Journal of Colloid and Interface Science 288 (2005) 371–376

www.elsevier.com/locate/jcis

Removal of dyes from colored textile wastewater by orange peel

adsorbent: Equilibrium and kinetic studies
Mokhtar Arami a,b,∗ , Nargess Yousefi Limaee a , Niyaz Mohammad Mahmoodi a ,
Nooshin Salman Tabrizi a
a Environmental Science and Engineering Department, Iran Color Research Center, Tehran, Iran
b Textile Engineering Department, Tehran Polytechnic University, Tehran, Iran

Received 5 January 2005; accepted 10 March 2005

Available online 28 April 2005

Abstract
The use of low-cost and ecofriendly adsorbents has been investigated as an ideal alternative to the current expensive methods of removing
dyes from wastewater. Orange peel was collected from the fields of orange trees in the north of Iran and converted into a low-cost adsorbent.
This paper deals with the removal of textile dyes from aqueous solutions by orange peel. Direct Red 23 (DR23) and Direct Red 80 (DR80)
were used as model compounds. The adsorption capacity Q0 was 10.72 and 21.05 mg/g at initial pH 2. The effects of initial dye concentration
(50, 75, 100, 125 mg/l), pH, mixing rate, contact time, and quantity of orange peel have been studied at 25 ◦ C. The Langmuir and Freundlich
models were used for this study. It was found that the experimental results show that the Langmuir equation fit better than the Freundlich
equation. The results indicate that acidic pH supported the adsorption of both dyes on the adsorbent. Orange peel with concentrations of
8 and 4 g/l has shown adsorption efficiencies of about 92 and 91% for DR23 and DR80, respectively. Furthermore, adsorption kinetics of
both dyes was studied and the rates of sorption were found to conform to pseudo-second-order kinetics with a good correlation (R
0.998).
Maximum desorption of 97.7% for DR23 and 93% for DR80 were achieved in aqueous solution at pH 2. Finally, the effect of adsorbent
surface was analyzed by scanning electron microscope (SEM). SEM images showed reasonable agreement with adsorption measurements.
 2005 Published by Elsevier Inc.

