Process Biochemistry 40 (2005) 3031–3044

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Removal of copper(II) ions from aqueous solution by

biosorption onto agricultural waste sugar beet pulp
Zümriye Aksu *, İ. Alper İşoğlu
Hacettepe University, Department of Chemical Engineering, 06532 Beytepe, Ankara, Turkey
Received 21 September 2004; received in revised form 13 January 2005; accepted 14 February 2005

Abstract

Dried sugar beet pulp, an agricultural solid waste by-product, was used as an biosorbent for the removal of copper(II) from aqueous
solution. A series of experiments were conducted in a batch system to assess the effect of the system variables, i.e. initial pH, temperature and
initial metal ion concentration. The results indicated that at 250 mg l
1 initial copper(II) concentration dried sugar beet pulp exhibited the
highest copper(II) uptake capacity of 28.5 mg g
1 at 25 8C and at an initial pH value of 4.0. The equilibrium data were analyzed using the
Freundlich, Langmuir, Redlich–Peterson and Koble–Corrigan isotherm models depending on temperature. The Langmuir model was found to
best describe the data in the concentration and temperature ranges studied. Simple mass transfer and kinetic models were applied to the
experimental data to examine the mechanisms of biosorption and potential rate-controlling steps such as external mass transfer, intraparticle
diffusion and biosorption process. It was found that the intraparticle diffusion played an important role in the biosorption mechanisms of
copper(II), and biosorption kinetics followed pseudo first- and pseudo second-order kinetic models rather than the saturation type kinetic
model for all temperatures studied. The activation energy of biosorption (EA) was determined as
58.47 kJ mol
1 using the Arrhenius
equation. Using the thermodynamic equilibrium coefficients obtained at different temperatures, the thermodynamic constants of biosorption
(DG8, DH8 and DS8) were also evaluated.
# 2005 Elsevier Ltd. All rights reserved.

Keywords: Biosorption; Copper(II); Dried sugar beet pulp; Equilibrium; Kinetics; Thermodynamics

1. Introduction tion, and the fertilizer industry, etc. Consequently, waste-

Copper is a widely used industrial metal used for
electrical wiring, plumbing, air conditioning tubing and
roofing. The properties of copper, which make it suitable for
these applications, include high electrical and thermal
conductivity, good corrosion resistance, ease of fabrication
and installation, attractive appearance, ready availability,
and high recyclability. Additionally, copper, which is an
essential nutrient to humans and other life forms, is biostatic/
biocidal to certain organisms. However, copper(II) is known
to be one of the heavy metals most toxic to living organisms
and it is one of the more widespread heavy metal
contaminants of the environment. The potential sources
of copper in industrial effluents include metal cleaning and
plating baths, pulp, paper board mills, wood pulp produc-
* Corresponding author. Tel.: +90 312 2977434; fax: +90 312 2992124.
E-mail address: zaksu@hacettepe.edu.tr (Z. Aksu).
waters of these industries contain high levels of copper(II)
ions and in order to avoid water pollution treatment is
needed before disposal [1–6].
The most widely used method for removing heavy metal
ions including copper(II) ions is coagulation and precipita-
tion. Heavy metals, for example, can be precipitated as
insoluble hydroxide at high pH or sometimes as sulfides. A
major problem with this type of treatment is the disposal of
the precipitated waste. Moreover, the precipitation itself
cannot reduce the contaminant far enough to meet current
water-quality standards. Ion exchange treatment is the
second most widely used method for metal removal. This
method does not present a sludge disposal problem and has
the advantage of reclamation of metals. It can reduce the
metal ion concentration to a very low level. However, ion
exchange does not appear to be practicable to wastewater
treatment from a cost stand point. Adsorption with activated
carbon can also be highly efficient for the removal of

