Twentieth International Conference on Solid Waste Technology & Management

3rd – 6th April 2005, Philadelphia

Sequentially Enhanced Electrokinetic Remediation for

Chromium Contaminated Soil

Dr. D.L.Shah L.S.Thakur Shah Siddharth G

Professor Lecturer PG Student
Applied Mechanics Department
Faculty of Technology & Engineering, The Maharaja Sayajirao University of Baroda,
Kalabhavan Vadodara – 390001, Gujarat, INDIA
dr_dlshah@yahoo.com

Abstract
Presently, the industries are developing fast. It is good sign of progress, but at the same time
industrial wastes thrown without any primary treatment becomes hazardous. In such situation
the natural resources, such as lakes, rivers and their tributaries, seashore and soil banks are
contaminated. The Authority should put an unusual positive spin on environmental
regulation, encouraging engineers and scientists to see waste management "as an opportunity
rather than a threat". There are many characteristics of the soil that influence the transport of
contaminants, such as: density, porosity, humidity and permeability. This phenomenon is also
influenced by some properties of the contaminants, such as vapour pressure and chemical
nature. After identifying the type of soil and the nature of the contaminants, a suitable
remediation technique must be chosen, and the effectiveness of the decontamination process
evaluated. The remediation technique i.e. electrokinetic remediation is primarily a separation
and removal technique for extracting contaminants form soil. The method applied here is
sequentially enhanced electrokinetic remediation. In this method DC supply is given to
contaminated soil using carbon electrodes, placed in the Anode and cathode compartments,
filled with respective purging solutions. The purging solutions are different during the
different stages of experiments for the method. For the first 408 hours tap water was used as
purging solution in Anode and cathode compartments. In the second phase(stage) stage 1M
Ethylene Diamine Tetra-acetic Acid was introduced at cathode while tap water was continued
at Anode for a further period of 360hours and in the last stage 1M Potassium Hydroxide was
introduced at anode while 1M Ethylene Diamine Tetra-acetic Acid was continued at cathode
for further period of 168 hours. Due to DC supply the processes of electrophoresis,
electromigration and electroosmosis occurs in the soil resulting in the transportation of the
contaminants either towards the anode or cathode compartments depending on their electric
charge. This method reduced concentration of Cr-VI by 99.7% and Total Chromium removal
was 73%, which shows the high effectiveness of this method for heavy metal contaminated
soil.

Keywords
Contaminated Soils, Chromium, Remediation, Electrokinetic, Removal, Acetic Acid,
Potassium Hydroxide.

Introduction
Electrokinetic technique is one of the most promising remediation processes, and offers high
efficiency in decontamination of low-permeability soils contaminated with heavy metals,

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3rd – 6th April 2005, Philadelphia

radionuclides, or organic compounds. This transport of nutrients or chemicals is particularly

difficult to achieve in fine-grained solids with low hydraulic conductivities; the electrokinetic
approach does not encounter such a limitation, since the electro-osmotic flow is independent
of pore size. This technology applies a low level DC supply to the contaminated soil using
different types of electrodes placed in the ground. The application of a low-level direct
current results in physicochemical changes in the medium to which it is applied, leading to
species transport by coupled mechanisms, of electromigration, electro-osmosis,
electrophoresis and the electrolysis of water in the solution. The electrolysis of water
produces hydrogen ions in the anode compartment, which causes an acid front to migrate
through the porous medium. This, in turn, causes contaminants to be desorbed and/or
dissociated, resulting in initiation of electrophoresis and electromigration, i.e., the transport of
ions and polar molecules under the influence of the applied electric field. The applied
electrical potential gradient also leads to the process known as electro-osmosis, i.e., the flow
of an ionic liquid under the action of an applied electric field relative to a charged surface.
Finally, the contaminants are transported towards either the cathode or the anode depending
on their electric charge i.e. cationic or anionic, and the direction of the pore water flow.
Contaminants collected at the electrodes can then be extracted and subsequently treated for
reuse. The concept of elecrokinetic remediation is shown in Figure 1.

Fig. 1 Concept of Electrokinetic Field

The various types of electrokinetic remediation methods are as follows.

