Desalination 185 (2005) 483–490

Experimental study of the removal of copper from aqueous

solutions by adsorption using sawdust

S. Larous, A.-H. Meniai*, M. Bencheikh Lehocine

1-Laboratoire de l’Inge´nierie des Proce´de´s d’Environnement, De´partement de Chimie Industrielle, Universite´
Mentouri, Constantine 25000, Algeria
Tel. þ213 31 61 32; Fax þ213 31 61 32; e-mail: meniai@caramail.com

Received 25 February 2005; accepted 15 March 2005

Abstract
The test and use of natural materials as adsorbents for the removal of various pollutants such as heavy
metals from industrial wastewater is under constant development. Consequently this work concerns the study of
copper adsorption by means of sawdust obtained as by-product from locally used wood.
The copper retention study has been carried out batchwise where the influence of physico-chemical key
parameters such as the solution pH, the temperature, the agitation speed, the initial concentration, the
contacting time, the liquid to solid ratio and the ionic strength has been considered. A desorption study for
the solid support regeneration has also been included.
The equilibrium adsorption capacity of sawdust for copper has been obtained by using linear Freundlich and
Langmuir isotherms. The results tend to explain the retention mechanism as an ion exchange process for
binding the divalent metal ions to the sawdust.

Keywords: Sawdust; Heavy metals; Copper; Adsorption; Ion exchange; Retention

1. Introduction mainly due to their non-degradability and

The discharge of toxic metals into water-
courses is a serious pollution problem which
may affect the quality of water supply.
Increasing concentrations of these metals in
the water constitute a severe health hazard
*Corresponding author.
toxicity. Numerous metals such as chromium
Cr (III) and Cr (VI), copper (Cu), lead (Pb),
manganese (Mn), mercury (Hg), cadmium
(Cd), etc, are known to be significantly toxic.
Copper, the metal considered in this
study, is a widely used material, where an
intake of excessively large doses by man

Presented at the Conference on Desalination and the Environment, Santa Margherita, Italy, 22–26 May 2005.
European Desalination Society.
0011-9164/05/$– See front matter Ó 2005 Elsevier B.V. All rights reserved
doi:10.1016/j.desal.2005.03.090
484 S. Larous et al. / Desalination 185 (2005) 483–490
may lead, as examples, to severe mucosal irrita-
tion, a central nervous system irritation, possible
necrotic changes in the liver and kidney, etc].
These facts have been the motivating
factor for an increasing number of research
works associated with copper, where the main
objective is the development of various
techniques for the the removal and recovery
of these metallic species from wastewater.
These methods include, among others,
chemical precipitation, electroflotation, ion
exchange, reverse osmosis and adsorption
which is the scope of this work.
The process of adsorption implies the
presence of an ‘adsorbent’: solid that efficiently
binds molecules by means of physical attractive
forces, ion exchange or chemical binding. It is
recommended that the adsorbent is available in
large quantities, of free or very low cost and easily
regenerable [1–3]. Consequently it is always
important to explore and test this kind of materi-
als, as far as the surface properties are concerned.
Agricultural by-products may constitute
an important source of this type of materials
which may be interesting to study and test as
heavy metal adsorbents and then see how
selective they are in retaining certain metallic
ions. In the literature, research in the use of
agricultural by-products for metal binding
studies has mainly concerned the use of fruit
shells and stones, wheat and rice bran, etc but
seldom sawdust [4]. Most cases have con-
firmed that the use of large quantities of
wastes from agricultural products for the
treatment of polluted water is an attractive
and promising option with a double benefit
for the environment:
 It reduces the residues whose disposal
becomes a major, costly problem and
 It converts the wastes into useful and inex-
pensive sorbents for water purification.
The aim of the present work is then to study
the capacity of sawdust issued from locally used
wood for the removal of copper (II).
2. Experimental
2.1. Apparatus and instrumentation
 Atomic absorption spectrophotometer AA-
varian-20 plus operating with an air-acety-
lene flame has been used for the determina-
tion of copper concentrations in aqueous
solutions. A priori, a calibration curve has
been established, preparing standard aqu-
eous solutions of copper (standard) of 1 g/l
[5] in order to be able to read the residual
concentrations of this metal.
 The pH measurements have been per-
formed with a Multiline P4 phmeter and.
The meter was standardized using buffer
solutions with pH values: 4.00, 7.00, 10.00.
 All filtration’s during this work have been
carried out by the means of the filter millipore
0.2 mm – Sartorius MINISART SRP 15.
2.2. Adsorbent
Sawdust obtained from locally used wood,
with a mean size of 0.331 mm has been
directly used without any pre-treatment, as
an adsorbent for the removal of copper (II)
from aqueous solution.
2.3. Adsorbate solution
Synthetic aqueous solutions containing
copper have been prepared by dissolution of
copper sulphate in locally distilled water.
2.4. Experimental procedure
Batch adsorption experiments have been car-
ried out by shaking 0.5 g of the sawdust with
100 ml of the copper solution of 10 mg/l con-
centration at 23 C. The suspension is agitated at
300 rpm for a known period of time ranging
between 5 and 120 min. At the end of the pre-
determined time interval the adsorbent is
removed by filtration and a sample of the filtrate
is analysed by means of the atomic adsorption. It
should be noted that the pH of the suspension in
 S. Larous et al. / Desalination 185 (2005) 483–490 485