1359-5113/$ – see front matter # 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.procbio.2005.02.004
3032 Z. Aksu, İ.A. İşoğlu / Process Biochemistry 40 (2005) 3031–3044
numerous trace elements from water, but the high cost of
activated carbon inhibits its large-scale use as adsorbent.
Then, the need for effective and economical removal of
heavy metal ions resulted in a research for unconventional
methods and materials that might be useful in this field [1–
6].
Biosorption is an alternative technology to remove heavy
metals from dilute aqueous solutions using inactive and dead
biomasses, such as agricultural and fermentation wastes,
various kinds of microorganisms, to bind and accumulate
these pollutants by different mechanisms such as physical
adsorption, complexation, ion exchange and surface micro-
precipitation [1,4–6].
In the past few years, extensive research has been
undertaken to develop alternative and economic adsorbents.
An economic sorbent is defined as one which is abundant in
nature, or is a by-product or waste from industry and
requires little processing. Agricultural waste biosorbents
generally used in biosorption studies are also inexhaustible,
low-cost and non-hazardous materials, which are specifi-
cally selective for heavy metals and easily disposed by
incineration. Agricultural by-products as a whole exceed
320,000,000,000 kg/year. Most of these by-products are
considered to be low value products. The agricultural by-
products such as peat, wood, pine park, banana pith, rice
bran, wheat bran, peanut shells, wool, rice milling by-
products (hulls and bran), sunflower and grape stalks wastes,
sugar beet pulp, olive mill solid residue, sawdust and leaves
have been demonstrated to remove heavy metal ions from
wastewater. Many examples are available in the literature
concerning the direct or activated use of these materials as
adsorbents [2,7–25].
One of these low-cost sorbents particularly suited to
biosorption is sugar beet pulp, a by-product of the sugar-
refining industry, which exhibits a large capacity to bind
metals. This material is very cheap and is mainly used as
animal feed. Sugar beet pulp is a natural polysaccharide and
is composed of 20% and more than 40% of cellulosic and
pectic substances, respectively. The pectic substances,
which account for more than 40% of the dry matter, are
complex heteropolysaccharides containing galacturonic
acid, arabinose, galactose and rhamnose as the major sugar
constituents. Due to the carboxyl functions of galacturonic
acid, pectic substances are known to strongly bind metal
cations in aqueous solution [22–25].
There are some reports of heavy metal biosorption by
sugar beet pulp, but little attention has been paid to the
investigation of temperature dependence of biosorption
process and evaluating equilibrium, kinetic and thermo-
dynamic parameters of the system, which are important in
the design of treatment systems. This paper presents the
study of biosorption characteristics of dried sugar beet pulp
for removing copper(II) from aqueous solutions. The
binding capacity of dried sugar beet pulp for copper(II)
was shown as a function of initial pH, temperature and
initial copper(II) concentration in this study. The biosorp-
tion equilibrium were expressed by the Langmuir,
Freundlich, Redlich–Peterson and Koble–Corrigan adsorp-
tion models and the effect of temperature on the model
constants was investigated. Batch studies were carried out
to identify the rate-controlling steps and determining
external mass transfer and intraparticle diffusion rate
coefficients. Only a limited number of studies have so far
been focused on the kinetic analysis of biosorption of
copper(II) in the literature so the experimental data were
also analyzed using three different adsorption kinetic
models and kinetic constants were calculated depending on
temperature. The activation energy of biosorption process,
which is an indicator of adsorption type, was also evaluated
by using a first-order saturation type kinetic model
constant. Since the evaluation of the heat change of the
biosorption process is very important for reactor design,
the thermodynamics of the adsorption process was also
investigated.
2. Materials and methods
2.1. Adsorbent
In this study, the waste pulp of sugar beet remaining from
extraction of sugar was used as metal biosorbent. The pulp
was obtained from the Ankara Sugar Mill, Turkey. Wet sugar
beet pulp was dried at 100 8C until constant weight,
grounded and sieved.
The adsorbent particle size is an important factor in
adsorption kinetics because it determines the time required
for transport of sorbate within the pore to adsorption sites.
The diffusional resistance to mass transfer is greater for
large particles but, the smallest size allows very fast removal
kinetics if the adsorption is to be primarily a surface
phenomenon. Moreover, increasing the surface area due to
small particle size also increases the number of sites, or
indirectly increases the adsorption capacity, so the
preliminary batch biosorption experiments were carried
out using three different particle sizes of 250, 350 and
500 mm. Since the adsorbent of the particle size 500 mm has
a poor adsorption capacity, the adsorbent of the particle size
250 mm was selected for adsorption studies due to its higher
adsorption capacity.
2.2. Chemicals
Stock solutions of copper(II) were prepared by dissolving
accurately weighed amount of analytical grade
CuSO45H2O (Merck) in 1 l double-distilled water. The
test solutions were prepared by diluting 1 g l
1 of stock
solution of copper(II) to the desired concentrations. The
range of concentrations of prepared copper(II) solutions was
25–250 mg l
1. Before mixing the adsorbent, the pH of each
test solution was adjusted to the required value with diluted
and concentrated H2SO4 and NaOH solutions, respectively.
 Z. Aksu, İ.A. İşoğlu / Process Biochemistry 40 (2005) 3031–3044
Insignificant decreases in the final equilibrium pH were
recorded, so during the uptake pH was assumed constant.
2.3. Adsorption studies
Sorption studies were conducted in a routine manner
using a batch technique. A number of stoppered Pyrex glass
Erlenmeyers containing a definite volume (100 ml in each
case) of solutions of copper(II) of desired concentration, pH
and temperature were placed in a thermostatic rotary shaker.
For the studies, 0.1 g of dried sugar beet pulp was treated
with 100 ml of copper(II) bearing solution at a defined pH
and temperature.
The flasks were agitated at a 150 rpm constant shaking
rate for 24 h to ensure equilibrium was reached. Samples
(5 ml) were taken before mixing the biosorbent and
copper(II) bearing solution and at pre-determined time
intervals and the copper(II) solution was separated from the
biosorbent by centrifugation at 5000 rpm for 5 min. Uptake
values were determined as the difference between the initial
copper(II) concentration and the one in the supernatant. All
the experiments were carried out in duplicates and the
average values were used for further calculations.
2.4. Analysis of copper(II)
The concentration of residual copper(II) in the biosorp-
tion medium was determined spectrophotometrically. 0.2 ml
of 1% (w/v) sodium diethyl dithiocarbamate solution, and
20 ml of 1.5N NH3 solution was added to the sample (1 ml)
containing lower than 60 mg l
1 of copper(II) ions and
diluted to 25 ml with double-distilled water. The absorbance
of the yellow–brown coloured solution was read at 460 nm
[1].
3. Results and discussion
Analysis of biosorption data is important for developing
equilibrium, kinetic and thermodynamic equations that can
be used for design purposes. The equilibrium, kinetic and
thermodynamic results obtained in the biosorption of
copper(II) on to dried sugar beet pulp are given as the
units of adsorbed copper(II) quantity per gram of adsorbent
at any time and at equilibrium [q = (C0
C)/X and
qeq = (C0
Ceq)/X] (q; qeq: mg g
1), respectively, unad-
sorbed copper(II) concentration in solution at any time and
at equilibrium (C; Ceq: mg l
1), respectively, adsorbed
copper(II) concentration in solution at equilibrium (Cad,eq:
mg l
1) and biosorption yield [Ad% = 100  (C0
Ceq)/
C0].
3.1. Effect of initial pH on copper(II) biosorption
pH is an important factor influencing heavy metal
biosorption on agricultural by-products. pH affects not only
3033
the surface charge of the adsorbent, but also the degree of
ionization and speciation of the heavy metal in solution. The
metal cations in aqueous solution convert to different
insoluble hydrolysis products due to pH. The hydrolysis
products of copper(II) are also a function of pH. The
dominant species of copper in the pH range 3–4 are Cu2+ and
CuOH+, while the copper at above 5.0 occurs as insoluble
Cu(OH)2. Fig. 1 indicates the effect of initial solution pH on
the biosorption of copper(II) on dried sugar beet pulp at
100 mg l
1 initial metal ion concentration and at 25 8C.
Copper(II) removal was strongly dependent on pH and
almost constant from pH 2.0 to 3.0 and increased
significantly with further increase in pH. The equilibrium
uptake of copper(II) increased from 10.8 to 24.6 mg g
1
with increasing pH from 2.0 to 4.0. The drastic decrease in
copper biosorption above pH 4.5 was probably due to the
precipitation of copper(II) ions as insoluble Cu(OH)2
precipitate and not due to biosorption.
It was verified that the raw sugar beet pulp is dominated
by negatively charged sites that are largely carboxylate
groups with some weaker acidic groups. The copper(II) ions
are mainly fixed on these acid sites. At low pH, the surface of
biosorbent would also be surrounded by hydronium ions
which decrease the copper interaction with binding sites of
the dried sugar beet pulp by greater repulsive forces. The
smaller biosorption values observed at low pH have been
attributed to the competition between the protons and the
ions released, i.e. sodium(I), phosphorus(III), calcium(II),
etc. by pulp into the solution. At pH 2, most of the potential
fixation sites are protonated and prevent copper(II) ions to be
fixed. Moreover, ion exchange with calcium(II) ions
neutralizing the carboxyl groups of the polysaccharide
may be the other predominant mechanism. As expected, the
capacities of fixation increase with pH. As the pH increased,
the overall surface on the dried sugar beet pulp became
negative and biosorption increased making true sorption
studies impossible. When the pH increases, fixation
Fig. 1. The effect of initial pH on the equilibrium copper(II) sorption
capacity of dried sugar beet pulp (T: 25 8C; C0: 100 mg l
1; X: 1.0 g l
1;
agitation rate: 150 rpm).
3034 Z. Aksu, İ.A. İşoğlu / Process Biochemistry 40 (2005) 3031–3044

capacities are improved due to the lower competition

between the protons and copper(II) ions [22–25].
As a result the working pH value for copper(II)
biosorption was chosen as 4.0 and the other biosorption
experiments were performed at this pH value.

