ust as electricity has been

ELECTROCHEMICAL
J
used to promote clean and
efficient lifestyles, it is now
being investigated a s a
method for cleaning u p
some of the country’s most
stubborn hazardous waste sites. At
a March workshop at the Electric
Power Research Institute (EPRI) in
R E M E D I AT ION
Palo Alto, CA, more than 60 repre-
sentatives of the private and public
sectors discussed the use of electric
TAKES TO THE = T L D
currents to clean contaminated soils
and groundwater in situ. “Partici-
pants, including EPRI, needed an
assessment of the field and a com-
parison with other remediation
technologies,” explained Fritz Will,
professor of chemical engineering at
the University of Utah and visiting
scientist at EPRI.
Although electrochemical reme-
diation generally is still in its in-
fancy, several presentations sug-
gested that the process is inching
toward commercialization in cer-
tain applications. “Right now its
strongest suit is the removal of inor-
ganic contaminants,” said Will. Al-
though studies of electrokinetic re-
mediation of organics are lagging
behind those of inorganics, Will
pointed out that EPRI has a strong
interest in the removal of organics,
including petroleum products.
Approximately nine field demon-
strations are being launched in the
United States this summer to ana- least half of the toxic than, conventional re-
lyze the effectiveness of electrore- waste sites in the coun- mediation methods.
mediation in treating a wide variety try. “Except for soil va- Efforts i n Europe
of pollutants. The field demonstra- por extraction, which have led the race to ap-
tions follow on the heels of labora- works only on certain ply t h e technology.
tory tests in which scientists re- contaminants in unsat- Geokinetics. based in

1
ported having achieved removal urated soils, in situ re- The Netherlands (see
efficiencies ranging from 44% to mediation technologies ESbT, Dec. 1993, p.
99% for a wide variety of contami-
nants, including sulfates, nitrates,
are for the most Dal
only i n the deveioF
remediation I is 26481 holds some of the
earliest European pat-
chromium, uranium, mercury, solu-
ble organics such as phenol and
m e n t stage,” sai’
Jonathan Herrmann, sr
inching toward LISon electroremedia-
in of soil. Geokinetics
benzene-toluene-xylene, and poly-
cyclic aromatic hydrocarbons.
pervisory environmer
tal engineer at EPA.
commercialization currently stripping
ixed toxic metals
Meanwhile, companies in Europe As a n i n situ ap
and Russia have begun to use the proach, electroremediz in certain Rhine sludges in
Rotterdam, one of Eu-
process commercially to remove tion holds an advantag
heavy metal contaminants includ- over standard “pumF applications. rope’s most environ-
entally damaged
ing uranium, mercury, and mixed and-treat’’ systems bt anufacturing areas.
metals. cause of its high level of control over While work is being done under con-
Electrochemical remediation has flow direction. Economics are also a fidentiality agreements on a variety
garnered considerable interest from driving force. Some researchers re- of mixed pollutants, Geokinetics has
U S . scientists and business repre- ported costs of $90-$130 per ton, started removing cyanide from gas
sentatives because it is the only in which are comparable to, if not lower works sites, reports Robert Clarke, di-
situ method that could work in low- rector of technology for the Electro
permeability clays and silt-laden Remediation Group, w h i c h has
soil-onditions that characterize at BY JEA NNE T RO MB LY teamed up with Geokinetics in EU-

0013-936X194/0927-289A$O4.50/0 0 1994 American Chemical Society

Environ. Sci. Technol., VoI. 28,No. 6, 1994 289 A
rope and the United States.
Several other collaborations are
under way, which suggests that
companies and researchers are posi-
tioning themselves to pursue this
rapidly developing technology. But
against the backdrop of promising
tests and limited overseas commer-
cialization, some scientists have ex-
pressed concern about moving too
quickly into field demonstrations.
“If you’re going to go into a messy
mixed waste s i t e with limited
knowledge, you’re going to fail, and
electroremediation is going to gain a
bad name,” said Ronald Probstein,
professor of mechanical engineer-
ing at the Massachusetts Institute of
Technology (MIT).
Probstein stressed the need to
couple laboratory models with lim-
ited field trials, especially at sites
where the contaminants are not
well characterized and soils are not
uniform. With U S . Department of
Energy funding, Probstein is devel-
oping a mathematical model that
determines how best to treat a site
by analyzing the effects of varying
conditions such as the background
chemistry of the groundwater, the
contaminants and soil characteris-
tics, and the existence of other con-
taminants. “It currently uses a Cray
computer, but we are adapting the
model for use on a PC so that it can
be brought to the field sites like a
mobile laboratory,” said Probstein.
Fritz Will agreed that lab and field
work should co-evolve, adding that
more soil chemists should be in-
Electroosmosis is one of the primary electrochemical transport mechanisms
whereby water moves through charged soil. Electroosmosis has shown good
results in removin soluble organics. (Adapted from U.S. Patent No. 5 074 986,
Dece-$4,. ,-s* i 19& .)
j_i
290 A Environ. Sci. Technol., Vol. 28, No. 6, 1994
volved because varying soil condi-
tions can affect outcome.