the experiments has been adjusted with NaOH present in sawdust. Decreasing in adsorption
0.1M (1M) and HNO3 0.1M (1M). at high pH may be due to the formation of
soluble hydroxy complexes [6]. At pH 6 there
are three species present in solution as sug-
3. Results and discussion
gested by [7] : Cu2þin very small quantity and
3.1. Effect of pH Cu(OH)þ and Cu(OH)2 in large quantities.
The pH of the aqueous solution is an These species are adsorbed at the surface of
important controlling parameter in the sawdust by ion exchange mechanism with the
adsorption process and thus the effect of pH functional groups present in sawdust or by
has been studied by varying it in the range of hydrogen bonding as shown below
2–10 as shown in (Fig. 1).
It can be observed that the retention of )
2ð  ROHÞ þ Cu2þ ! 2ðROÞCu þ 2Hþ
copper by sawdust increases while the pH
increasing until a certain value, it increases  ROH þ CuOHþ ! ðROÞCuOH þ Hþ
between pH 2.0 and a pH about 6.29, after
Ion exchange
that the capacity of adsorption decreases
slightly in pH range of 8–10. The maximum 2ðROHÞ þ CuðOHÞ2 ! ðROHÞ2
sorption efficiency in the range of 2–8 may be CuðOHÞ2 H  bonding
due to the interaction of Cu2þ, Cu(OH)þ,
Cu(OH)2 with surface functional groups Where-R represents the matrix of sawdust.

pH = 2.06
pH = 4.03
pH = 6.29
pH = 8.04
pH = 10.02

2,0 2.0
q (mg deCu/gd'adsorbant)
q (mg de Cu/g d'adsorbant)