3.2. Effect of temperature on copper(II) biosorption

In most cases, biosorption decreases with increasing

temperature. The equilibrium uptake of copper(II) by dried
sugar beet pulp was also affected by temperature and
decreased notably with increasing temperature up to 45 8C
(Table 1). At 100 mg l
1 initial copper(II) concentration the
equilibrium uptake capacity of sorbent decreased from 24.6
to 12.3 mg copper(II) per gram of adsorbent with increasing
temperature from 25 to 45 8C. Copper(II) biosorption was
exothermic thus the extent of biosorption increased with
decreasing temperature so the sorption of copper(II) by dried
sugar beet pulp may involve mainly physical sorption. The
decrease in biosorption capacity of dried sugar beet pulp at
higher temperature may be attributed to the deactivation of
the adsorbent surface or the destruction of some active sites
on the adsorbent surface due to bond rupture.
3.3. Effect of initial copper(II) concentration on
temperature-dependent copper(II) biosorption
The initial concentration provides an important driving
force to overcome all mass transfer resistance of copper(II)
between the aqueous and solid phases, hence a higher initial
concentration of copper(II) will increase the biosorption
rate. The equilbrium copper(II) uptake values at different
initial metal ion concentrations are given in Table 1 with
respect to temperature. It is clear that the equilibrium
sorption capacity of dried sugar beet pulp for copper(II)
increased with increasing initial copper(II) concentration up
to 250 mg l
1, and decreased with increasing temperature up
to 45 8C. Then, the equilibrium uptake did not change with
further increase in initial metal ion concentration at any of
the temperature studied showing a saturation trend at higher
copper(II) concentrations due to a finite number of surface
binding sites. At 25 8C, when the initial copper(II)
concentration increased from 25.6 to 258.8 mg l
1, the
loading capacity of dried sugar beet pulp increased from
11.8 to 28.5 mg g
1. The temperature also influenced
Fig. 2. The biosorption curves of copper(II) obtained at 100 and 200 mg l
1
initial copper(II) concentrations and at different temperatures (initial pH
4.0; X: 1.0 g l
1; agitation rate: 150 rpm).
equilibrium copper(II) uptake as shown in Table 1. With
the change in temperature from 25 to 45 8C, the uptake
capacity decreased from 28.5 to 16.1 mg g
1 at 250 mg l
1
initial copper(II) concentration. However, the removal
percentage of copper(II) showed an opposite trend and
decreased with increasing initial metal ion concentration.
The biosorption yield of copper(II) decreased from 45.9 to
11.0% at 25 8C with increasing initial copper(II) concentra-
tion from 25.6 to 258.8 mg l
1. In the case of lower
concentrations, the ratio of initial number of metal ions to
the available sorption sites is low and subsequently the
fractional biosorption becomes independent of initial
concentration. At higher concentrations, however, the
available sites of biosorption become fewer and subse-
quently the removal of metals depends on the initial
concentration. As a result, the purification yield can be
increased by diluting the wastewaters containing high metal
ion concentrations.
3.4. Biosorption kinetics
Fig. 2 shows the results of kinetic experiments conducted
to determine the equilibrium time required for the uptake of

Table 1
Effect of initial copper(II) concentration and temperature on the equilibrium uptake capacity and biosorption yield of dried sugar beet pulp
25 8C 35 8C 45 8C

1
1
1
1
C0 (mg l ) qeq (mg g ) Ad% C0 (mg l ) qeq (mg g ) Ad% C0 (mg l
1) qeq (mg g
1) Ad%
25.6 11.8 45.9 26.7 8.8 32.9 25.1 5.3 21.0
52.9 19.6 37.1 48.2 11.9 24.6 49.5 8.8 17.7
106.1 24.6 23.9 100.9 16.7 16.5 104.4 12.3 11.8
153.9 27.6 17.9 143.4 19.7 13.8 150.0 14.5 9.6
198.2 28.1 14..2 212.3 21.1 9.9 205.3 15.8 7.7
258.8 28.5 11.0 258.0 21.2 8.2 252.9 16.1 6.3
 Z. Aksu, İ.A. İşoğlu / Process Biochemistry 40 (2005) 3031–3044
copper(II) ions by the dried sugar beet pulp. The curves at 25,
35 and 45 8C were obtained by plotting the copper(II) uptake
capacity, q, versus time at 100 and 200 mg l
1 initial
copper(II) concentrations. For the given concentrations and
temperatures the amount of copper(II) adsorbed by dried
sugar beet pulp increased linearly with time in the beginning,
then non-linearly at a slower rate and finally attained
saturation called the equlibrium time which was dependent on
time and temperature. The data showed that a contact time
ranging from about 1 to 3 h depending on temperature was
sufficient to achieve equilibrium and biosorption did not
change subsequently up to 24 h (data not shown). For both
initial copper(II) concentrations the biosorption capacity of
dried sugar beet pulp decreased significantly with increasing
temperature. In general, as the concentration of copper(II)
increased, although the time to reach equilibrium did not
change notably, copper(II) removal increased without regard
to temperature. For all initial copper(II) concentrations initial
sorption of copper(II) occurred rapidly and the majority of
copper(II) uptake occurred within the first 30 min (Fig. 2). At
25 8C, 71.3 and 78.4% of total adsorbed amount of copper(II)
was removed by biosorbent in the first 30 min of contact at
100 and 200 mg l
1 initial metal ion concentrations,
respectively. At 35 8C, dried sugar beet pulp adsorbed up
to 74.4 and 83.1% of the total sorbed quantity of copper(II)
within the initial 30 min at the same initial metal ion
concentrations, respectively. At 45 8C, about 85.7 and 88.9%
of the total metal ion sorption was achieved within 30 min at
100 and 200 mg l
1 initial metal ion concentrations,
respectively, with little further biosorption over the next
30 min. The rapid uptake of copper(II) in all cases indicates
that the uptake of metal ion occurs predominantly by surface
binding and that available sites on the biosorbent are the
limiting factor for the biosorption.
3.5. Modelling of biosorption equilibrium depending
on temperature
Equilibrium data, commonly known as adsorption
isotherms, are basic requirements for the design of adsorption
systems. In order to discover the sorption capacity of beet pulp
the experimental data points were fitted to the Freundlich,
Langmuir, Redlich–Peterson and Koble–Corrigan equations
applicable to sorption process. For each isotherm initial
copper(II) concentrations were varied while the adsorbent
weight in each sample was held constant.
The Langmuir equation which is valid for monolayer
sorption onto a completely homogeneous surface with a
finite number of identical sites and with negligible
interaction between adsorbed molecules is given by Eq. (1).
Q0 bCeq
qeq ¼ (1)
1 þ bCeq
where Q0 is the maximum amount of the copper(II) per unit
weight of dried sugar beet pulp to form a complete mono-
3035
layer on the surface bound at high Ceq, and b is a constant
related to the affinity of the binding sites. Q0 represents a
practical limiting biosorption capacity when the surface is
fully covered with copper(II) and assists in the comparison
of biosorption performance, particularly in cases where the
sorbent did not reach its full saturation in experiments [26].
The empirical Freundlich equation based on a monolayer
adsorption by the adsorbent with a heterogeneous energy
distribution of active sites is given below by Eq. (2).
1=n
qeq ¼ KF Ceq (2)
where KF and n are the Freundlich constants characteristic
on the system. KF and n are indicators of biosorption
capacity and biosorption intensity, respectively. The Freun-
dlich isotherm is also more widely used but provides no
information on the monolayer biosorption capacity, in con-
trast to the Langmuir model [27].
The three-parameter Redlich–Peterson equation has been
proposed to improve the fit by the Langmuir or Freundlich
equation and is given by Eq. (3). It has a linear dependence
on concentration in the numerator and an exponential
function in the denominator.
KRP Ceq
qeq ¼ b
(3)
1 þ aRP Ceq
where KRP, aRP and b are the Redlich–Peterson parameters.
b lies between 0 and 1. For b = 1 Eq. (3). converts to the
Langmuir form [28].
Koble–Corrigan model is another three-parameter
empirical model for the representing equilibrium biosorp-
tion data. It is a combination of the Langmuir and Freundlich
isotherm type models and is given by
n
ACeq
qeq ¼ n
(4)
1 þ BCeq
where A, B and n are the Koble–Corrigan parameters. This
model is valid when n > 1 [29].
Fig. 3 shows the experimental isotherm data of copper(II)
on dried sugar beet pulp at three different temperatures. In
the copper(II) concentration range examined, the resulting
isotherms were positive, regular, concave to the concentra-
tion axis, indicating an affinity for biosorption, and showed a
saturation trend at higher copper(II) concentrations;
indicating a complete monolayer of copper(II) covering
the surface of sorbent. The uptake of the metal ions
decreased with an increase in temperature thereby indicating
the process to be exothermic.
The criteria for selection of the most suitable isotherm
model were average percentage error and deviation from
experimental value. The corresponding Langmuir, Freun-
dlich, Redlich–Peterson and Koble–Corrigan parameters at
different temperatures are obtained by non-linear regression
analysis and listed in Table 2 along with the average
percentage errors. The average percentage errors between
the experimental and predicted values are calculated using
3036 Z. Aksu, İ.A. İşoğlu / Process Biochemistry 40 (2005) 3031–3044

