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and
J. Kenneth Wittle
Electro-Petroleum, Inc., Suite 1118, Old Eagle School Road, Wayne, PA
Application of Electrokinetics to Soil Decontamination The clays used in preparing the soil matrices were kaolinite
(Georgia kaolinite) and Na-montmorillonite (bentonite), both
obtained commercially. The sand specimens were prepared
Electrokinetics have been used for dewatering of soils and with washed New Jersey beach sand passing No. 40 sieve and
sludges since the first recorded use in the field by Casagrande retained on No. 100 sieve. This variation in soil mineral matrix
in 1939 [12]. Work and subsequent research in electrokinetic was intended to investigate the process in so assumed difficult
decontamination of soils have been accelerated in recent years, situations of remediation when the ionic species are strongly
probably after the report of the detection of high concentra- held on the clay surface (Na-montmorillonite case), or when
tions of metals and organics in electroosmotically drained water the electroosmotic flow efficiency might be reduced due to
of a dredged sludge in the field by Segall and co-workers in reduced surface charge density (sand case). The sand matrix
1980 1131. Other field work [14, IS] has been conducted since was prepared with the clean beach sand mixed homogeneously
then with reasonable success of heavy metal transport. with 10% Na-montmorillonite by dry weight.
Hamnett [ I d j performed laboratory studies on electrically The pore solutions were distilled water, humic solution and
induced movement of ions in sand. In evaluating the electro- simulated groundwater. The humic solution was prepared by
lytic migration of ions of different salts, he found that smaller dissolving a commercially obtained humus product in distilled
ions (i.e., Na) were more mobile than larger ions (i.e., K , Ca, water at a concentration of 900 ppm. The organic carbon
Ni). Acar et al. [ I 7 and Hamed et al. [I81 showed that the content of this stock solution was 257 as measured in mg
migration of an acid front from the anode toward the cathode C/1. This corresponded to DOC values typically measured in
is significant in the removal of heavy metals from clay soils. groundwaters associated with very high organic carbon fields,
Shapiro and co-workers [3] developed a model for electroos- such as oil fields. The pH of this solution was 9.4. The sim-
mosis to predict transient behavior of concentration profiles ulated groundwater was prepared following an approximate
for chemical species in solution. The model agreed well with formula of the groundwater salt constituents typically found
experimental results of acetic acid removal from soil via elec- in the Jefferson County of Idaho State. The pH of groundwater
trokinetics. sampled in that region was measured at 8.2, and contained a
A simple prediction method was suggested by Khan [5] re- substantial amount of (212 ppm) bicarbonate. The simulated
cently. The theoretical approach developed for electroosmotic groundwater did not contain this component. Its pH was
flow was used to predict the contaminant removal from soil measured as 7.9.
when the contaminants are either present at low concentrations The salts used in preparing solutions of the 4 metals and the
in the soil pores or they are not adsorbed onto the charged metal concentration of each resulting solution as well as the
surfaces, so that the true electroosmotic flow is the dominant resulting concentration of the metal in soil and the soil pH
mechanism for their migration. Tracer experiments in kaolinite prior to electrokinetic treatment are given in Table 1. Some
clay utilizing O-Nitrophenol and zinc as representative con- of these metal solutions were prepared at so called high and
taminants were conducted. O-Nitrophenol represents a poorly low concentrations to represent variable degree of contam-
adsorbed organic compound, the adsorbtion of which was ination of the soil matrix. In general the pHs of the mixtures
measured on the order of 0.01 mg/g of soil. The zinc concen- were moderately acidic or near neutral. In most cases the pH
tration used was 325 mg/kg of dry soil which was slightly over was reduced with the addition of the metal salt, probably
than the typical maximum concentration of naturally occurring because they all were salts of strong acids.
zinc (10-300 mg/kg) in soils. There was good agreement be-
tween the measured removal of the contaminant and the pre-
dicted removal using electroosmotic flux of water based on
clay surface current.
