Water Research 36 (2002) 24832490

Removal of lindane and malathion from wastewater using

bagasse y ashFa sugar industry waste
Vinod K. Guptaa,*, C.K. Jainb, Imran Alib, S. Chandraa, S. Agarwala
a

Department of Chemistry, Indian Institute of Technology Roorkee (Formerly University of Roorkee), Roorkee 247 667,
Uttaranchal, India
b
National Institute of Hydrology, Roorkee 247 667, Uttaranchal, India
Received 1 December 2000; received in revised form 1 October 2001; accepted 25 October 2001

Abstract
The bagasse y ash, obtained from the local sugar industry, has been used as inexpensive and effective adsorbent for
the removal of lindane and malathion from wastewater. The optimum contact needed to reach equilibrium was found
to be 60 min. Maximum removal takes place at pH 6.0. The removal of the pesticides increases with an increase in
adsorbent dose and decreases with adsorbent particle size. The optimum adsorbent dose is 5 g/l of particle size 200
250 mm. Removal of the two pesticides was achieved up to 9798% under optimum conditions. The material exhibits
good adsorption capacity and follows both Langmuir and Freundlich models. Thermodynamic parameters also
indicate the feasibility of the process. The adsorption was found to be exothermic in nature. At lower concentrations,
adsorption is controlled by lm diffusion, while at higher concentrations, it is controlled by particle diffusion
mechanisms. The adsorbent is a very useful and economic product for the removal of lindane and malathion. r 2002
Elsevier Science Ltd. All rights reserved.
Keywords: Adsorption; Removal; Wastewater; Bagasse y ash; Lindane; Malathion

1. Introduction
Water pollution by organic and inorganic compounds
is of great public concern. Adsorption technology is
currently being used extensively for the removal of such
pollutants from wastewaters. Among the various adsorbent systems available for the removal of pollutants
from wastewater, activated carbon is being widely used
in developed countries [13]. However, the high cost of
activated carbon and difculties associated with its
regeneration [4], limits its use in developing countries.
This has led to interest in the development of low cost
alternatives to activated carbon. Thus a variety of
materials, as adsorbents for the removal of different
pollutants, have been tried by various workers [522].
*Corresponding author. Tel.: +91-1332-74458; fax: +911332-73560.
E-mail address: vinodfcy@rurkiu.ernet.in,
vinodfcy@yahoo.com (V.K. Gupta).

All the materials studied have their own advantages and

limitations and therefore, there is still a need for
developing low cost adsorbents.
Pesticides are very dangerous and harmful because of
their toxic and carcinogenic nature [23]. The EEC
Directive [24] for pesticides concentrations in water for
human consumption is 0.1 g/l. Lindane and malathion
are the two most commonly used pesticides in India and
are very toxic [2530]. The pesticides contaminate water
through agricultural, domestic and industrial activities
and therefore their removal is important. The characteristics and chemical composition of bagasse y ashFa
sugar industry waste, as a low cost adsorbent, were
reported earlier [22]. It is reported that y ash is stable in
water, dilute acids and bases and has a surface area
(BET) of 450 m2/g (particle size 200250 mm) and had
successfully been tried for the removal of pollutants
from aqueous solutions. In continuation, an attempt has
been made to examine the utility of this material for the
removal of lindane and malathion from water and

0043-1354/02/$ - see front matter r 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 3 - 1 3 5 4 ( 0 1 ) 0 0 4 7 4 - 2

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V.K. Gupta et al. / Water Research 36 (2002) 24832490

wastewaters. The effects of various operating variables

(e.g. pH, adsorbent dose, adsorbate concentration,
temperature, particle size, etc.) on removal has been
studied to arrive at optimum conditions for the process.
The results are presented and discussed in this communication.

