.293

Total Volume of Dilution to be Appiied

25,274 25,377
(est, gaiions)

TOTAL PRODUCT COSTS ($) $37,000 $49,167

Application Costs
Number of Injection Points Required 42 100

Cost per injection weii (3/dav x S3,500/day) $49,000 $117,000

Oversight Costs ($750/day) $10,500 $25,000

TOTAL APPLICATION COSTS $59,500 $142,000

TOTAL COST OF PRODUCT AND
$96,500 $191,167
APPLICATION ($>
* Per pound pricing is tor "standard emulsion." HRC Advanced standard emulsion is prepared on-site as a 1:10 micro-
emuision avoiding the excess shipping costs associated with transporting pre-mixed oii in water emulsions.

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mercially due to the logistics of applying the hydrogen gas itself
into the subsurface. Research conducted in a variety of university
laboratories around the world then focused on the potential of
comnn)n organic substnites and their ability to ferment in the
subsurface thus releasing hydrogen in place.
When employing a
controlled-release substrate for
chlorinated solvent bioremedia-
tion, the initial subsurface
distribution of the product is
key to the success of
the project.
Fermentation through the use of many low-cost, common,
soluble substrates has been shown lo result in adequate hydrogen
generation within the subsurface environment and to stimulate
reductive dcchlorination. Such soluble substrates include: sugar
solutions, organic acids such as lactate, alcohol and others. Each of
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these compounds are easily pumped into the subsurfece and rapidly
dissolved in groundwater.
It was soon realized, however, that while these soluble substrates
were low-cost on a por-pound basis, the cost of application was often
high, leading to very high life cycle project costs.'" The unexpected
aists of using soluble substrates are usually associated with:
• Rapid fermentation, resulting in much of the hydrogen gen-
orating methane rather than stimulating dcchlorinalion. This
requires either a continuous addition of the substrate or fre-
quent reapplication. It is not uncommon to require monthly
reapplications of soluble substrates such as laclate solutions.
• Fouling of iniection wells due to rapid biological growth during
continuous injection requiring injection well maintenance
• "Washout" as fast-moving groundwater systems can carry thc
soluble substrate down gradient out of the treatment zone.
Controiled-Releose Substrates
A variety of controlled-release substrates have been developed that
ofter the remediation industry a lower-cost approach to injecting
soluble organic compounds. These alternatives include compounds
such as specialized polylactale esters that slowly relea,se lactate'", to
varying formulations of emulsified vegetable oils that are applied in
high volumes through multiple wells onsite. The common element
of all of these products is that upon application to the subsurface.
OCTOBER2007 www.poHution0ngin00ring.com
they produce a controlled-release of the
hydrogen needed tor chlorinated solvent
contaminant reduction without the need for
cosdy reapplication. The use of these prod-
ucts, while higher on a unit costs basis (dol-
• 90+% dry solids
• Class A Exceptional Quality
• Minimal off-gas volume
lars per pound of substrate), usually result in
much lower overall project life-cycle costs.'"
When employing a controlled-release
substrate for chlorinated solvent biore-
mediation, the initial subsurface distribu-
tion of the product is key to the success
of the project. Without necessary hydro-
gen within the target treatment zone, thc
desired contaminant degradation wilt
not be achieved. The question put before
the remediation design engineer is how
to most cost-effectively distribute thc
product within the aquifer matrix? This
requires maximizing the subsurface vol-
ume impacted by the controlled-release
product from each point of subsurface-
injection (boring or well).
One of the most important factors influ-
encing the distribution of bit)remediation
substrates is hydrophiie/Hpophile balance
(HLB). The HLB is an index used to
describe the tendency for a chemical sub-
stance to dissolve in water (hydrophilic) or
oil (lipophllic).''' The more hydrophilic a
compound (high HLB) the more readily it
dissolves and distributes in the subsurface.
Conversely, the more lipophilic (low HLB)
the less likely it will dissolve in water and
the more likely it will bind to thc aquifer
or soil matrix and distribute poorly. A
substrate with very high HLB such as
lactate (HLB 30) will distribute rapidly in
the subsurface through diffusion and flow
with groundwater movement, but as men-
tioned previously, the high solubility nia\-
cause it to ferment too rapidly and may
wash out of the treatment area.

• Low operating cost (Conversely, emulsified oil substrates have

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a very low HLB (-6), which significantly
limits its distribution. Emulsitled oil sub-
strates, when injecled into the subsurface,
Contact K-S for information tend to rapidly bind to the aquifer-mineral
and an evaluation of your surface. This generally occurs within thc
drying needs: first 1 to 2 meters from the injection point.
'"*' Laboratory studies have shown, and fiekl
data has corroborated, that the distribution
call: 1800 225 5457
of emulsified oil substrates is indepcndenl
lax: 1000 328 7457 of concentration of the oil emulsion injected
mail: 12 Holland Av and of the speed with which the emulsion is
Peapack, NJ 07077 applied. Unfortunately, injecting amounts of
additional "chase water" does not push these
e-mail: into^komline.com emulsified oil sub.strate droplets further out
web: www.komline.com as once il is bound to the aquifer thc oil is
immobile.