Enhanced Removal: Transport of contaminants towards polarized electrodes to
concentrate the contaminants for subsequent removal and ex-situ treatment.
Electrokinetic Extraction: The contaminant is extracted from the soil and subsequently
collected in aqueous phase in a collection well or deposited at the electrode site
Electrokinetic Stabilization: Fixing the toxic substance in place thereby rendering it less
likely to move elsewhere under ambient hydro geological conditions.
Electrokinetic Injection: Addition of species to aid in electrokinetic extraction or other
processes e.g. Surfactants, Nutrients, Electron acceptors, Electron donors
Treatment without Removal: Electro-osmotic transport of contaminants through
treatment zones placed between electrodes. The polarity of the electrodes is reversed

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3rd – 6th April 2005, Philadelphia

periodically, which reverses the direction of the contaminants flow back and forth through the
treatment zones.

Experimental Programme
Material Used: The soil used here was imported from the contaminated site taken from a
depth of 3 ft below ground level. The soil is found to be of CL type. (Table 1)
Table 1 Concentration of Various Elements in the Contaminated Soil

Elements Calcium Chloride Cr VI Total Cr Sodium Sulphate Silica

Concentration
2123.18 6098.11 70 95.7 2315 60 89.6
(mg/l)

Electrokinetic Cell: The electrokinetic cell used for this purpose is made of Perspex sheet
with an internal width of 260 mm, length between two Perspex end compartments is 400 mm.
The anode and cathode compartment are each of 25 mm length. The internal compartments
used are of Perspex sheet, and made pervious by making drill holes of 3mm. Two more
internal pervious compartments are made from Perspex sheet for placing a sand filter. Carbon
electrodes are used as Anode and Cathode. Using a AC to DC converter, DC supply is given
to the model which also has a capability of varying the DC output as well as measuring DC
current. (Fig. 2 a & b)
The contaminated soil was laid in three layers at 75% mdd (i.e. γ = 1.42gm/cc) with moisture
content on the wet side of omc i.e. w=26% using hand compaction. Filter papers were placed
between soil & sand filter compartments before laying contaminated soil. Different purging
solutions were used during different stages
For first 408hr, tap water at anode and cathode;
Second 360hr, tap water at anode and 1M EDTA solution at cathode;
Last 168hr, 1M KOH solution at Anode and 0.1M EDTA at cathode.

Fig 2 (a) Line Diagram of Electrokinetic Cell

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3rd – 6th April 2005, Philadelphia

D.C. current is then given to soil through Carbon electrodes. pH readings were taken at
regular intervals using a soil pH meter near anode & cathode compartment sections and at
four sections along the length of the samples (Fig. 3). Readings of current and voltage were
continuously taken till the end of experiment. (Fig. 4)

Fig. 2(b)Test Setup of Electrokinetic Cell

16 Anode Soil Section 1

Soil Section 2 Soil Section 3
14 Soil Section 4 Cathode

12

10
pH

0
0 5 10 15 20 25 30 35 40
Time in Days
Fig. 3 Variation of pH at Various Sections During the Test

About 10ml solution was collected each day, from anode and cathode compartments before
adding the new solution to respective compartments. Samples collected were for three parts
i.e. the three stages of sequential enhancement using various solutions and at the end of the

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3rd – 6th April 2005, Philadelphia

process. The concentration of Chromium VI and Total chromium were measured by leachate
of treated soil, and to know the trend of removal efficiency the analysis of solution collected
every day was made from both the compartments. (Table 2)

2.5

2
Current in Milli-Ampere

1.5

0.5

0
0 5 10 15 20 25 30 35 40
Time in Days

Fig. 4 Variation of Current During the Test

In the first stage of sequential enhancement, the contaminants are allowed to migrate toward
the respective electrodes without any enhancement for a period of 408 hrs. Then, acetic acid
was added at the cathode compartment for removal of cationic contaminants that already
precipitate in the soil close to the cathode. When EDTA is introduced into the cathode
reservoir, it migrates toward the anode through the soil as a negatively charged species under
an induced electric potential. As the EDTA species migrate through the soil, they complex
with the cationic metals. These EDTA metal complexes are also negatively charged, and
these complexes will migrate toward the anode under an electric field. The negatively
charged EDTA species do not complex with Cr-VI, since Cr-VI exists in the pore solution as
an anionic species.
Table 2 Concentration of Elements the End of Each Enhancement Stage