2. Experimental methodology
2.1. Reagents and equipment
All chemicals and reagents used were of analytical
grade and were obtained form E. Merck, India and
Sigma Chemical Co., USA. Stock solutions of sodium,
potassium, calcium, magnesium, chloride, sulphate,
nitrate and phosphate were prepared in deionized water
while that of lindane and malathion were prepared in
n-hexane. A pH meter (Hach, USA) was used for pH
measurements. The surface area of the adsorbent was
measured by a surface area analyser (Quantasorb Model
QS-7). The concentrations of lindane and malathion
were determined by gas chromatography (GC) (Aimil
Nucon Model 5700) using Electron Capture Detection.
2.2. Adsorbent development
Bagasse y ash, a waste material of the sugar industry,
was collected from a sugar factory at Iqbalpur, U.A.,
India. The material was treated with hydrogen peroxide
at 601C for 24 h. It was then washed with de-ionized
water, dried at 1001C, powdered, ground and sieved to
produce particle sizes; 100150, 150200 and 200
250 mm. The material was stored in a vacuum desiccator
prior to further use. The stability of the adsorbent was
determined by keeping the material over night in
different solvents (water, dilute acids and bases) and
determining the presence of its constituents in these
solvents. The various constituents and other properties
of the prepared material were determined as reported
earlier [22].
2.3. Adsorption studies
Adsorption experiments were carried out in batch
mode using a series of Erlenmeyer asks of 50 ml
capacity covered with teon sheets to prevent contamination. The effect of time, concentration, solution pH,
adsorbent dose and temperature were studied. Isotherms
were obtained by adsorbing different concentrations of
lindane and malathion at various temperatures and pH.
After prescribed contact times, the solutions were
centrifuged and the concentrations of lindane and
malathion in the supernatant were determined.

2.4. Column studies

The experimental set-up for column studies is shown
in Fig. 1. The upper end of the column was attached to a
wastewater tank to regulate the ow of wastewater. The
adsorbent material was kept for 12 h in de-ionized water
and then used for packing the column. The column was
left overnight to settle and saturate. Column elution was
carried out up to a point of 90% of the breakthrough
capacity. The regeneration of the column was tried with
different eluents (methanol, ethanol, sodium hydroxide,
potassium hydroxide, sulphuric acid, hydrochloric acid
and nitric acid).
2.5. Pesticide analysis
Lindane and malathion were extracted from aqueous
solutions using n-hexane. The extracts were concentrated on water bath and water content removed using
anhydrous sodium sulphate. The extracts were then used
for quantication of lindane and malathion by gas
chromatograpy. All GC analyses were carried out at
150721C, 200721C and 225721C temperatures for
column, injector and detector, respectively. The mobile
phase used was nitrogen at a ow rate of 60 ml/min. The
glass column used was of 120
3 mm size packed with
80100 mesh size CH.W.H.P.
The chromatograms of pure lindane and malathion
were also recorded under the same experimental
conditions for qualitative and quantitative comparisons.
The extracted concentration of lindane and malathion
were found to be 98.5% and 98.0%, respectively and
a correction factor of the loss of lindane and malathion
in extraction procedure was used to calculate the
concentration of the two pesticides in adsorption
studies.

3. Results and discussion

3.1. Effect of particle size
The adsorption of lindane and malathion decreases
with increasing particle size of the y ash. The percent
adsorption of lindane was found to be 99.9%, 95.0%
and 88.0% for 100150, 200250 and 300350 mm size
of the y ash. Fly ash of particle size 200250 mm
was selected for further adsorption studies due to its
sufcient adsorption capacity and ease of preparation. Moreover, the centrifugation of this particle
size did not require any special attention during
experiment. It was observed that adsorbent of particle
size 300350 mm has a poor adsorption capacity, and it is
very difcult to prepare the adsorbent of the particle size
100150 mm.

V.K. Gupta et al. / Water Research 36 (2002) 24832490

2485

Fig. 1. The set up for column experiments.

3.2. Equilibrium time

The adsorption data for the uptake of pesticides
versus contact time (at a dispersion concentration of 5 g/
l) are shown in Fig. 2. The adsorption of pesticides
increases with increasing contact time and becomes
almost constant after 60 min. This represents the time at
which an equilibrium pesticide concentration is presumed to have been attained.

higher solution concentrations the amount adsorbed

remained constant at about 2 mg/g (Fig. 3).
3.4. Effect of pH
The adsorption of lindane and malathion was studied
over the pH range 2.09.0 (Fig. 4). The maximum
uptake of lindane and malathion takes place at pH
6.0. The adsorption remains constant beyond this pH
value. Therefore the optimum pH for the removal of
lindane and malathion is 6.0.