temperatures of 25, 35, 45 and 55 8C. Basically, if most of

the data are distributed around the 458 line, this indicates that
the model represent well the experimental data of the system
so as shown in the figure. On this basis, the Langmuir model
could reasonably fit the data well with an average percentage
error in the range 1.82–3.35 suggesting that the monolayer
sorption, mainly due to ion-exchange, would not be
disturbed by lateral interactions between cations sorbed
with similar sorption energies. The other two-parameter
model of Freundlich could fit the equilibrium data with an
average percentage error more than 4.57. In order to further
minimize error and hence to get better representation of data,
Redlich–Peterson and Koble–Corrigan three-parameter
models were tried and compared. Again, Redlich–Peterson
model could fit the data of copper(II) well. Morever, the
Fig. 3. Non-linearized adsorption isotherms (experimental equilibrium Koble–Corrigan model also seemed to agree well with the
data) of copper(II) obtained at 25, 35 and 45 8C (initial pH 4.0; X:
experimental data of copper(II) considering that obtained
1.0 g l
1; agitation rate: 150 rpm).
percentage error values are lower than 8.13% in all cases.
Adsorption model constants, the values of which express
Eq. (5). In Eq. (5), the subscripts ‘exp’ and ‘calc’ show the the surface properties and affinity of the adsorbent, can be
experimental and calculated values and N the number of used to compare the adsorptive capacity of dried sugar beet
measurements. pulp for copper(II).
PN KF, one of the Freundlich constants has been used as a
i¼1 jqeq;i;exp
qeq;i;calc =qeq;i;exp j relative measure of biosorption capacity (KF reaches the
e% ¼  100 (5)
N value of qeq when the equilibrium concentration Ceq
approaches to unity, thus can be considered as an indicative
Fig. 4 depicts the comparison of experimental and parameter of the adsorption strength). n, the other
predicted amounts of copper(II) adsorbed on dried sugar Freundlich constant is related to intensity of biosorption.
beet pulp obtained from these adsorption models at the From Table 2, the magnitude of KF showed a high copper(II)
adsorptive capacity of dried sugar beet pulp from aqueous
Table 2 solution at all temperatures studied and decreased with the
Comparison of the Freundlich, Langmuir, Redlich–Peterson and Koble– rise in temperature. The highest KF value was found as 3.94
Corrigan biosorption constants obtained from the Freundlich, Langmuir, at 25 8C. Table 2 also indicated that n is greater than unity,
Redlich–Peterson and Koble–Corrigan adsorption isotherms of copper(II) at indicating that copper(II) is favourably adsorbed by dried
different temperatures
sugar beet pulp at all the temperatures studied.
Temperature ( 8C) KF [(mg g
1)(mg l
1)
1/n] n e (%) Values of Q0 and b calculated from the Langmuir model
at different temperatures are also tabulated in Table 2. While
Freundlich model the Freundlich model does not describe the saturation
25 3.94 2.41 11.98
behaviour of the biosorbent, Q0, the mono-component
35 3.30 2.32 4.57
45 1.52 2.23 6.86 Langmuir constant represents the monolayer saturation at
equilibrium or the total capacity of the adsorbent for
Temperature ( 8C) Q0 (mg g
1) b (mg g
1) e (%) copper(II). The biosorption capacity of sorbent also
Langmuir model decreased with increasing the temperature. The value of
25 31.4 0.043 1.98 Q0 obtained at 25 8C (i.e. maximum uptake and equal to
35 24.6 0.028 3.35 31.37 mg g
1) appears to be higher in comparison with the
45 19.9 0.019 1.82
uptakes obtained at the other temperatures. The other mono-
Temperature ( 8C) aRP [(l mg
1)b] KRP (l g
1) b e (%) component Langmuir constant b, is related to the free energy
Redlich–Peterson model of biosorption, DG (b / e
DG/RT) and indicates the affinity
25 0.043 1.36 1.000 1.98 for the binding of copper(II). Its value is the reciprocal of the
35 0.035 0.69 0.963 3.17 concentration at which half of the saturation of the adsorbent
45 0.022 0.37 0.973 1.88
is attained (or copper(II) amount of Q0/2 is bound). A high b
Temperature ( 8C) A (ln mg1
n g
1) B (l mg
1)n n e (%) value indicates a high affinity. The higher value of b obtained
Koble–Corrigan model at 25 8C also implied strong bonding of copper(II) to the
25 1.28 0.041 1.025 1.74 dried sugar beet pulp at this temperature.
35 1.92 0.060 0.639 2.75 Related biosorption parameters were also calculated
45 1.24 0.014 0.505 8.13
according to the three-parameter isotherm of Redlich–
 Z. Aksu, İ.A. İşoğlu / Process Biochemistry 40 (2005) 3031–3044
Fig. 4. Comparison of the experimental qeq values with the theoretical qeq values obtained from the Langmuir, Freundlich, Redlich–Peterson and Koble–
Corrigan adsorption models at different temperatures for copper(II) biosorption.
Peterson using non-linear regression method for copper(II)
and are tabulated in Table 2 at different temperatures.
Redlich–Peterson constant KRP indicated that the adsorption
capacity of biosorbent also decreased with increasing
temperature. It is noted that b normally lies between 0
and 1, indicating favourable biosorption.
The corresponding Koble–Corrigan parameters of A, B
and n for different temperatures along with percentage errors
are also given in Table 2. Koble–Corrigan constant A
indicated that the biosorption capacity and affinity of
biosorbent to copper(II) ions also decreased with increasing
temperature.
3.6. Modelling of biosorption kinetics depending on
temperature
Adsorption on an adsorbent from the aqueous phase
involves three steps: (1) the transport of the adsorbate from
the bulk phase to the exterior surface of the adsorbent (film
diffusion); (2) the transport into the adsorbent by either pore
diffusion and/or surface diffusion (intraparticular diffusion);
and (3) the adsorption on the surface of the adsorbent. The
slowest of these steps determines the overall rate of the
adsorption process. When removing copper(II) from
aqueous solution by dried sugar beet pulp, these steps are
possible. Sorption kinetics show a large dependence on the
physical and/or chemical characteristics of the sorbent
material which also influences the sorption mechanism. In
order to investigate the mechanism of sorption and potential
3037
rate-controlling steps such as external mass transfer,
intraparticle diffusion and adsorption processes and also
for design purposes, mass transfer and kinetic models have
been used to test the experimental data and attempts were
made to calculate the coefficients of these models.
In the first step of adsorption, the film diffusion is an
important rate-controlling step. The change of copper(II)
concentration with respect to time can be written as follows:
dC
¼
kL AðC
CS Þ (6)
dt
where C is the bulk liquid phase concentration of copper(II)
at a time t, CS the surface concentration of copper(II), kL the
external mass transfer coefficient and A the specific surface
area for mass transfer. It is assumed that during the initial
stages of adsorption, the intraparticle resistance is negligible
and the transport is mainly due to film diffusion mechanism.
At t = 0 the surface concentration of copper(II), CS, is
negligible and C = C0. With these assumptions Eq. (6)
can be simplified as
 