1,5 1.5

Run 1
1,0 1.0 Run 2
Run 3

0,5 0.5

0,0 0.0
0 20 40 60 80 100 120 0 2 4 6 8 10
Temps (min) PH

Fig. 1. Effect of pH on the retention of copper by sawdust Conditions: C0 = 10 mg/l, V = 300 rpm, T = 23 C0,
d = 0.331 mm, t = 120 min, r = 5g/l.
486 S. Larous et al. / Desalination 185 (2005) 483–490
1.5
q (mg de Cu/g d'adsorbant)
1.0
0.5
0.0
0 20 40 60 80
Le temps (min)
Fig. 2. Effect of the temperature on the retention of copper
by sawdust Conditions: C0 = 10 mg/l, V = 300 rpm,
t = 120 min, d = 0.331 mm, pH = 6.29, r = 5g/l.
3.2. Effect of the temperature
Fig. 2 shows that the retention of copper
by sawdust increases while the temperature is
increasing until a certain value. The increase
in adsorption capacity with temperature sug-
gested that the active surface sites, available
for adsorption have increased with tempera-
ture. The increase of the temperature
encourages the process of agglomeration in
a very determined sense, until a certain tem-
perature limit, beyond which the desorption
becomes more important and hence reducing
the rate of adsorption, as time goes on. This
temperature limit can be regarded as an opti-
mal temperature that varies around 40 C.
Also the increase of the temperature can
change the pore sizes which become wider,
and can induce a certain activation of the
surface of the solid support.
3.3. Effect of the agitation speed
The agitation speed is an important para-
meter in any transfer phenomena, since it can
promote a certain turbulence which insures
an intimate contact between the phases, a
fact which contributes to the improvement
of mass transfer.
In order to assess the effect of the agitation
speed, three different speeds have been chosen
as shown in Fig. 3, where it can be noted that
the retention of copper increases progressively
T = 20 C°
with the agitation speed as time goes on. There-
T = 35 C° fore it can be concluded that the agitation speed
T = 45 C° encourages a better transfer of species between
T = 60 C°
the two phases (adsorbent–adsorbate).
100 120
3.4. Effect of the initial concentration
Fig. 4 shows that the increase in initial
concentration of copper (II) decreases the
adsorption and increases the amount of metal
uptake per unit weight of the adsorbent (mg/g)
The percentage decrease is between 90.4%
(0.180 mg/g) and 70.84% (3.742 mg/g) where
the initials concentrations are increase between
1 and 25 mg/l. This is because at higher initial
concentrations, the ratio of initial number of
moles of copper (II) to the available adsorp-
tion surface area, is high.
1,5
q (mg de Cu/g d'adsorbant)
1,0
V = 80 rpm
V = 300 rpm
V = 500 rpm
0,5
0,0
0 20 40 60 80 100 120
Le temps (min)
Fig. 3. Effect of the agitation speed on the retention
of copper by sawdust Conditions: C0 = 10 mg/l,
T = 23 C0, d = 0.331 mm, pH = 6.29, r = 5g/l.
 S. Larous et al. / Desalination 185 (2005) 483–490 487

C0 = 1 mg/l important to study its effect on the capacity

C0 = 5 mg/l
C0 = 10 mg/l
of retention of copper by sawdust.
C0 = 25 mg/l Fig. 5 has the typical form of a saturation
4.0
curve. It clearly shows that the equilibrium is
3.5
attained just after only 5 minutes. The
q (mgde Cu/g d'adsorbant )

3.0 increase in contacting time has increased the

2.5 copper uptake and this can be explained by
the affinity of the support towards copper.
2.0

1.5
3.6. Effect of the liquid to solid ratio
1.0
To study the influence of the liquid
0.5
to solid ratio on the retention of copper,
0.0
0 20 40 60 80 100 120
three different values have been taken by
Temps (min) varying the sorbent amount of the support
while keeping the volume of the metal
Fig. 4. Effect of the initial concentration on the retention solution constant as shown in Fig. 6 where
of copper by sawdust Conditions: C0 = 10 mg/l, it can be seen that the adsorption increases
V = 300 rpm, t = 120 min, d = 0.331 mm, pH = 6.29, with the increase in the amount of sawdust.
r = 5 g/l. This can be explained by a greater availability
of the exchangeable sites or surface area at
3.5. Effect of contacting time
higher concentration or amount of the sorbent.
Also contacting time is inevitably a funda-
mental parameter in all transfer phenomena 3.7. Effect of the ionic strength
such as adsorption. Consequently it is
Fig. 7 shows the in fluence of the ionic
strength on the capacity of adsorption. It

1.5
1.5
q (mg de Cu/g d'adsorbant)

q (mg de Cu/mg d'adsorbant)

1.0
1.0

Run n° 1
0.5
Run n° 2
0.5 r = 1 g/l
Run n° 3
r = 3 g/l
r = 5 g/l

0.0
0 20 40 60 80 100 120
0.0
Time (min) 0 20 40 60 80 100 120
Time (min)