As civil and mechanical engi-
neers, electrochemists, biochemists,
and soil chemists team up on elec-
trochemical remediation efforts, the
process gains more names. It has
been called “electroremediation,”
“electroreclamation,” “electroresto-
ration,” and “electrokinetic remedi-
ation and restoration.”
Although different mechanisms
guide the process, electroremedia-
tion occurs when low-voltage di-
rect-current electric fields are ap-
plied to contaminated sites by
means of electrode arrays. Electric
current flows between pairs of posi-
tive anodes and negative cathodes
placed in the ground. Whether situ-
ated horizontally in trenches or ver-
tically in drilled tunnels around the
marked site, the electrodes serve as
goal posts to migrating heavy met-
als, soluble organics and, in some
cases, insoluble organics. Once the
charged ionic contaminants or s o h -
bilized pollutants have accumu-
lated at the electrode, they are more
easily extracted in their concen-
trated form for treatment by conven-
tional methods or remediated i n
contained treatment zones.
Electrochemical remediation is
characterized by electromigration,
electroosmosis and, less commonly,
electrophoresis. Electromigration is
the movement of ions in an electric
field from one electrode to another.
Because most organics aren’t ion-
ized, this process works primarily
on highly soluble ionized inorgan-
ics including alkali metals, chlo-
rides, nitrates, and phosphates in
moist soil environments. Addition-
ally, heavy metals such as lead,
mercury, cadmium, and chromium
have responded favorably, some
with the aid of complexing agents.
In some instances, it is necessary
to treat the area around the cathode
to adjust pH levels to prevent pre-
cipitation of the metals in the soil.
For example, the removal of zinc
w o u l d require a low pH level,
whereas chromium- and uranium-
tainted soils would be treated to
yield a high-pH solution. Most elec-
tromigration tests have taken place
in low-permeability, nearly satu-
rated soils, but Eric Lindgren of
Sandia National Laboratories (Albu-
querque, NM) is working on remov-
ing chromate from unsaturated
sandy soils. Dry soils, however, re-
quire more electricity, which is
likely to increase remediation costs.
Electroosmosis is the other pri-
mary transport mechanism whereby
water moves through charged soil.
Water molecules are essentially
pried away from minute soil parti-
cles in low-permeability environ-
ments, and the water moves the pol-
lutants with it. Electroosmosis
works efficiently only with fine-
grained soils and clays. The process
has shown good results in removing
soluble organics. Dale Schultz of
DuPont reported positive results at
a site in the eastern United States
contaminated with an unnamed sol-
uble organic. Contaminant concen-
trations were reduced below detec-
tion levels by electroosmotically
driving about 1.5 pore volumes of
water through the soil. Moreover,
neutralizing pH at the anode with
lime or sodium hydroxide signifi-
cantly increased the efficiency of
the process. Results from a field
trial planned this summer should
reveal more details, Schultz said.
Even though insoluble organics
such as heavy hydrocarbons pose
more of a challenge for electroosmo-
sis, Sibel Pamukcu, professor at Le-
high University (Bethlehem, PA),
reported removal efficiencies of 44-
70% for some components of coal
tar-contaminated soil with the aid
of surfactant injection. The material
tested was excavated from a former
Illinois Power Company manufac-
tured gas plant site in Champaign.
Given preliminary promising re-
sults of electroremediation for treat-
ing heavy metals and organics, both
the Office of Environmental Resto-
ration and Waste Management at
the U.S. Department of Energy
(DOE) and EPA’s Risk Reduction
Engineering Laboratory in Cincin-
nati have been actively involved in
electrochemical cleanup demon-
strations. “Out of the 3700 hazard-
ous waste sites on DOE’S list, there
are 213 sites where electrokinetics
may be applicable,” reported Den-
nis Kelsh of Science Applications
International Corporation, who is
working on t h e DOE program.
“We’re giving electrokinetics five
years to prove its validity in the
field,” said Kelsh. Facing mandated
cleanup requirements in the year
2019, DOE is focusing on cost-effec-
tive in situ approaches.
In what may become one of the
quickest demonstrations of elec-
troremediation technology emerg-
ing from laboratory to field testing,
Monsanto, DuPont, a n d General
Electric, in cooperation with DOE
and EPA, are working together to
test the “lasagna” process, named
for the application of layered treat-
ment zones. Developed by Philip
Brodsky, director of corporate re-
search and environmental technol-
ogy for Monsanto, the lasagna pro-
cess takes the concept of migrating
pollutants one step farther. “By
combining electrokinetics with
other proven remediation ap-
proaches, this process cleans u p
hazardous wastes as they are mov-
ing,” said Brodsky.