3.3. Effect of concentration

3.5. Effect of adsorbent dose
The effect of pesticide concentration on the adsorption is shown in Fig. 3. The equilibrium concentration of
pesticides on y ash was found to increase with initial
concentration of pesticides in the range 010 ppb. At

The effect of the adsorbent dose on removal of

lindane and malathion is depicted in Fig. 5. The
adsorption of lindane and malathion increases in the

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V.K. Gupta et al. / Water Research 36 (2002) 24832490

Fig. 2. Effect of contact time on adsorption of lindane and

malathion.

Fig. 4. Effect of pH on adsorption of lindane and malathion.

Fig. 3. Effect of initial concentration of lindane and malathion

on adsorption.

Fig. 5. Effect of adsorbent dose on adsorption of lindane and

malathion.

range 15 g/l and then becomes constant indicating that

5 g/l of adsorbent is sufcient for the optimum removal
of lindane and malathion.

3.6. Effect of temperature

The adsorption isotherms at three different
temperatures are presented in Figs. 6 and 7 for the
removal of lindane and malathion, respectively. The
adsorption is almost unaffected with rising temperature
at lower concentrations of lindane and malathion.
However, it decreases at higher concentration for both
the pesticides. The adsorption in both cases follow the
order 301C>401C>501C. Since the adsorption is
decreasing at higher temperatures, it is exothermic in
nature.

Fig. 6. Adsorption isotherm of lindane at different temperatures.

V.K. Gupta et al. / Water Research 36 (2002) 24832490

2487

Fig. 8. The graphical representation of Langmuir isotherm.

Fig. 7. Adsorption isotherm of malathion at different temperatures.

Table 1
Langmuir and Freundlich constants for the uptake of lindane and malathion
Adsorbate

Langmuir constants

Freundlich constants

Qo (mg/g)

Lindane
Malathion

Kf

301C

401C

501C

301C

401C

501C

301C

401C

501C

301C

401C

501C

2.51
2.08

2.48
2.04

2.40
2.00

1.33
1.54

1.36
1.58

1.40
1.63

17.41
17.58

18.01
18.11

18.82
18.90

1.91
1.81

2.00
1.90

2.11
1.96

3.7. Effect of interfering ions

A decrease in the scavenging efciency of the
adsorbent takes place in the presence of various ions.
In the presence of 10100 ppm sodium, 550 ppm
potassium, 10100 ppm calcium, 550 ppm magnesium,
25300 ppm chloride, 2550 ppm sulphate, 550 ppm
nitrate and 210 ppm phosphate ions, the order of
decrease was 4.0%, 7.5%, 6.0%, 4.5%, 2.0%, 1.8%,
1.6% and 1.5% for lindane and 4.3%, 8.0%, 6.0%,
4.5%, 2.0%, 1.7%, 1.6% and 1.4% for malathion,
respectively. As the decrease is not very appreciable, the
adsorbent can be used for removal of lindane and
malathion in the presence of these ions.
3.8. Adsorption isotherm
The results obtained on the adsorption of lindane and
malathion were analysed by the models given by
Langmuir and Freundlich.
The Langmuir isotherm has been used by various
workers for the sorption of a variety of compounds. The
model assumes uniform energies of adsorption on to the
surface and no transmigration of adsorbate in the plane
of the surface. The linear form of Langmuir isotherm is

given by the following equation:

1=qe 1=Qo 1=bQo Ce ;

where qe is the amount adsorbed (mg/g), Ce is the

equilibrium concentration of the adsorbate (mg/l) and
Qo and b are the Langmuir constants related to
maximum adsorption capacity and energy of adsorption, respectively. When 1=qe were plotted against 1=Ce ;
straight lines were obtained (Fig. 8), which show that the
adsorption of lindane and malathion follow the Langmuir isotherm. The Langmuir constants, b and Qo ; are
calculated and the values of these at three different
temperatures are listed in Table 1.
The adsorption data of lindane and malathion was
also analysed using the Freundlich model. The logarithmic form of the Freundlich model is given by the
following equation:
log qe log KF 1=n log Ce ;

where qe is the amount adsorbed (mg/g), Ce is the

equilibrium concentration of the adsorbate (mg/l) and
KF and n are Freundlich constants related to adsorption
capacity and adsorption intensity, respectively [31].
When log qe were plotted against Ce ; straight lines were
obtained (Fig. 9), which show that the adsorption of

