Remediation and Reutilization of Contaminated Solid Waste

Dr. D. L. Shah L. S. Thakur Sheth Dipali

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
The impact of rapid industrialization around the globe and unsafe waste management
practices have become increasingly significant within the last two decades as the number of
unenigneered facilities and contaminated sites steadily grow and the anticipated remediation
costs increases. Soil is the ultimate receptor for most pollutants released into the
environment. Chemicals adsorbed to particulate matter that is released into the atmosphere
are eventually deposited onto soils or surface water. A new service sector is emerging across
the world in waste containment, soil remediation and environmental restoration.
Environmental geotechnology is concerned with safe disposal and containment of wastes, to
turn hazardous waste into non- hazardous waste by intermediate treatment process, the
remediation of contaminated sites and groundwater and reutilization of this contaminated
waste. Electrokinetic remediation uses the combined effect of electric, chemical and
hydraulic potential for remediation of problematic soil. A low DC voltage is applied to soil
through electrodes and the metals are extracted from contaminated soil. This method is one of
the most promising remediation processes; also it has low operational cost and potential
applicability to a wide range of contaminant types. Soil washing, on the other hand is an on-
site clean up technology that works on the principle of waste minimization. Soil washing
separates finer material from coarser and scrubs the surface of large particles leaving a
contaminated fine fraction, plus clean sand and gravel fraction. The waste selected for the
study was a multiple heavy metal contaminated waste from one of the factories near
Vadodara, Gujarat. For electrokinetic remediation a sequential enhancement method was
selected which included basically enhancement using tap water, 1M NaCl, and 1M MgCl2 as
the purging solutions for varying time intervals. For the soil washing phase, a model was
developed with PVC pipes in laboratory, the heavy metal contaminated waste was filled in all
the three models with hand compaction, washed with tap water for one month. After one
month washed with Ethylene Diamine Tetra Acetic Acid (EDTA) of 0.05M and other model
washed with Sulphuric Acid with starch for one month. After laboratory testing it was found
that removal of copper is maximum and zinc formed leachates with EDTA, which are
insoluble in water so could not be detected in the leachate. Soil washing with sulphuric acid
and starch, leached out copper, chromium (T) and iron only in higher concentrations leaving
other heavy metals unleached in the waste, but the strength of the remediated waste reduced
to half.

Keywords
Contaminated Soil, Heavy Metals, Remediation, Soil Washing, Electrokinetic Remediation,
Ethylene Diamine Tetra Acetic Acid (EDTA), Sulphuric Acid With Starch, Sodium Chloride
(NaCl), Magnesium Chloride (MgCl2).
Introduction
Electrokinetic processes represent one of the most promising alternatives, to substitute
hydraulic gradient with an electrochemical thereby facilitating the flow of fluids in low
permeability soils. The fluid flow in presence of water-soluble organic solvents, allows the
solubilisation of the contaminants or their mobilization in the presence of surfactants. This
technology applies a low level DC supply to the contaminated soil using different types of
electrodes placed in the ground. This applied electric field induces electroosmosis,
electrophoresis and electromigration through with the truly dissolved or micelle solvated
species are placed in motion towards one of the electrodes. 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. This
transport of dissolved complex salts 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. The
concept of electrokinetic remediation is shown in Fig. 1.

Fig. 1 Concept of Electrokinetic Remediation

The soil washing method involves separating the small and large soil particles. As the metals
are primarily bound to the smallest particles, separating them out and leaving the remainder
of the soil rather clean. Soil washing will be particularly useful on sandy soils where
subsequent clean up of the fine particles could perhaps be undertaken using electrokinetic
remediation. Soil washing, both in-situ and ex-situ, is considered as the removal method of
the toxic substance from the contaminated soil. Heavy metal in contaminated soil exists
mostly on the soil particle surface by adsorption, complex formation, precipitation, etc. A
large granule has a relatively small surface area, and they contain little volume of heavy
metal compared with finer portion. Therefore, the soil particle classification can realize the
purification of contaminated soil, by removing the finer soil containing heavy metals (Fig. 2).
Soil washing is the method of wet classification, which exists on soil particle surface. It is a
positive method of high applicability for sandy soil, because of the reduction of the soil
volume needing treatment and thus reducing remediation costs.