Procedures
The slurries would be mixed at 100% water content of the
INVESTIGATION kaolinite clay, 50% water content of the sand mixture, and
200-300% water content of Na-montmorillonite clay, all by
Experimental Procedures dry weight of the solid components. The mixing would be done
in large batches (2-3 gallons) with a tall hand held mixer. Then
An extensive laboratory program was undertaken to inves- the slurry would be poured into individual compression units
tigate the feasibility of electrokinetic treatment of clay mixtures referred to as consolidometers. The operation of these units
containing heavy metals. The test matrices were prepared in are presented elsewhere [5]. The main features of the conso-
the laboratory by compressing slurries of clay to compact sat- lidometers are that they are capable of applying some incre-
urated soil samples. Each clay slurry was mixed with solution ments of sustained stress (pneumatically) while allowing for
the excess fluid to drain out slowly. This procedure creates, is no standard apparatus for measuring electrokinetic water
homogeneous, near saturated soil matrices compacted to a flow in soils. The ones that are used in similar work elsewhere
constant density and pressure. The most beneficial aspect of have been shown to produce consistent results. The equipment
these custom manufactured units is that at the end of the used in this particular program was developed with attention
consolidation process, the densified soil sample is packed into given to a few concerns. These were addressed by providing
a cylindrical soil chamber (3.556 cm ID and 7.62 cm long) larger electrode surfaces than soil surface to achieve low current
which can be detached from the unit and installed into the density, by isolating the electrodes from soil surfaces to min-
electrokinetic cell used in this investigation. Therefore the re- imize electrode reactions at these boundaries, and by providing
sulting soil specimen is not disturbed by handling such as convenient ports for gas expulsion from the electrode sites and
trimming and placement. also extracting inflow (anode site) and outflow (cathode site)
All the specimens were consolidated to 200 kPa pressure. water samples for analysis. The main features of these units
Although there is evidence, from this work and others [22] are: the electrodes reside in water tight chambers which are
that, electroosmotic flow increases with consolidation pressure connected to measuring burettes at one end, and to the soil
in clay soils, it is not well known to what extent the increased specimen cylinder at the other end. The soil specimen is sep-
flow contributes to decontamination when the contaminant arated from these water filled chambers by carborandum po-
migration is not governed by electroosmosis. The average in-
itial densities and water contents of the five artificial soil types Table 2 Average water content and density of speci-
are given in Table 2. mens before and after electrokinetic treatment
At the completion of each consolidation period, the tube
containing the packed soil would be removed, the top extruding Initial Final
portion trimmed and stored for quantitative chemical and water Sample density density
content analysis. Samples of the waters extracted during con- Code w 070 k/cm) w 070 (n/cm3)
solidation were also taken for chemical analysis to assess the
degree of metal retention by clays. The approximate period of KS 47.25 1.64 56.19 1.62
consolidation to 200 kPa pressure was around 24 hours for KH 51.35 1.66 54 1.54
kaolinite and it was around 7 days for Na-montmorillonite KG 32.8 1.83 39.5 1.73
clays slurries. This period was much less for the sand + ben- MS 271.8 1.14 321.62 1.03
tonite specimens, but pressure increment periods were main- ss 51.25 1.67 52.95 1.66
tained similar to that of kaolinite for consistency. When the
KS: Kaolinite-distilled water
soil cylinder was removed from the consolidometer, weighted KH: Kaolinite-hurnic solution
and sampled, it would be ready for mounting on the electro- KG: Kaolinite-ground water
kinetic apparatus. MS: Montrnorillonite-distilled water
The details of the electrokinetic apparatus used in this study SS: Sand & 10% Montrnorillonite-distilled water
are also provided elsewhere [5]. It should be noted that there
! i
i.:.J Ai
12-
k *
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-
.-
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RESULTS
INITIAL CONCENT
2
-0.2 0.0 02 0.4 0.6
MIX WAIER
CONCENTRATION
0.8
I
1.0
,A
OF Cd- I000 m g / l
1.2
-1
0
1.0 1.2
NORMALIZED DISTANCE FROM ANODE NORMALIZED DISTANCE FROM ANODE
END OF SOIL, X/L (L=3 in) END OF SOIL. X/L (L=3 in)
2
< 9573E-03 1 241E-02
Q/l.'