dðC=C0 Þ
¼
kL A (7)
dt
Since it was not possible to determine the specific surface
area A, due to the poor porosity of particles, it is
approximated as the external surface area. Assuming the
adsorbent particles are spherical, A is calculated from Eq. (8)
as 0.2575 cm
1.
3038 Z. Aksu, İ.A. İşoğlu / Process Biochemistry 40 (2005) 3031–3044
6X
A¼ (8)
dp r p
where X is the sorbent mass concentration in the solution, dp
average particle diameter and rp the density of the sorbent.
By plotting C/C0 against t, the value of kL may be deter-
mined from the slope at t = 0 [30–33].
External mass transfer is characterized by the initial rate
of solute diffusion for the system studied. The effect of
initial copper(II) concentration and temperature on the
external diffusion rate was given by a plot of C/C0 versus
time for 100 and 200 mg l
1 initial copper(II) concentra-
tions and at 25, 35 and 45 8C temperature values (Fig. 5). It
was seen that the concentration of copper(II) falls very fast
during the initial uptake before intraparticular diffusion
could begin to control the adsorption kinetics for all cases.
The kinetic data presented in the figure were fitted to Eq. (7)
for the initial uptake phase and the external mass transfer
coefficients were determined from the slopes as t
0 and
presented in Table 3. The results show that both the
increasings in initial copper(II) concentration and tempera-
ture resulted in a decrease in the initial rate, respectively. It is
clear that, as expected, external mass transfer resistance
cannot be neglected even for a high agitation speed, although
this resistance is only significant for the initial period of
biosorption time. Weber and Morris [30] have concluded
that, for processes which are controlled by external
diffusion, the initial rate will be directly proportional to
the solute concentration. The non-proportionality shown in
Fig. 6, therefore, indicates that external mass transfer is not
the rate-controlling step.
Fig. 5. C/C0 vs. t plots obtained at 100 and 200 mg l
1 initial copper(II)
concentrations and at different temperatures (initial pH 4.0; X: 1.0 g l
1;
agitation rate: 150 rpm).
Fig. 6. Variation of kL with C0 with respect to temperature.
In the model developed by Weber and Morris [30], the
rate of intraparticular diffusion is a function of t0.5 and can be
defined as follows:
!0:5
Dt
q¼ f 2 ¼ Kt0:5 (9)
rp
where rp is particle radius, D is the effective diffusivity of
solutes within the particle, and K is intraparticular diffusion
rate constant. If intraparticle diffusion occurs, then q versus
t0.5 will be linear and if the plot of q versus t0.5 passes
through the origin, then the rate-limiting process is only due
to the intraparticle diffusion. Otherwise, some other
mechanism along with intraparticle diffusion is also
involved. If such types of plots present a multi-linearity,
imply that two or more steps occur. The first, sharper portion
is the external surface adsorption stage. The second linear
portion is the gradual adsorption stage, where the intrapar-
ticle diffusion is rate-limited. The third portion is final
equilibrium stage where the intraparticle diffusion starts
to slow down due to extremely low solute concentration
in the solution and surface. A good correlation of rate data in
this model can justify the mechanism and K values can be
obtained by linearizing the curve q = f(t0.5) [30–33].
Fig. 7 shows the effect of initial copper(II) concentration
and temperature on intraparticular diffusion at 100 and
200 mg l
1 initial copper(II) concentrations and at 25, 35
and 45 8C temperatures. As seen from the figure all the plots
have the same general feature. They all have an initial curved
portion, followed by an intermediate linear portion and a
plateau. The initial portion of these plots which extent is
related to initial copper(II) concentration is due to external
mass transfer and the intermediate linear part is due to
intraparticle diffusion. At a certain time limit (between 5 and
60 min at all initial copper(II) concentrations and at all
temperatures studied) the curves revealed a linear char-
acteristic. The values of K evaluated from these linear parts
of q versus t0.5 plots are also tabulated in Table 3. These are
rate parameters with units mg g
1 min
0.5 and as such, are
 Z. Aksu, İ.A. İşoğlu / Process Biochemistry 40 (2005) 3031–3044 3039