Fig. 2 Schematic Diagram Of Soil Washing

Experimental Programme
The waste is taken from a site near Vadodara, which contains various heavy metals such as
Copper, Zinc, Lead, Aluminum, Chromium, and Cadmium.
Concentrations Of Heavy Metals In The Waste

Metals mg/lit Fe Cu Zn Pb Al Cr (T) Cr+6 Cd Ca Mg

TCLP 0.094 7.0 7.86 8.16 11.0 ND* 0.007 0.27 160 97.2
10% Leachate ND* 1.58 42.65 ND* 4.76 0.007 0.007 0.38 232 174.96
Dry weight 0.063 1.4 9.21 8.67 45 0.19 0.03 ND* 408 340.2

(ND*=Not Detected)

Soil Washing
The soil-washing model consists of 150mm diameter PVC pipe of approximately 300mm
length with perspex sheet being used at one end to cap it. This has a PVC nipple attached to it
as an outlet to collect leachate. Inside the model a perforated perspex sheet is placed with a
7.5cm thick sand filter at the bottom over which the waste is placed and a similar
arrangement is also kept on the top of the waste. Different chemicals were passed through
waste for a period of one month by recycling the chemicals i.e. each day whatever leachate
was collected was reused the next day for washing. After one month of recycling, the
chemical analysis of this leachate was carried out along with the TCLP (Toxicity
Characteristics Leaching Procedure) analysis of treated waste.

The waste is washed with 0.05M EDTA for the first experiment and in the second set of
experiments with a solution containing 450ml Sulphuric Acid and 100gm starch in 1000ml
water. During the test the leachate is collected and after washing has completed the waste is
again oven dried for chemical analysis. When chemical analysis of waste is carried out by
10% leachate method, the concentration of copper is 1.58 mg/lit while that of treated waste
after washing with EDTA using the same method is 0.77 mg/lit and is 1.46 mg/lit in the
leachate collected after washing with sulphuric acid and starch giving almost 93% removal
with it. The concentration of zinc in waste is 42.65 mg/lit but is not detected in treated waste
after washing with EDTA giving 100% removal. The concentration of aluminum in waste is
4.76 mg/lit while that of the treated waste with EDTA is 0.49mg/lit whereas it is 1.65mg/lit in
it after washing with sulphuric acid giving better washing with EDTA. Concentration of
chromium (T) is 0.007mg/lit in waste while it is 0.0004 mg/lit in treated waste after washing
with EDTA and is 0.0066mg/lit in waste after washing with sulphuric acid and starch, thus
washing with EDTA is a better option. (Fig. 3)

Tap Water EDTA

Sulphuric Acid + Starch Waste

120

100
42.65

107.57
95.03

80
1.58

60

4.76

0.007
50.08

0.426
40
32.06
0

0.031
0
22.44

20
2.28

0
Cu Zn Al Cr (Total)
Fig. 3 Comparison of Metal Removal Treated By Soil Washing

The concentration of heavy metals removed in soil washing with sulphuric acid and starch is
more as compared to when with EDTA. The copper removed is around 50% with EDTA
while washing with sulphuric acid it is 93%. Chromium (T) is removed 95% by sulphuric
acid washing and aluminum is also removed by 35%. The geotechnical properties of waste
and washing with EDTA are same but the removal of hazardous metals is less in EDTA as
compare to washing with sulphuric acid. But washing with higher percentage of sulphuric
acid breaks the chemical bonds and reduces the strength. The compressive strength is 50%
less than the original strength of waste.