V.K. Gupta et al. / Water Research 36 (2002) 24832490

2488

lindane and malathion also follow the Freundlich

isotherm. The Freundlich constants, KF and n; were
calculated and the values of these at three different
temperatures are also listed in Table 1.
The thermodynamic parameters of the adsorption
processes were calculated by using the equations
described earlier [22] and the values are given in
Table 2. The free energy increases with increase in
temperature thereby indicating a decrease in adsorption
at higher temperature and exothermic nature of the
adsorption. The values of Ea ; Di ; Do ; and DSx, as
calculated using the equations and methods described
earlier [22], are given in Table 3. The effective diffusion
coefcients Di in these systems is mainly comprised of

two components which are due to the simultaneous

diffusion of the ingoing adsorbates through the pores of
different widths and different electronic elds along the
diffusion path. The diffusion within the pores of wider
paths and weaker retarding forces of electrostatic
interaction (particularly at the surface of the adsorbent)
accounts for the faster component, and one within the
pores of narrower mesh widths and stronger retarding
forces accounts for the slower component of Di : As the
temperature increases, the contribution of the faster
component of Di decreases. It is due to the decreasing
mobility of ingoing species at higher temperature, which,
to some extent, overcomes the inuence of the retarding
forces.
3.9. Column studies
It is seen (Fig. 10) that almost 100% lindane and
malathion are removed at low ow rates but this
decreases with increase in ow rate. Further, the
optimum removal takes place at a ow rate of 1.2 ml/
min. The breakthrough curves were used to calculate the
column capacity at complete exhaustion, and this was
found to be 4.5 mg/g, which is higher than the batch
experiment (1.9 mg/g). The system has been used in the
laboratory to remove lindane and malathion from
wastewater and surface water of some Indian rivers. It
was observed that the system is capable of removing
these pesticides up to 98%. Therefore, this system can be
used for the successful removal of lindane and
malathion from wastewater and other efuent.
Desorption of the two pesticides and regeneration of
the columns could be achieved by 5% NaOH. It was

Fig. 9. The graphical representation of Freundlich isotherm.

Table 2
Thermodynamic parameters for the uptake of lindane and malathion
Adsorbate

Lindane
Malathion

DG 0 (kJ/mol)

DH 0 (kJ/mol)

DS0 (J/mol)

301C

401C

501C

301C

401C

501C

301C

401C

501C

0.719
1.090

0.799
1.190

0.903
1.310

1.77
2.02

2.44
2.62

2.09
2.31

8.22
10.26

10.35
12.17

9.27
11.20

Table 3
Other parameters for the uptake of lindane and malathion
Di

(a)
(b)

301C

401C

501C

5.63
1012
2.48
1012

6.01
1012
2.90
1012

6.69
1012
3.29
1012

Do

Ea

DSx

7.16
1012
3.85
1012

7.096
11.506

110.96
116.12

aFLindane; bFMalathion; Di FEffective diffusion constant in the adsorbate phase at different temperatures at 60 min;
Do FEffective diffusion constant in the adsorbate phase at 24 h (p time); Ea FEnergy of activation of adsorption and DSxFEntropy
of activation.

V.K. Gupta et al. / Water Research 36 (2002) 24832490

Fig. 10. Effect of ow rate on the percent adsorption of lindane

and malathion.

observed that the column lost (about 2%) of its capacity

after the rst run and about 35% after more than ve
runs. The treatment of the column with 1.0 M HNO3 at
a ow rate of 1.0 ml/min restored the lost capacity to
almost the original value and the column could be
further used for ten runs without signicant loss of
capacity.

4. Conclusion
It may be concluded that bagasse y ash is an effective
and inexpensive adsorbent for pesticide removal from
wastewater. The removal of the lindane and malathion
by this adsorbent takes place via partial diffusion.
Adsorption follows both Langmuir and Freundlich
models. The adsorption was found to be exothermic in
nature. Lindane and malathion are adsorbed by the
adsorbent up to 9495% at pH 6.0. The removal of the
two pesticides was achieved up to 9798%.

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