IGC – 2008, Bangalore

ELECTROKINETIC REMEDIATION OF COPPER CONTAMINATED

EXPANSIVE SOIL BY SURFACTANT & CHELATING AGENTS

Bala Ramudu. P
Lecturer, Department of Civil Engineering, Institute of Technology-Banaras Hindu University, Varanasi-221005
R.K. Srivastava
Professor, Department of Civil Engineering, Motilal Nehru National Institute of Technology, Allahabad-211004
R.P. Tiwari
Professor, Department of Civil Engineering, Motilal Nehru National Institute of Technology, Allahabad-211004
ABSTRACT: This paper presents outcomes from a study pertaining to the remediation of copper contaminated soil by electro-kinetic
(EK) remediation method. The objective of the study was to evaluate remediation of copper from alkaline expansive clayey soil, and
to determine the effect of purging chemicals on the overall copper remediation. Soil used in experiments was spiked with copper at a
maximum sorption concentration found from batch sorption studies. The applied voltage was 35 V and duration of tests was 120 h.
Presented outcomes demonstrate the remediation efficiency of copper for a short duration of treatment. The results show copper
removal as high as 30.0% within treatment duration with Ammonium Citrate (1M) as both saturating as well as purging solution.
Higher accumulation of copper towards the cathode was observed in all experiments. All the purging solutions have not made the pH
of soil below the pH required to maintain solubility of copper. The X-ray diffraction (XRD) and Scanning Electron Microsscope
(SEM) studies indicate that there were no significant changes in mineral composition.

1 INTRODUCTION copper’s capability of forming different ligands present in the

soil. Ottosen et. al. (2004) suggested that copper is mobile at
The soil, a main part of the terrestrial ecosystem, is a habitat for high pH.
a great number of organisms but at the same time, it is perhaps
the most endangered component of our environment, open to 2 MATERIALS
influence from a variety of different pollutants arising from
human activities like industrial, agricultural etc. (Djingova and For the present study, field soil was obtained from unpolluted
Kuleff, 2000; Morton-Bermea et al., 2002). Air and soil site Meja village, Allahabad district (Uttar Pradesh, India) at
pollution resulting from both automobile exhaust fumes on depth of 1-2 m. Soil sample was washed and collected through
highways and the emission of fumes and smoke from industrial 0.425 mm sieve to obtain fine grained soil. Various physical and
plants is recognized as a major problem in developing countries. geochemical characterization tests were carried out. The
Close to 50% of the world population lives in urban areas, important physico-chemical properties of the soil are presented
compared with only 15% in 1900 (Vegter, 2007). Urbanization in table 1. Qualitative X-ray diffraction (XRD), scanning
will increase environmental pressures and impacts on soils. electron microscopy (SEM) characterization tests were
Urbanisation is not only 'sealing' of soil. It will also lead to other performed for thorough understanding of soil mineral structure
pressures such as contamination. Moreover, the newer (Figs. 1&2). The expansive nature of soil is evidently due to
contamination is likely to diffuse more and may involve many presence of dominant Illite clay mineral.
different substances which makes it more difficult to assess risks
and impacts compared to the more pronounced pollutions at
historically contaminated sites, where a few 'key' substances
may determine the risks for human health and the environment.
Contaminated site may give rise to hazards and that implies a
degree of risk which also involves a problem of definition.
Furthermore, the attitudes of different states to contaminated
ground and its redevelopment vary appreciably. Great efforts
have been made on the studies for removal of contaminants from
soil in recent past. There were few remedial technologies like
soil flushing, phytoremediation, bioremediation etc. but all these
technologies are not satisfactory in low permeable soils where
electrokinetic has proved its own ability in such soils
(Stichnothe et al., 1996). Remediation of contaminated soils by
electrokinetic process is a complex in-situ technology.

Copper is a non-essential heavy metal pollutant of the

environment resulting from various agricultural, mining and
industrial activities. The natural concentration of copper in Figure 1. XRD pattern of virgin soil
terrestrial soil is about 30 mg kg-1 and is only toxic in high
concentrations. Contaminated soil has typically a copper Q-Quartz; F-Feldspar; C-Calcite; D-Dolamite; I-Illite; K-
concentration between 50-22,000 mg/kg (Nystrom, 2001). In an Kaolinite
electric field, species of copper (Cu+2) migrate toward the
cathode and subsequent removal from soil is feasible. In an
electric field, almost all copper can be found in the cathode
compartment, a certain amount may be found in anion
membrane (Virkutyte et. al., 2002). Reddy et al. (1997)
suggested that some copper may be found in the anode due to