Electrokinetic Remediation
The electrokinetic cell used for this purpose was made using perspex sheet, had an internal
width of 260mm, and length between two perspex end compartments was 400mm. (Fig. 4)
The anode and cathode compartments were each of 25 mm length. The internal compartments
made were of Perspex sheet and made pervious by making holes of 3 mm diameter. Carbon
electrodes having diameter 10 mm and 15 cm long were used as anode and cathode. A DC
power supply was given to the model, which had ability to measure the voltage and current
applied to the cell. The waste was laid in three layers at 75% of MDD with moisture content
of 26% using hand compaction. Filter papers were placed between waste and sand filter
compartments before laying the waste. Different purging solutions used during the different
stages of the experiment are as below:
For first 600 hrs, tap water at anode and cathode;
Second 360 hrs, 1M NaCl at anode and tap water at cathode;
Last 360hrs, 1M MgCl2 solution at anode and tap water at cathode.

Fig. 3 Electrokinetic Test Set-up

pH readings were taken at regular intervals using soil pH meter near cathode and anode
compartments and at three sections along the length of the compartment. The readings of
current and voltage were also continuously noted till the end of experiment by keeping
constant voltage of 25 volts. (Fig. 4)

0.25 1
Current
0.9
Current Density
0.2 0.8

Current Density in mA/sq.cm.

0.7
Current in Ampere

0.15 0.6

0.5

0.1 0.4

0.3

0.05 0.2

0.1

0 0
1 5 9 12 16 19 23 26 30 33 37 40 45 48 52 55
Time Elapsed in Days

Fig 4. Variation Of Current And Current Density With Time

Almost 10ml solution was collected each day, from anode and cathode compartments before
adding the new solution to respective compartments. The purging solutions were collected
from anode and cathode compartment at the end of each sequence of purging solutions. At
the end of the experiment the treated waste was chemically analyzed by TCLP standards. The
soil pH at the start of the experiment at the anode, cathode and along the length of the
specimen is the same and then varies as shown in Fig. 5.
 12 pH at Anode Section
pH at Cathode section
pH at Middle Section
10

8
pH

0
1 5 9 12 16 19 23 26 30 33 37 40 45 48 52 55
Time Elapsed in Days

Fig. 5 Variation Of Soil pH At Different Section With Time

Fig. 6 Concentration Of Heavy Metals At Anode With Different Purging Solution

The principle of electrokinetic remediation, which relies upon application of a low-intensity

direct current through the soil, creates an acidic front at the anode and a basic front at the
cathode. Due to electrolysis reactions, hydrogen and hydroxyl ions are produced which move
towards the cathode and anode respectively responsible for the consequently in the variation
of the soil pH. The rapid variation in the pH is whenever addition of purging solution takes
place at the anode and cathode.
In the beginning there is no foaming at anode and cathode compartment so the current was
steady. Within a short period of time, the current reaches a peak value because the mobile
ions associated with the soil through the adsorption of ions or ions in the form of salt
precipitates are dissolved into the pore solution. As time passes, the current decreases and
stabilizes because the initial amount of mobile ions is gradually depleted as they migrate
toward the respective electrode chamber, where they may concentrate or precipitate. But with
change in the purging solution there is a little increase in the current value after which it
becomes steady once again.

The removal of copper is 84%. Lead is also removed upto 97% in electrokinetic remediation
process. Aluminum is also removed 46%. The removal of zinc in the enhanced with MgCl2 is
more in compare to enhance with NaCl. Copper is removed maximum at cathode when
enhanced with NaCl while lead is removed in the anode region when enhanced with NaCl.
During unenhancment the copper ions are found maximum at anode. (Fig. 6) But when
enhanced with NaCl and MgCl2 the removal of copper ions is maximum at cathode (Fig. 7)
just because in enhanced remediation process copper is in cationic form and moves towards
cathode as free Cu +2 ions. The low pH at anode as compared to cathode is indicative that the
acid produced dissolves and thus mobilizes the copper. In the electrokinetic remediation
process the value of iron is more which indicates that when tap water is used in
unenhancment and at cathode during enhancement, tap water contains dissolved Fe+2 and
Fe+3 as complexes of Sulphate or nitrate so the value of iron is more as compared to the
original waste.