Purging Concentration (mg/lit)

Stage Compartment
Solution Cr - VI Total Cr
Unenhanced Anode Tap water 0.7 1.36
0 – 408 Hr. Cathode Tap water 0.1 0.26
Enhanced- Anode Tap water 0.38 1.21
408 – 768 Hr. Cathode 1M EDTA 0.1 0.23
Enhanced- Anode 1 M KOH 0.34 0.68
768 – 936 Hr. Cathode 1M EDTA 0.02 0.19

At the later stage of experiment i.e. after 768 hrs form the start for the experiment, an alkaline
solution of 1M KOH is added in the anode compartment for the removal of anionic

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3rd – 6th April 2005, Philadelphia

contaminants that have adsorbed to the soil near anode. Most of the chromium migrated into
the anode reservoir; very small percentage of the chromium was found in the soil existed as
Cr-III.

1.6

1.4 1.36

1.21 Cr VI
1.2
Total Cr
Concentration in mg/lit

0.8 0.7 0.68

0.6

0.38
0.4 0.34

0.2

0
Unenhanced 0-408hrs Enhanced 408-768hrs Enhanced 768-936hrs

Fig. 5 Concentration of Chromium at Anode Compartment

0.3

0.26 Cr VI
Total Cr
0.25
0.23
Concentration in mg/lit

0.2 0.19

0.15

0.1 0.1
0.1

0.05
0.02

0
Unenhanced 0-408hrs Enhanced 408-768hrs Enhanced 768-936hrs

Fig. 6 Concentration of Chromium at Cathode Compartment

This Cr-III immediately precipitated as hydroxides due to a high pH value resulting

form usage of potassium hydroxide in the anode reservoir. The sequence of using the purging
solutions greatly affects chromium migration and removal. Thus the removal of Cr-VI is

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Twentieth International Conference on Solid Waste Technology & Management
3rd – 6th April 2005, Philadelphia

almost 100% because almost 70% migrated in anode reservoir and 30% was approximately
converted to Cr-III.

Table 3 Concentration of Elements in Soil Before and After Treatment

Concentration (mg/l)
Elements Contaminated Soil Treated by Sequentially
soil Enhanced Electrokinetic
Remediation
Cr – VI 70 0.21
Total Cr 95.7 0.26

Conclusion
The sequentially enhanced electrokinetic remediation method is very effective method
to remove the considered heavy metal here chromium from the contaminated soil. The type
of purging solution used and their sequence for application at various stages play a crucial
role in contaminant transport. The contaminant transport is mainly due to the process of
electromigration rather than the electroosmotic process. Contaminant adsorption,
precipitation, and reduction are greatly affected by the type of the soil matrix and by the
conditions that develop in the soil due to the electrolysis reactions at the electrodes.

References
(i) EPA-Environmental Protection Agency, “In Situ Treatment of Soil and Groundwater
Contaminated With Chromium”, Technical Resource Guide, EPA/625/R-00/004 & 005,Oct
2000.
(ii) Pamukcu S, “Electro-Chemical Technologies for In-Situ Restoration of Contaminated
Subsurface Soils”, Lehigh University, Bethlehem, PA 18015, USA [EJGE PAPER 1997].
(iii) Reddy K R, Chaparro C, “Electrokinetic Remediation Of Mercury-Contaminated
Soils”, Proceedings of the International Containment & Remediation Technology
Conference, Orlando, Florida, USA, June 2001.
(iv) Reddy K R, Charlie Y Xu, Chinthamreddy S, “Assessment of electrokinetic removal
of heavy metals from soils by sequential extraction analysis”, Journal of Hazardous Materials
B84 (2001) 279–296.
(v) Reddy K R, Chinthamreddy S, “Sequentially Enhanced Electrokinetic Remediation of
Heavy Metals in Low Buffering Clayey Soils”, Journal of Geotechnical Engineering, Vol
129,NO. 3, March 2003, page no. 263-277.
(vi) USAEC- US Army Environmental Center, “In-Situ Electrokinetic Remediation of
Metal Contaminated Soils Technology Status Report”, Report Number: SFIM-AEC-ET-CR-
99022 July 2000.