Fig. 5. Effect of contacting time on the retention

of copper by sawdust Conditions: C0 = 10 mg/l, Fig. 6. Effect of the liquid to solid ratio on the reten-
V = 300 rpm, T = 23 C0, d = 0.331 mm, pH = 6.29, tion of copper by sawdust Conditions: C0 = 10 mg/l,
r = 5g/l. V = 300 rpm, T = 23 C0, d = 0.331 mm, pH = 6.29.
488
1.6
1.5
q(mg de Cu/g d'adsorbant )
1.4
1.3
1.2
1.1
1.0
0.00 0.02
Ionic strength (M)
Fig. 7. Effect of the ionic strength on the retention of
copper by sawdust Conditions: C0 = 10 mg/l,
V = 300 rpm, T = 23 C0, d = 0.331 mm, t = 120 min.
has been tested by the addition of sodium
chloride to the copper solution. The increase
in ionic strength between 0.001 and 0.1 has
decreased the percentage of adsorption
between 71.20 and 49.70 %. This may be
due to the following two reasons :
a) The electrostatic attraction seems to be a
significant mechanism, as indicated by the
results where at high ionic strength, the
increased amount of NaCl can help to render
the surface of the sawdust not easily accessi-
ble to copper (II) ions and hence decrasing
the adsorption rate. In fact according to the
Surface Chemistry Theory developed by
Guoy and Chapman [8], when solid adsor-
bent is in contact with sorbate species in solu-
tion, they are bound to be surrounded by an
electrical diffused double layer, the thickness
of which is significantly expanded by the pre-
sence of electrolyte. Such expansion inhibits
the adsorbent particles and Cu (II) from
approaching.
b) The relative competition between sodium
ions and copper species for the active sites of
sawdust, can also be an explaining factor.
S. Larous et al. / Desalination 185 (2005) 483–490
3.8. Desorption study
A desorption study is also important since
NaCl it is useful in the recycling of the adsorbent
and recovery of metal. For this study differ-
ent extractant reagents have been tested as
shown in Fig. 8. The sodium chloride NaCl
0.2M eluted a rather significant quantity of
copper ions from sawdust. An efficiency of
33.8% has been obtained by using NaCl
0.2M. In contrast the other extractants
reagents NaNO3, NaCl þ HCl, HNO3, HCl
were not efficient in the desorption of Cu (II)
0.04 0.06 0.08 0.10 ions.
3.9. Analysis of the adsorption capacity by
means of the Langmuir and Freundlich models
The study of the adsorption isotherm is
fundamental, and plays an important role in
the determination of the maximal capacity of
adsorption. In order to adapt for the consid-
ered system, an adequate model that can
reproduce the experimental results obtained,
equations of Langmuir and Freundlich
shown in Table 1, have been considered. Gen-
erally the Langmuir equation applies to the
cases of adsorption on completely homoge-
neous surfaces where interactions between
adsorbed molecules are negligible. While the
equation of Freundlich applies fairly well
0.35
0.3
0.25
0.2
Desorption (%)
0.15
0.1
0.05
0
7.66 6.62 7.82 7.02 8.038
NaNO3 NaCl HNO3 HCl NaCl + HC
Fig. 8. Extractant (0.2 M) Conditions: C0 = 10 mg/l,
V = 300 rpm, T = 23 C0, t = 120 min.
 S. Larous et al. / Desalination 185 (2005) 483–490 489

Table 1 Freundlich isotherms, as show the following

Langmuir and Freundlich constants for the Figs. 9a and b.
adsorption of Cu (II) on sawdust Explicitly the Langmuir and the Freun-
Models Equations a b R2 dlich equations are expressed, respectively,
a:b:Ce as follows
Langmuir Qe ¼ 1þb:C e
8.45197 0.0942 0.93877
Freundlich Qe ¼ a:Ceb 1.34776 0.42698 0.93412 ð8:45197Þð0:0942ÞCe
Qe ¼ ð1aÞ
Where Ce is the equilibrium concentration of the 1 þ ð0:0942ÞCe
solution (mg/l); Qe is the amount of solute adsorbed
by unit mass of adsorbent (mg/g); a, b constants; R
Qe ¼ 1:34776Ce0:42698 ð1bÞ
the correlation factor.