Fig. 7 Concentration Of Heavy Metals At Cathode With Different Purging Solution

Waste Stabilization
The stabilization of waste was taken into account to reutilize the waste in a form
commercially viable. This was tried by mixing the waste with various proportions of flyash
and lime. Bricks of size 23cm x 11cm x 8 cm were cast and thereafter kept for air curing for 7
days followed by one day of oven drying. These bricks were tested for their compressive
strength and water absorption capacity. The mixes selected were also used to find the change
in the geotechnical properties of the waste for use as fill material.

Liquid limit of waste is increased from 37% to 59.5% with addition of different proportion of
lime upto 8% with 5% flyash. Increase in percentage lime causes increase in the plastic limit
also. Increase in percentage lime with 5% flyash shows increase in shrinkage limit and
similarly when percentage of flyash is varied again the shrinkage limit shows a linear
increase. This change can be attributed to the adsorption of water by dry lime and the initial
reaction of lime, which decreases the plasticity index and also increase the shrinkage of the
mix on the whole. Free swell of mix with 5% lime increase with addition of higher
percentage of flyash to a limit of 35% and then decrease drastically. With variation of lime
maximum dry density in the beginning increases and is maximum for a mix with 5% lime and
25 % flyash. With higher percentage addition of flyash the maximum dry density decreases
rapidly as flyash is a lighter material. This trend is seen with the optimum moisture content
also. Unconfined compressive strength of waste varies in the range of 2.39kg/cm2 to
2.97kg/cm2 and 2.76 kg/cm2 to 4.15kg/cm2 for one and seven days of air curing respectively
with 5% lime and percentage flyash varying from 25% to 45% (Fig. 8).

4.50
1 day Compressive Strength
Unconfined Compressive Strength kg/sq.cm.

3 day Compressive Strength

4.00
7 day Compressive Strength

3.50

3.00

2.50

2.00
20.0 25.0 30.0 35.0 40.0 45.0 50.0
% Flyash

Fig. 8 Variation of UCS with variation in Percentage of Flyash with 5% Lime

Compressive strength of brick of mix 20% lime and 35% flyash with 45% waste is the
maximum in all proportions used for the study. The increase in flyash content is the reason
behind the overall trend of decrease in density and unconfined compressive strength, as with
higher percentage of flyash, bleeding of the mix water starts making it unavailable to lime for
its reaction. This becomes also the reason for decrease in the compressive strength of bricks
with higher percentage of flyash with lower lime contents, but when the content of lime is
increased with the increase in the flyash content the strength of the mix increases. The
addition of lime decrease the overall particle size and allows the formation of sand size
weakly cemented waste aggregates of calcium silicate and calcium aluminate hydrates
formed by reaction of lime and water along with pozzolanic activity of flyash in presence of
lime.
Conclusions
The removal of heavy metals is more when washing with sulphuric acid and starch, as
compared to washing with EDTA. The geotechnical properties of waste washed with
Sulphuric acid and starch are deteriorated as compared to the original contaminated waste.
The unconfined compressive strength of treated waste is 50% less than the contaminated
waste.

By sequentially enhanced electrokinetic remediation, removal of copper is 84% while

percentage removal of lead and aluminum is 97% and 46% respectively. Other heavy metals
are also removed in higher percentages by adopting sequentially enhanced electrokinetic
remediation than any other method.

It has been tried to stabilize the waste and make bricks from the waste by adding of different
proportion of lime and flyash. The maximum compressive strength of bricks made from
waste with 20% lime and 35 % flyash is 12.42 kg/sq.cm which is much less than that allowed
by IS for normal bricks which is 35 kg/sq.cm and therefore such bricks can be used in light
weight structures. Further improvement can be tried by adding some percentage of gypsum
and cement after which leachate analysis can be carried out for the good bricks.

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