1 825E-02 2 113E-02 2 295E-02
I~'l,llllllllllj(~'r,Illll~llll/llli,l~~)l
' ' 7302E-03 8.048E-03 ' 1.671E-02
Q/F lCoulornb/(Couloinb/mole)l
' 2.452E-02 '
l
FIGURE 11. Average pH distribution from anode to cath- FIGURE 13. Average pH distribution from anode to cath-
ode end in 3 duplicate specimens of five soil types with ode end in 3 duplicate specimens of four clay types with
strontium at the end of electrokinetic treatment. cobalt at the end of electrokinetic treatment.
(KS: kaoliniteldistilled water, KH: kaolinitelhumic sol. (KS:kaoliniteldistilled water, KH: kaolinitelhurnic sol.
KG: kaolinitelgroundwater,MS: Na-montmorilloniteldist. KG: kaolinitelgroundwater, MS: Namontmorilloniteldist.
water, SS: clayey sandldistilled water) water)
I I
CONCENTRATION
1.2-
1-
I I ' '
1
0.8- I 1
1 1
1 1
1
0.6-
uk 8
0
a
\
3
0
G1
c
U I
0.000 0.003 0.006 O.( 39 0.1 2 0. 15
FIGURE 15. The variation of normalized cumulative inflow versus the number of moles of electrons transmitted in
distilled water specimens of kaolinite with Cd, Co, Ni or Sr.
such a conclusion is not made at this time until further data should create suitable environments for the metal ions to re-
is processed. main in solution as single species, so that realistic predictions
In Figure 15 normalized inflow versus moles of electrons is of rate of electrokinetic extraction can be made.
reproduced for kaolinite only. The slope of approximate The following specific conclusions were obtained from this
straight line correlations change as the metal in the pore fluid study:
varies. In general the trends are similar to those of metal + 1 . Electroosrnosis is probably the dominant mechanism of
Na-montmorillonite mixtures shown in Figure 14. In this case, electrokinetic extraction of metal contaminants when they are
Sr and Cd specimen data coincide, exhibiting the largest flow present at low concentrations. At high concentrations of the
per mole of electronvalue, whereas Ni shows the smallest value, metal, electrolytic migration of their ionic species plays a more
among the four metal mixtures. The reduced flow may be due important role than the electroosmotic transport.
to the formation of complex species of ions produced as pH 2. The removal of the 4 metals tested in this study from a
changes across a specimen. At times when there are predom- variety of soil types, including rnontmoritlonite, kaolinite,
inantly negative complexes of a metal, these species may carry clayey sand, clay with simulated groundwater and clay with
significant number of molecules of water as they migrate in humic acids was achieved at 85-95'70 of the original concen-
the opposite direction of electroosmotic water flow, reducing tration, characterized as typical high concentration of these
the net flow towards cathode. metals occurring in some common sites.
3. At low concentration of Cadmium, the flow efficiency
was higher than the high concentration case of the metal.
CONCLUSIONS However, percent removal was 16.5 as opposed to 84 percent
for the latter case.
The main conclusion of this research has been that electro- 4. Among the 3 soil types tested, kaolinite exhibited highest
kinetics promises to be a viable technology to remove contam- efficiency of electrokinetic water flow, followed by clayey sand.
inants from soils. The interaction of various processes that The lowest efficiency appeared to occur with Na-montmoril-
take place simultaneously is yet to be understood to better lonite. Kaolinite exhibited consistent efficiency with little var-
predict the efficiency of the process in a variety of soil-con- iation with respect to the metal ion type. Whereas,
taminant situations. The results presented in this paper shed montmorillonite and clayey sand appeared to be more affected
some light on the influence of electrochemistry and physico- by the type of metal ion.
chemistry of the soil-contaminant system on the process. The
transient acid front movement in soil from anode site to cath-
ode, is beneficial for metal desorption and dissolution, which
in turn contributes to the removal process. However, the tran- ACKNOWLEDGMENTS
sient pH condition cause formation of complex species of some
metals which may hinder the process, or in some cases enhance This research was funded by the Office of Technology De-
it. Therefore pH control at both ends (anode and cathode) velopment, Office of Environmental Restoration and Waste