Table 3
Effect of initial copper(II) concentration and temperature on the external mass transfer coefficients (kL) and intraparticle diffusion rate constants (K)
25 8C 35 8C 45 8C
2 2
C0 kL  10 K C0 kL  10 K C0 kL  102 K
(mg l
1) (cm min
1) (mg g
1 min
0.5) (mg l
1) (cm min
1) (mg g
1 min
0.5) (mg l
1) (cm min
1) (mg g
1 min
0.5)
25.6 17.7 1.99 26.7 11.8 1.44 25.1 7.0 0.83
52.9 12.7 2.76 48.2 8.0 1.89 49.5 5.9 1.23
106.1 7.3 3.54 100.9 4.9 2.65 104.4 4.1 1.96
153.9 6.3 4.04 143.4 4.1 3.10 150.0 3.4 2.40
198.2 5.3 4.26 212.3 3.5 3.45 205.3 2.8 2.72
258.8 4.1 4.38 258.0 3.1 3.52 252.9 2.2 2.84

not a direct quantification of the rates. Nevertheless, they can
be interpreted in relative terms. Examined in this way, the
data show the rate of diffusion increased with a raise in
initial copper(II) concentration and decreased with increas-
ing temperature of solution. This may be due to a greater
driving force with increasing C0. At all temperatures when
C0 is increased from 25 to 200 mg l
1 there is a marked
effect on the rate of intraparticular copper(II) diffusion.
Above C0 200 mg l
1 the effect is small. It is also observed
that the higher the value of K the more rapid is the uptake of
copper(II). The linear plots at each concentration and
temperature did not pass through the origin and this
indicated that the intraparticle diffusion is not only rate-
controlling step. Moreover, according to the theoretical
equations for diffusion, when intraparticle diffusion is the
only rate-determining step, the rate parameter is also directly
related to the square root of the initial concentration (C00:5 ).
Such a plot given in Fig. 8 also confirmed that intraparticle
diffusion is not the only operative mechanism [30]. These
two results show that increasing the copper(II) concentration
in the solution seems to reduce the diffusion of metal ions in
the boundary layer and to enhance the diffusion in the solid.
On the other hand the biosorption kinetics may be
described by pseudo first-order [34], pseudo second-order
[35] and saturation type kinetic models [36,37]. These three
models basically include all steps of adsorption such as
external film diffusion, adsorption, and internal particle
diffusion, so they are pseudo-models.
The pseudo first-order rate expression based on solid
capacity is generally expressed as follows:
dq
¼ k1;ad ðqeq
qÞ (10)
dt
where k1,ad is the rate constant of first-order biosorption.
After integration and applying boundary conditions, t = 0 to
t and q = 0 to qeq; the integrated form of Eq. (10) becomes:
k1;ad
logðqeq
qÞ ¼ logqeq
t (11)
2:303
A straight line of log(qeq
q) versus t suggests the
applicability of this kinetic model. In order to fit Eq. (11) to
experimental data, the equilibrium sorption capacity, qeq,
must be known. In many cases qeq is unknown and as
biosorption tends to become unmeasurably slow, the amount
sorbed is still significantly smaller than the equilibrium
amount. For this reason, it is necessary to obtain the real

Fig. 7. q vs. t0.5 plots obtained at 100 and 200 mg l
1 initial copper(II)
concentrations and at different temperatures (initial pH 4.0; X: 1.0 g l
1;
agitation rate: 150 rpm). Fig. 8. Variation of K with C00:5 with respect to temperature.
3040 Z. Aksu, İ.A. İşoğlu / Process Biochemistry 40 (2005) 3031–3044
Fig. 9. Variation of rad with C0 with respect to temperature.
equilibrium sorption capacity, qeq, by extrapolating the
experimental data to t = 1 or by using a trial and error
method. Furthermore, in most cases the first-order kinetic
model does not fit well for the whole range of contact time
and is generally applicable over the initial 20–30 min of the
sorption process.
The pseudo second-order equation is also based on the
sorption capacity of the solid phase and is expressed as:
dq
¼ k2;ad ðqeq
qÞ2
dt
where k2,ad is the rate constant of second-order biosorption.
For the same boundary conditions the integrated form of
Eq. (12) becomes
t 1 1 temperature. As seen from the table, besides very high
¼ 2
þ t
q k2;ad qeq qeq
If second-order kinetics are applicable, the plot of t/q
against t of Eq. (13) should give a linear relationship, from
which qeq and k2,ad can be determined from the slope and
intercept of the plot and there is no need to know any
parameter beforehand.
The plot of q versus time can be used to find the initial
biosorption rate (rad) by differentiating the plot at t = 0 as
defined in Eq. (14).
 are also presented in Table 4. The results indicated that
dq
¼ rad (14)
dt t¼0
From experimental data, it was shown that the initial
biosorption rate is proportional to the first power of the
initial copper(II) concentration at lower bulk copper(II)
concentrations (first-order kinetics) and at higher copper(II)
concentrations, the rate becomes independent of initial
copper(II) concentration (zero-order kinetics) (Fig. 9).
Eq. (15) can be used to describe the rate of biosorption
very accurately in both situations. This kind of rate equation
is also defined as ‘saturation type’.
kad C0
rad ¼ 0 C (15)
1 þ kad 0
where kad is the first-order rate constant of saturation type
0
biosorption. The expression of kad/kad defines the zero-order
rate constant (k0,ad). A straight line of 1/rad versus 1/C0
suggests the applicability of this kinetic model and kad and
k0,ad can be determined from the slope and intercept of the
plot. This model predicts the biosorption behaviour over the
whole studied concentration range of copper(II) at a constant
temperature.
The first-order rate constant of the saturation type
biosorption reaction (kad) is expressed as a function of
temperature by the following Arrhenius type relationship:
 

EA
kad ¼ A0 exp (16)
RT
where A0 is the frequency factor, EA is the activation energy
of sorption, R is the gas constant and T is the solution
temperature. When ln kad is plotted versus 1/T, a straight
line with slope
EA/R is obtained. The magnitude of
activation energy may give an idea about the type of sorp-
tion.
The validity of all models can be checked from the linear
plots.
The first-order rate constant (k1,ad) and qeq values were
(12) determined from the plots of linearized form of the pseudo
first-order model at all concentrations and at all temperatures
studied for the initial 30 min (data not shown) and are
presented in Table 4 along with the correlation coefficients.
The first-order rate constants decreased slightly with
increasing both the initial concentration of copper(II) and
(13)
regression coefficients (>0.992), experimental qeq values
agreed very well with qeq values obtained from Lagergren
plots. This indicated that pseudo first-order kinetic model
describes the kinetics adequately in the studied concentra-
tion and temperature range.
Using Eq. (13), t/q was plotted against t at 25, 35 and
45 8C, and second-order adsorption rate constants (k2,ad) and
equilibrium uptake values (qeq) were determined from the
slope and intercept of the plots (data not shown). The values
of the parameters k2,ad and qeq and of correlation coefficients
second-order rate constants were also affected by both the
initial copper(II) concentration and temperature and
diminished with increasing these parameters. The correla-
tion coefficients of all temperatures and concentrations
studied were also found very high in this case. Moreover, the
theoretical qeq values found from the second-order kinetic
model also agreed very well with the experimental qeq
values. This showed that the adsorption of copper(II) also
follows the pseudo-second-order kinetic model.
The saturation type kinetic model was also applied to the
experimental data at different temperatures changing from
25 to 45 8C to describe the batch biosorption kinetics. The
 Z. Aksu, İ.A. İşoğlu / Process Biochemistry 40 (2005) 3031–3044 3041