Instead of merely attracting toxins
to one spot via electric charge, the
lasagna process takes advantage of
electroosmotic movement by luring
stubborn organic chemical deposits
through multiple layers of remedia-
tion treatment zones that are estab-
lished through hydrofracturing and
sheet piling. First, low-voltage elec-
trical current draws contaminated
water by electroosmosis out of tiny
pores in silt and clay where it may
be trapped. The water is slowly
pulled, typically, toward the cath-
ode, moving a few inches per day
through treatment zones that utilize
existing remediation methods such
as biodegradation, catalytic dechlo-
rination, and absorption.
The lasagna consortium has just
started to demonstrate a vertical
electroosmotic system at a DOE site
in Paducah, KY. A horizontal lasa-
gna process, more applicable to
deeper sites, is being tested concur-
rently by EPA near Cincinnati,
where the agency is already con-
ducting a hydraulic fracturing ex-
periment.
Several other collaborations un-
der way are moving the technology
into field tests. New Orleans-based
ISOTRON~ has
~ collaborated with
Russian scientists on a process to
clean up heavy metals. According
to Henry Lomasney, president of
ISOTRONTM,the Russians have
successfully remediated six sites in
Uzbekistan and Kazakhstan where
acid leachates from mines have con-
taminated the groundwater. Despite
crude techniques, such as using
electrodes made of steel instead of
more advanced materials available
in the United States, Lomasney re-
ported achieving extraction effi-
ciencies of 99.5% for heavy metals,
including 97% for uranium and
69% for sulfates.
I S O T R O N ~is~ working w i t h
HAZWRAP, a subsidiary of Martin
Marietta, to replicate the Russian
process at an Oak Ridge, TN, site for
DOE. ISOTRONTMhas also devel-
oped a patented system utilizing cy-
lindrical electrodes that is being
used at a DOE-funded project con-
ducted by Westinghouse Savannah
River Company at the Savannah
River site’s old TNX Seepage Basin,
from which results are expected
this year.
DuPont Environmental Remedia-
tion Services has teamed up with
Corrpro Companies, Inc., which has
worked in the cathodic protection
industry for decades. Corrpro li-
censed MIT’s patented electroos-
motic purging process, and the team
is developing a panel electrode ar-
ray to achieve more uniform electric
fields.
Both research and field tests are
receiving support from the federal
government. At a total investment
of more than $2 million, DOE has
sponsored six projects in 1993, in-
cluding the lasagna project, the de-
velopment of Probstein’s mathemat-
ical m o d e l , a n d t h e d r y - s o i l
experiments at Sandia. EPA is also
cosponsoring demonstrations, but
instead of funding research, it is fo-
cusing its limited resources on field
demonstrations. By folding electro-
kinetics into one of its own field
tests, EPA will be conducting elec-
troosmosis tests at a hydrofractur-
ing project under way near Cincin-
nati. Particular attention is being
paid to time-dependent flow condi-
tions, nonuniform treatment of
soils, the costs associated with
chemical a d d i t i v e s a n d above-
ground treatment, a n d efficient
electrode configurations.
In addition, EPRI and Southern
California Edison have been fund-
ing research in electroremediation
for a number of years and jointly
Environ. Sci. Technol., Vol. 28,No. 6,1994 291 A
sponsored the recent workshop.
Ishwar Murarka and Ammi Amar-
nath, managers of EPRI’s electrore-
mediation projects, report that EPRI
has so far invested approximately
$500,000 in three university studies
and plans to continue sponsoring
research in this area.
Several concerns about future re-
search strategies were raised by par-
ticipants at the workshop. Site char-
acterization factors need to be
identified so that sites best suited
for electrokinetic treatment can be
determined. Knowing whether large
metallic objects are in the soil is im-
portant because pipes or other
metal objects can slow down or
even defeat the process. Likewise,
poor in situ performance can result
from the presence of other chemi-
cals in the soil such as humic sub-
stances and naturally occurring
electrolytes. Potential side effects
such as acidification of the soil and
the migration of pollutants into un-
polluted areas need to be identified
and completely understood. One
participant pointed out that surface
structures such as power lines and
fences can conduct the electricity
away. In one experiment at a na-
tional laboratory, an electric charge
was carried to a nearby fence that
was undergoing repair.
Just as significant is the need to
accurately estimate the costs of
electroremediation, even though
such estimates are site-specific.
Some presenters included rough
cost data-General Electric cleaned
up chromate for $130 a ton, DuPont
cleaned up organics for $90 a ton-
but cost estimates were generally
not included in bench-scale test re-
sults.
One participant expressed reser-
vations about the cost advantage of
using electricity to treat groundwa-
ter because aquifer flow rates can be
extremely slow and conventional
pump-and-treat methods are rela-
tively inexpensive. “Electrokinetics
might be a little ahead of demand,”
said Schultz. Regulators have had
little choice but to accept pump-
and-treat remediation systems be-
cause no other practical methods
have been available. “Once the ef-
fectiveness of electroremediation
has been demonstrated, regulators
may start demanding it, and create
more of a market” he predicted.
Jeanne Trombly is a San Francisco-
based freelance science writer spe-
cializing in science a n d environ-
ment.