Komline-Sanderson Due to its very low HLB and insolubil-

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distribute by diffusion or groundwater flow.

46 Poliution Engineering OCTOBEH2007

Instead, emulsified oil substrates remain
sorbed to the aquifer directly in the area The self-distributing property of these
injected. The result is that the proper use of substrates allows for better penetration of
enuilsiHed oil substrates requires many injec-
tion points or wells packed closely together the contaminated aquifer...
in order to achieve adequate coverage of the
aquifer volume to be treated.
However, after sorbing to the aquifer sur-
ControUed-Release face, the majority of the substrate droplets
Substrates with balanced re-dissolve into groundwater, leaving behind
HLB only a thin coating of the substrate rather
In an effort to lower the cost of apply- than a heavy layer of adhered oil droplets.
ing bioremediation substrates, re.searcbers The dissolved substrate then moves with
at Regenesis, San Clemente, Calif., have thc groundwater flow and diffusion until it
developed a substrate with a balanced re-adsorbs nearby onto the aquifer surface.
HLB having tendencies to adsorb, yet Research has shown that if the dissolved
also to dissolve. This product (known as concentration of these balanced HLB sub-
3-D Micremulsion) is injected into the strates exceeds what is referred to as the
subsurface as a suspension mixed with critical micelle concentration, or CMC, the
water and has a tendency to sorb onto the dissolved substrate can actually tbrm molec-
aquifer matrix, similar to emulsified oil ular spheres containing very small droplets
substrates. (0.01 to 0.05 microns) of the substrate called
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"micelles." These micelles move outward in
the subsurface until adhering nearby to the
aquifer matrix.'"^'
Once attached, this qfcle of partial dis-
solution/transport/adsorption repeats until
a thin layer of substrate coats the aquifer
matrix target area, where it then stimulates
the desired bioremediation. The self-dis-
tributing property of these substrates allows
tor better penetration of the contaminated
aquifer than has been available in a con-
trolled-release biological substrate.
The benefit of gaining increased distri-
bution in the subsurface upon injecting
a substrate is very apparent: much lower
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capital cost. The .self-distributing property of
advanced substrates allows the remediation
engineer to achieve treatment of the target
area with fewer injection wells and appli-
cation of less substrate material. A typical
aquifer treatment design and cost summary
i.s presented in Figure 2.
The technical approaches used in the
bioremediation of chlorinated solvent con-
tamination in groundwater and soils have
evolved substantially over the past two
decades. This is very apparent when select-
ing a substrate for injection into contami-
nated zones. While a range of options are
available, controlled-release substrates have
been shown to present lower overall project
costs by saving time and money on opera-
tions and reappHcation.
Recent advances in substrate chemistry
now offer the remediation engineer the
opportunity to utilize a controlled-release
substrate that self-distributes over the target

Expandingy" volume of the subsurface. This allows lower

up-front capital life cycle costs in projects
treating cblorinated solvents in-situ. PE
Your Possibilities Scott B, Wilson Is president ond CEO of Regenesis.
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References
1. Cost Estimating Toois for Enhanced Anaerobic
Bioremediation: Josh Fartenberry, et ai.j
Proceedings of the Fourth International
Conference on Remediation of Chlorinated
ond Recalcitrant Compounds. Monterey.
Cailf., 2004.
2. A Comprehensive Performance Analysis ot
Hydrogen Reiease Compound (HRC): 1999-
2004; Anna Wiiiett and Stephen Koenigsberg;
Proceedings of the Fourth International
Conference on Chlorinated and Recalcitrant
Compounds. Monterey. Caiif., 2004.
3. DaviesJ: 1957. "A quantitative kinetic theory of
emuiston type, i. Physlcai chemfelry of the emui-
slfying agent." Gas/Liquid and ilquld/iiquid
Inierface. Proceedings of /he International
Congress of Surface Activity. 426-438.
4. Borden et, ai,, 2005 Workshop on Enhanced
Anaerobic Bioremediation using Emuisified
Edibie OII, Eighth internationai Insitu and
On-Site Bioremediation Symposium, Baltimore.
5. Impact of Eiecrton Donor Hydrophiie/Upophiie
Baiance on Subsurface Distribution; Wilson,
Keiiey, Mork. Cormack; Ninth internationai
in-Situ and On-Site Boremediaticn Symposium,
Baltimore, 2007.

46 Pollution Engineering OCTOBER2007