Table 4
Comparison of the first- and second-order reaction rate constants and experimental and calculated qeq values obtained at different initial copper(II)
concentrations and temperatures
Temperature (8C) C0 (mg l
1) qeq,exp (mg g
1) First-order kinetic model Second-order kinetic model
k1,ad  102 (min
1) qeq,cal (mg g
1) R2 k2,ad  103 (g mg
1 min
1) qeq,cal (mg g
1) R2
25 25.6 11.8 7.09 11.8 1.000 66.61 11.8 1.000
52.9 19.6 5.90 19.5 1.000 44.86 19.7 1.000
106.1 24.6 5.09 24.3 1.000 34.10 24.7 1.000
153.9 27.6 4.72 27.4 1.000 21.45 27.7 1.000
198.2 28.1 4.35 27.2 0.996 15.85 28.3 1.000
258.8 28.5 3.96 27.1 0.996 15.12 28.7 1.000
35 26.7 8.8 6.86 8.9 1.000 42.87 8.8 1.000
48.2 11.9 5.23 11.8 1.000 32.39 12.0 1.000
100.9 16.7 4.35 16.5 1.000 25.49 16.8 1.000
143.4 19.7 3.82 19.5 1.000 19.16 19.8 1.000
212.3 21.1 2.92 21.1 1.000 11.46 21.1 1.000
258.0 21.2 2.35 20.6 0.992 11.28 21.0 1.000
45 25.1 5.3 6.13 5.3 1.000 28.59 5.3 1.000
49.5 8.8 4.95 8.8 1.000 22.80 7.3 1.000
104.4 12.3 3.98 12.3 1.000 17.25 12.3 1.000
150.0 14.5 3.02 14.4 1.000 14.17 14.5 1.000
205.3 15.8 2.46 15.7 1.000 9.21 15.8 1.000
252.9 16.1 2.10 15.3 0.998 9.05 16.0 1.000

values of kad and k0,ad were determined from the plots of
linearized form of the saturation type kinetic model at all
temperatures studied (data not shown). The plots indicated
that such saturation type kinetic expression is not so valid to
the present system (R2 < 0.982 for all temperatures).
However, the values of kad and k0,ad at 25, 35 and 45 8C
are still listed in Table 5 for reference. Table 5 shows that
both the biosorption rate constants were affected with
increase in temperature and decreased notably with
increasing temperature.
These suggest that the biosorption of copper(II) at 25, 35
and 45 8C is not a saturation type reaction and may be best
described by the pseudo first- and second-order kinetic
models with fairly high correlation coefficients. The change
of rate constant due to temperature also showed that one of
the rate-controlling steps is biosorption reaction. Applying
the Weber and Morris principles to the variation in the initial
rate with C0 (Fig. 9) indicated that the rate was not directly
proportional to C0 and also confirmed that sorption process
was not the only rate-limiting step. The data also confirmed
that both mass transfer and pore diffusion are important in
determining the biosorption rates and that their relative
significance depends on the initial copper(II) concentration
and temperature.
The activation energy for the biosorption system of
copper(II) onto dried sugar beet pulp was found as

58.47 kJ mol
1 from the slope of ln kad against 1/T linear
plot with a correlation coefficient of 0.939 in the temperature
range studied (data not shown). Since negative value of
activation energy have no obvious physical significance, the
biosorption study of this metal ion should be performed at
much more lower solution temperatures to obtain biosorp-
tion activation energy.
3.7. Thermodynamic parameters of biosorption
The thermodynamic parameters reflect the feasibility and
spontaneous nature of the process. Thermodynamic para-
meters such as free energy change, enthalpy change and
entropy change can be estimated using equilibrium
constants changing with temperature. The biosorption
process of copper(II) can be summarized by the following
reversible process which represents a heterogeneous
equilibrium.
copperðIIÞin solution $ copperðIIÞ-biosorbent (17)
The apparent equilibrium constant (KC0 ) of the biosorp-
tion is defined as:

Table 5 Cad;eq
Comparison of the saturation type kinetic rate constants obtained at
KC0 ¼ (18)
Ceq
different temperatures
Temperature ( 8C) kad  102 k0ad  102 R2 where Cad,eq is the concentration of copper(II) on the
(l g
1 min
1) (l mg
1) biosorbent at equilibrium. In this case the activity should
25 4.35 2.32 0.982 be used instead of concentration in order to obtain the
35 2.61 1.87 0.951 standard thermodynamic equilibrium constant (KC0 ) of the
45 1.39 1.16 0.972 biosorption system. If infinite dilute value of KC0 can be
3042 Z. Aksu, İ.A. İşoğlu / Process Biochemistry 40 (2005) 3031–3044
found by calculating the apparent equilibrium constant (KC0 )
at different initial concentrations of copper(II) and extra-
polating to zero, this value will give KC0 . When 1 g l
1 of
adsorbent is used, this value can be taken equal to the
opposite value of intercept of Ceq/qeq versus Ceq plot
(=bQ0), which shows the linearized form of Langmuir
equation. The Kc0 value is used in the following equation
to determine the free energy change of the biosorption
reaction (Gibbs free energy) (DG8) at 25 8C.
DG
¼
RT ln KC0 (19)
where R the universal gas constant and T the absolute
temperature. The free energy change indicates the degree
of spontaneity of the biosorption process and the higher
negative value reflects a more energetically favourable
adsorption. The equilibrium constant may be expressed in
terms of enthalpy change of biosorption (DH8) and entropy
change of biosorption (DS8) as a function of temperature.
The relationship between the KC0 and temperature is given by
the van’t Hoff equation:
DS
DH
The comparison of results of this work with the others
lnKC0 ¼
(20)
R RT
DH8 and DS8 can be obtained from the slope and intercept of
a van’t Hoff plot of ln KC0 versus 1/T.
The KC0 value at 25 8C evaluated from the Cad,eq/Ceq versus
Ceq plot (data not shown) as 1.35 was used to find the DG8
value. The standard Gibbs free energy for the biosorption
process was obtained as
0.74 kJ mol
1 using Eq. (19). A
negative value of DG8 confirms the feasibility of the process
and spontaneous nature of biosorption at 25 8C. The standard
enthalpy and entropy changes of biosorption determined from
the ln KC0 versus 1/T plot (R2 = 0.976) were
66.3 kJ mol
1
and
0.22 kJ mol
1 K
1, respectively. The negative value of
DH8 indicates an exothermic biosorption reaction while
negative DS8 confirms the decreased randomness at the solid–
solution interface during biosorption.
3.8. Comparison of results with the literature
The copper(II) adsorption capacity of dried sugar beet
pulp was compared to the adsorption capacities of some
other adsorbents reported in literature. Differences of metal
uptake are due to the properties of each adsorbent such as
structure, functional groups and surface area.
Namasivayam and Kadirvelu [10] examined the adsorp-
tion of copper(II) by coirpith carbon and found a
39.7 mg g
1 copper(II) uptake capacity. Sun and Shi [12]
used the sunflower stalks as an adsorbent for the removal of
heavy metal ions and found a 29.3 mg g
1 uptake capacity
for copper(II). Gupta and Ali [14] studied with the bagasse
fly ash for the biosorption of copper(II); the biosorption
capacity of sorbent was only 2.26 mg g
1 at 30 8C and at
optimum pH of 4.0. Yu et al. [14] indicated that sawdust has
a distinctly lower uptake capacity for copper(II)
(1.8 mg g
1). Ho and McKay [3] used peat for the
biosorption of copper(II) and they found that at 200 mg l
1
1 initial copper(II) concentration 14.3 mg copper(II) was
adsorbed per gram of sorbent. Pagnanelli et al. [17] tested
olive mill solid residue for copper(II) adsorption and found
13.5 mg g
1 uptake capacity at pH 5.0. Ho [19] reported the
biosorption capacity of tree fern for copper(II) as
10.6 mg g
1. Basci et al. [20] observed that wheat shell
adsorbed copper(II) from aqueous solutions to a maximum
of approximately 10.8 mg g
1. Villaescusa et al. [21] also
studied the sorption of this metal ion by grape stalks wastes
achieving an uptake of 10.1 mg g
1 dry mass. Ozer et al. [7]
investigated the biosorption of copper(II) on dehydrated
wheat bran. At 100 mg l
1 initial copper(II) concentration
and at 1 g l
1 biosorbent concentration they found the
biosorption capacity of sorbent as 51.5 mg g
1 at an
optimum pH value of 5.0 and at 60 8C. Dronnet et al.
[22] and Gerente et al. [23] used washed and activated sugar
beet pulp and they found that 21.1 and 17.1 mg copper(II)
was adsorbed per gram of sorbent, respectively, at 20 8C and
at pH 4.0.
found in the literature showed that copper(II) uptakes found
in this work were similar to those obtained using sunflower
stalks wastes and washed sugar beet pulp and much more
higher than the reported ones by the other referred wastes
except that coirpith carbon and dehydrated wheat bran.
4. Conclusions
In this work, dried sugar beet pulp has been used
successfully as an adsorbing agent for the removal of
copper(II) ions from aqueous solutions. Adsorption was
influenced by various parameters such as initial pH,
temperature and initial copper(II) concentration. The
maximum uptake of copper(II) by dried sugar beet pulp
occurred at an initial pH of 4.0 and adsorption increased with
increasing copper(II) concentration up to 250 mg l
1 and
decreased with temperature. The maximum copper(II)
uptake capacity of biosorbent was 28.5 mg g
1; this value
is comparable to other sorbent media tested for copper(II)
biosorption.
The Freundlich, Langmuir, Redlich–Peterson and Koble–
Corrigan adsorption models were used for the mathematical
description of the adsorption equilibrium of copper(II) on to
dried sugar beet pulp depending on temperature and the
isotherm constants evaluated from the isotherms were used
to compare the adsorptive capacity of the dried sugar beet
pulp. The biosorption of copper(II) on to dried sugar beet
pulp was found to exhibit non-linear favorable biosorption
behaviour that could be characterized well by the Langmuir,
Redlich–Peterson and Koble–Corrigan isotherm models in
the studied concentration range at all the temperatures
studied. Assuming the batch adsorption as a single-staged
equilibrium operation, the separation process can be
 Z. Aksu, İ.A. İşoğlu / Process Biochemistry 40 (2005) 3031–3044
mathematically defined using these isotherm constants to
estimate the residual concentration of copper(II) or amount
of adsorbent for desired purification.
The adsorption process rate and dynamic behaviour of
the system are very important factors for the process
design and operation control. The rate of diffusion may be
valid in many realistic situations. Three simplified models
including pseudo first-order, pseudo second-order and
saturation type kinetic models were used to test the
adsorption kinetics. It was shown that the adsorption of
copper(II) on to dried sugar beet pulp could be best fitted
by the pseudo first- and second-order models. A film
diffusion model and an intraparticle diffusion model
developed by Weber and Morris were used to find both the
boundary and intraparticle diffusion rate constants. The
sorption data indicated that the mechanism of copper(II)
biosorption by dried sugar beet pulp is rather complex and
is probably a combination of external mass transfer,
intraparticle diffusion and sorption process. The obtained
kinetic parameters can be used for reactor design. It may
be suitable to apply such simple kinetic models to a well-
agitated batch biosorption system.
Thermodynamic constants were also evaluated using
equilibrium constants changing with temperature. The
negative value of DG8 indicated the spontaneity and the
negative values of DH8 and DS8 showed the exothermic
nature and increase in order of copper(II) biosorption,
respectively.
We believe that application of biosorption by dried sugar
beet pulp in purification of wastewater for the removal of
copper(II) from industrial wastewaters can be suitable for
the fabrication and designing of wastewater treatment plants
by using these kinetic parameters. Since sugar beet pulp, an
agricultural solid waste, used in this investigation, is freely,
abundantly and locally available, the sorbent is expected to
be economically viable for wastewater treatment.
Appendix A
aRP Redlich–Peterson adsorption constant [(l mg
1)b]
A Koble–Corrigan adsorption constant (ln mg1
n g
1)
A0 frequency factor
b Langmuir adsorption constant (l mg
1)
B Koble–Corrigan adsorption constant (l mg
1)n
C residual copper(II) concentration at any time
(mg l
1)
C0 initial copper(II) concentration (mg l
1)
Cad,eq adsorbed copper(II) concentration at equilibrium
(mg l
1)
Ceq residual copper(II) concentration at equilibrium
(mg l
1)
dp particle diameter (cm)
EA activation energy of sorption (kJ mol
1)
DG8 The Gibbs free energy of biosorption (kJ mol
1)
DH8 Enthalpy change of biosorption (kJ mol
1)
3043
k, k0 rate constants of saturation type adsorption
(l g
1 min
1; l mg
1)
k1 first-order rate constant (min
1)
k2 second-order rate constant (g mg
1 min
1)
kL external mass transfer coefficient (cm min
1)
K intraparticular diffusion rate (mg g
1 min
0.5)
KC0 standard thermodynamic equilibrium constant of
the adsorption system
KC0 apparent equilibrium constant of the biosorption
system
KF Freundlich adsorption constant [(mg g
1)
(mg l
1)n]
KRP Redlich–Peterson adsorption constant (l g
1)
n Freundlich and Koble–Corrigan adsorption con-
stants
q adsorbed copper(II) quantity per gram of dried sugar
beet pulp at any time (mg g
1)
qeq adsorbed copper(II) quantity per gram of dried sugar
beet pulp at equilibrium (mg g
1)
Q0 Langmuir adsorption constant (mg g
1)
rad initial adsorption rate (mg g
1 min
1)
R gas constant (=8.314 J mol
1 K
1)
R2 correlation coefficient
DS8 Entropy change of biosorption (kJ mol
1)
T solution temperature (8C, K)
X dried sugar beet pulp concentration (g l
1)
Greek letters
b Redlich–Peterson biosorption constant
rp particle density (g ml
1)
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