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 R.P. Tiwari, R.K. Srivastava & Bala Ramudu. P
Table 1. Physico-chemical Properties of Soil Used contaminated soil. A schematic test setup used in this
experiment is shown in figure 4.
Property Value
Gravel (%) 6.6
Sand (%) 18.4
Silt (%) 60.0
Clay (%) 15.0
Liquid Limit (%) 45.8
Plastic Limit (%) 17.0
Plasticity Index (%) 28.8
Shrinkage Limit (%) 12.8
Specific Surface Area (m2/g) 0.18
Cation exchange capacity (USEPA) 22
(meq/100 g)
pH 8.36
Organic Content (%) 6.25
Loss on Ignition (LOI) (%) 9.93
CaCO3 (%) 2.5
Soil classification (USCS) CL Figure 3. Scanning electron image of Cu++ contaminated spiked
Cu (mg g-1) 0.15 soil

Cathode electrode chamber Anode Reservoir

Dummy Electrodes

Contaminated soil

Battery

Anode electrode chamber

Figure 4. Schematic diagram of electro-kinetic test set-up

Table 2. Basic Information of Experiments

Figure 2. Scanning electron image of virgin soil Test Soil Saturation Anolyte
EKCuD Deionized water Deionized water
Ammonium citrate has been reported to be, at slightly alkaline
Tween – 20 (0.2 % v/v),
environment, a good enhancement solution for polluted EKCuF Deionized water
(pH 6.4)
calcareous soils (Ottosen et al., 2001). Electrodialytic Studies on
EKCuSC Deionized water SC(1M) (pH 8.6)
the mobilization and electrochemical removal of Cu, Cr and As
using ammonium citrate has been shown to be successful EKCuAC Deionized water AC(1M) (pH 10)
(Ottosen et al., 2004). Sodium citrate displays high extracting EKCuAA AC (1M) (pH 5) AC(1M) (pH10)
capabilities similar to EDTA within certain limits of the pH
values. It has been reported that sodium citrate can also be a EKCuD: Electrokinetic remediation of copper contaminated soil
more convenient ligand than ammonia (Lopez et al., 2003). using Deionized water;

3 EXPERIMENTAL STUDY EKCuF: Electrokinetic remediation of copper contaminated soil

using tween-20 non-ionic surfactant;
The basic information of the experimental program and
parameters used in each test is summarized in table 2. EKCuSC: Electrokinetic remediation of copper contaminated
Unenhanced EK tests were conducted (EKCuD) as a baseline, soil using sodium citrate;
and the remaining tests (EKCuF, EKCuSC, EKCuAC,
EKCuAA) were run with different purging enhancement EKCuAC: Electrokinetic remediation of copper contaminated
solutions. Out of five tests four experiments were run when soil soil using ammonium citrate;
was saturated with de-ionised water and one experiment was
conducted when the soil was saturated with AC and same as the EKCuAA: Electrokinetic remediation of copper contaminated
purging solution was used. DI water was the catholyte in all soil saturated with ammonium citrate and same used as flushing
experiments. Initial Cu concentration for EK remediation tests is agent.
determined as 15.88 mg/g which was assessed by soil digestion
process conducted on soils already contaminated artificially for
its sorption value 20 mg/g figure 3. shows the SEM of Cu

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 ELECTROKINETIC REMEDIATION OF COPPER CONTAMINATED EXPANSIVE SOIL BY SURFACTANT & CHELATING
AGENTS
4 RESULTS & DISCUSSION 4
3.5 Initial EKCuD
900
3 EKCuF EKCuSC

Cu remained (%)
EKCuD
800 EKCuAC EKCuAA
EKCuF 2.5
700 EKCuSC 2
EKCuAC
600 EKCuAA 1.5
Current (mA )