when describing the adsorption in aqueous 4. Conclusions

systems. This study shows clearly that sawdust
It can be seen that the correlation factor is which is a cheap and abundant material can
close to unity for both models, indicating a be used as an effective adsorbent for removal
good representation of the experimental of copper from wastewater. This adsorption
results by using linear Langmuir or process is also dependent on numerous

8
7.5
7
qe (mg de Cu / g d'adsorbant )

6
qe ( mg de Cu / g d'adsorbant )

6.0

4.5
4

3
Experimental values
3.0

Experimental values 2

1.5 1

0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70
Ce (mg de Cu / l) Ce (mg de Cu / l)

(a) (b)
Langmuir isotherm of copper Freundlich Isotherm of copper
Fig. 9. Adsorption isotherms using Langmuir and Freundlich models Conditions: V = 300 rpm, pH = 6.29,
r = 5g/l, d = 0.331 mm, T = 23 0C.
490 S. Larous et al. / Desalination 185 (2005) 483–490
factors such as the solution pH, the tempera-
ture, the agitation speed, the initial concen-
tration, the contacting time, the liquid to
solid ratio, the ionic strength, etc. The max-
imum percentage removal occurs between the
pH range 2.0–8.0. The study of the ionic
strength and the pH effects, has confirmed
that ion exchange is the major mechanism of
retention of copper by sawdust undergoing
no treatment, and showing a high efficiency
The isotherm study indicates that the sorp-
tion data can be modelled by both Langmuir
and Freundlich isotherms..
The study of desorption was also carried
out and shows that the sodium chloride
(NaCl) 0.2 M is the best extractant.
5. References
[1] J.V. Rios, L. Bess-Oberto, K.J. Tiemann and
J.L. Gardea-Torresdey, Investigation of Metal
ion Binding by Agricultural By-Products. Pro-
ceedings of the. Conference on Hazardous
Waste Research, 1999 125.
[2] S. Arris, M. Bencheikh-Lehocine, A.-H. Meniai,
M. Morcellet, M. Bacquet, B. Martel and
A. Mansri, ‘Study and Identification of Reten-
tion Process of Heavy Metals by Adsorption on
Agricultural By-Products’ Chemical Engineering
& Technology. Eng. Life Sci., 3 (2003) 9.
[3] N. Gherbi, A.-H. Meniai, M. Bencheikh-Lehocine,
A. Mansri, M. Morcellet, K. Bellir, M. Bacquet
and M. Martel, ‘Study of The Retention Phenom-
ena of Copper II by Calcinated Wheat Bypro-
ducts’. Desalination, 166 (2004) 363–369.
[4] S.R. Shukla and V.D. Sakhardane, Column stu-
dies on metal ion removal by dyed cellulosic
materials. Journal of Applied Polymer Science,
44 (1992) 903–910.
[5] K. S. Binay and N.S. Rawat, Comparative sorp-
tion Kinetic studies of phenolic compounds on
fly ash impregnated fly ash. J.Chem. Technical
Biotechnol, 61 (1994) 57–65.
[6] K. Anoop Krishnan and T.S. Anirudhan, Removal
of Cadmium (II) from Aqueous Solutions by
Steam-Actived Sulphurised Carbon prepared from
Sugar-Cane Bagasse Pith: Kinetics and Equilibrium
Studies, Department of Chemistry, University of
Kerala, Water SA, 29(2) 2003.
[7] H.A. Elliot and C.P. Huang, Water Res, 15
(1981) 849.
[8] L. Osipow 1 ‘Surface Chemistry: Theory and
Industrial Applications’, Krieger, New York
1972.