500 1

400 0.5
0
300
0 0.2 0.4 0.6 0.8 1
200 Normalised distance from anode
100
Figure 7. Residual copper distribution along the length
0
0 20 40 60 80 100 120
Distribution of copper concentrations in the soil after EK
Time (h) process is shown in figure 7. The pH distribution is also shown
Figure 5. Variation of current with time during EK treatment to further explore the observed copper distribution in figure 8.
Due to the electrolysis of water, the pH near the anode area
Figure 5. shows the profile of electric current during the tests. decreased to 5.8 and it was much lower than that of initial pH
For EKCuD and EKCuF the current was initially high. After 70- value 8.1 in case of EKCuD. The Cu concentrations appeared
75 h, the trend showed sharp decrease and initially increased to very high at anode side in EKCuD. It indicates that due to low
80-100 mA up to time of 20-25 h. On the other hand, during pH at anode, the anionic form of Cu species migrated towards
EKCuSC, and EKCuAC current was high and it was increasing anode side. The ration of residual concentration and initial
through out the experiment gradually. The current flow in concentration was (C/C0) of Cu was greater than 1 at all the
EKCuAA was observed very high, it started at 500 mA initially sections. Similar observations were identified in case of EKCuF
within few minutes of commencement of test and the trend also. The overall concentration in EKCuF was also higher than
continued up to 20-30 h later on it showed decreasing trend and the initial concentrations, corresponding pH value ranging from
stabilized at around 350 mA at 62 h. The sharp decrease of 7.5-8.5. The developed pH environment was not at all suitable
current after 24 h with time in EKCuAA reflects the total for migration of copper. The pH values were ranging from 7.8 to
electric resistance in the soil system. The decrease in 8.5. Cu was significantly low in the case of EKCuSC at anode
conductivity with time is probably due to a decrease in the side. Overall pH ranging from 8.1 to 10.2. Except in section 3, in
concentration of dissolved copper species, which is caused by all other sections the Cu concentration was below the initial Cu
formation of precipitates in the cathode region. concentration. In EKCuAC also, overall C/C0 was below 1
except in section 5 which is near cathode side. The pH values
Direction of fluid flow was from the anode to cathode (zeta ranged from 8.2 to 9.2. The pH profiles in case of EKCuAA
potential < 0). Figure 6 shows the plot for cumulative volume of appeared higher at anode than at cathode. There was significant
effluent versus time during the electrokinetic process. When DI amount of decrease in Cu in case of EKCuSC, EKCuAC and
water and tween-20 were purged (EKCuD and EKCuF), the flow EKCuAA. But it increased in the middle of the cell, due to the
rate was relatively low, compared to other tests. Cumulative increase in pH. At this point Cu starts to precipitate as hydroxide
effluent collected after the total duration of test run ranged from [Cu(OH)2] or begins to re-adsorb to the soil. These pH values
190-575 mL. With this data, the coefficient of electroosmotic were not low enough to achieve the complete desorption and
conductivity (ke) was calculated. The sequence of the EO flow dissolution of copper.
in all tests was
EKCuSC>EKCuAC>EKCuF>EKCuAA>EKCuD. 12.5
11.75
11
700 EKCuD 10.25
9.5
600 EKCuF
pH value

8.75
EKCuSC
E O Flow (m L )

8
500 7.25
EKCuAC Initial pH EKCuD
6.5
400 EKCuAA 5.75 EKCuF EKCuSC
5 EKCuAC EKCuAA
300
4.25
3.5
200
0 0.2 0.4 0.6 0.8 1
Normalised distance from anode
100
0 Figure 8. Soil pH profile of the EK treated Cu contaminated soil
14 34 54 74 94 114
The solubility of Cu during EK treatment was checked by
Time (h) conducting sequential extraction studies at DI water (pH 7) on
Figure 6. Cumulative electroosmotic flow measured during all EK treated soils (Fig 9). In case of experiment run for
electrokinetic remediation EKCuD, there was no identification of Cu in extracted solutions.
It indicates Cu was not at all desorbed from soil surface. In case

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 R.P. Tiwari, R.K. Srivastava & Bala Ramudu. P
of EKCuF also there was no identification of Cu. It indicates been confirmed that the experiments run on Cu contaminated
whatever Cu was desorbed in these tests did not migrate towards soils saturated with AC and purged with the same shown high
cathode due to increase of pH of soil. The pH gradient generated removal efficiency.
in soil from anode to cathode significantly affected the migration
of Cu in case of EKCuD and EKCuF (It has been observed from 6 REFERENCES
the variations of soluble Cu concentrations). Significant soluble
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Segovia, N. (2002) Heavy metal concentrations in surface soil
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Soluble Cu Conc. (mg/g)

8
EKCuAA enhanced electrodialytic soil remediation. Master Thesis, The
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20 EKCuF EKCuSC the Total Environ., 289: 97-121.
EKCuAC EKCuAA
10

0
0 0.2 0.4 0.6 0.8 1
Normalised distance from anode

Figure 10. Variation of moisture content with distance after

treatment

5 CONCLUSIONS

Presented outcomes demonstrate the remediation efficiency of

copper for a short duration of treatment by electro-kinetic
remediation methods. The results show copper removal values
as high as 30.0% within treatment duration. Higher
accumulation of copper towards the cathode was observed in all
experiments. The solubility of copper is diminished beyond pH
6. All the purging solutions have not made the pH of soil below
the pH required to maintain solubility. The XRD and SEM
studies indicate that there were no significant changes happening
in mineral composition. From the EK remediation tests, it has

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