Keywords: Orange peel; Adsorption; Desorption; Isotherms; SEM

1. Introduction
Dyes are used in many industries, such as food, paper,
carpet, rubber, plastics, cosmetics, and textile, in order to
color their products [1–3]. The discharge of colored waste-
water from these industries into natural streams has caused
many significant problems, such as increasing the toxicity
and COD (chemical oxygen demand) of the effluent, and
also reducing the light penetration, which has a derogatory
effect on photosynthetic phenomenon. From the aesthetic
point of view, the presence of dyes, in particular carcino-
genic compounds, in surface and underground waters is not
safe, pleasant, or welcomed. Recently, all governments have
* Corresponding author. Fax: +98 2535206.
E-mail address: mokhtar_arami@yahoo.com (M. Arami).
0021-9797/$ – see front matter  2005 Published by Elsevier Inc.
doi:10.1016/j.jcis.2005.03.020
been under severe pressure by their people to stop this type
of effluent to the public watercourses, unless it is treated
properly. So the removal of color from waste effluents has
become environmentally important [4,5]. The USEPA (En-
vironmental Protection Agency) has classified textile wastes
into four groups, dispersible, hard-to-treat, high-volume,
and hazardous and toxic wastes [6]. Many physicochemi-
cal methods have been tested but only that of adsorption
is considered to be superior to other techniques. This is
attributed to its low cost, easy availability, simplicity of de-
sign, high efficiency, ease of operation, biodegradability, and
ability to treat dyes in more concentrated form [4,7,8]. Ac-
tivated carbons are widely used as adsorbents because of
their high adsorption abilities for a large number of organic
compounds. However, the price of activated carbons is rel-
atively high, which limits their usage [9,10]. As a result,
372 M. Arami et al. / Journal of Colloid and Interface Science 288 (2005) 371–376
Fig. 1. Chemical structure of DR23.
Fig. 2. Chemical structure of DR80.
many researchers have investigated low-cost, biodegradable
substitutes made from natural resources to remove organic
contaminants such as dyes from wastewater. In this study,
orange peel was used as an adsorbent to remove two dyes,
DR23 and DR80, from aqueous solution. Effective para-
meters such as adsorbent dosage, dye concentration, pH,
kinetics, and isotherm studies were conducted to evaluate
the adsorption capacity of orange peel.
2. Materials and methods
2.1. Chemicals and materials
Orange peel was obtained from a local fruit field in the
north of Iran. The peels were first washed to remove the ad-
hering dirt and then were dried, crushed, and sieved. They
were dried at room temperature (25 ◦ C) for 36 h. After dry-
ing, they were sieved through a 3.36-mm mesh. Direct dyes
used in this study were DR23 and DR80. The dyes were pur-
chased from Ciba Ltd. The chemical structures of these dyes
are shown in Figs. 1 and 2. Other chemicals were Analar
grade from Merck. The pH of the solutions was adjusted by
adding a small amount of 2 M H2 SO4 or NaOH. A CECIL
2021 UV–vis spectrophotometer was used to determine the
dye uptake.
2.2. Adsorption procedure
The adsorption measurements were conducted by mixing
various amounts of orange peel (0.5–2 g) for DR23 and (0.2–
1 g) for DR80 in jars containing 250 ml of a dye solution
(50 mg/l) at various pHs (2–10). pH studies were conducted
to determine the optimum pH at which maximum color re-
moval could be achieved with orange peel for each of the
two dyes. Experiments were carried out at concentrations
of 25, 50, 75, 100, and 125 mg/l using 2 g adsorbent for
DR23 and 1 g adsorbent for DR80 at pH 2 and 25 ◦ C for
24 h to attain equilibrium conditions. The changes of ab-
sorbance were determined at certain time intervals (15, 30,
45, 60, 120, 180, 240, 300, 360, 420, 480, and 1440 min)
during the adsorption process. Equilibrium was established
after 15 min. Different agitation rates were applied and there
was no significant difference between stirring rates of 30–
200 rpm. After experiments, the samples were centrifuged
by Hettich EBA20 and then the dye concentration was de-
termined. The results were fitted to the Langmuir adsorption
isotherm with correlation coefficients of 0.9762 and 0.9997
for DR23 and DR80, respectively.
2.3. SEM studies
The surface images of orange peel before and after ad-
sorption process were captured by scanning electron mi-
croscopy (SEM). The SEM used was a Philips XL30. The
experiments were conducted with 250 ml dye solutions
(DR23 and DR80) with concentration of 50 mg/l at pH 2.
To this solutions, 2 and 1 g orange peel was added for DR23
and DR80, respectively, and mixed for a period of 15 and
1440 min. After the mixing, the orange peel powders were
separated from the solutions by filtration using Whatman
No. 42 filter paper and dried for 1440 min at 50 ◦ C. Then
the orange peel samples were visually examined by SEM.
2.4. Desorption studies
The adsorbent that was used for the adsorption of 50 mg/l
of dye solution was separated from the solution by centrifu-
gation. After separation of the adsorbent, it was agitated with
250 ml of distilled water at different pH values (2–12) for the
predetermined equilibrium time of the adsorption process.
The desorbed dye was estimated as before.
3. Results and discussion
3.1. Adsorption studies
The adsorption efficiencies of DR23 and DR80 dyes on
orange peel were evaluated by determining the percentage
decrease of the absorbance at 505 and 540 nm, respectively,
 M. Arami et al. / Journal of Colloid and Interface Science 288 (2005) 371–376
using the equation [11]


A0 − A
Dye removal (%) = × 100,
A0
where A0 is the initial absorbance and A is the final ab-
sorbance of the dye solution.
The effects of initial concentration of both dyes on the
percentage of dye removal were studied. Quantities of 2 and
1 g of adsorbent were added to 250 ml of DR23 and DR80
solutions, respectively, at concentrations of 50, 75, 100, and
125 mg/l. Fig. 3 illustrates that 92% of DR23 was removed
with an initial concentration of 50 mg/l, 89% at 75 mg/l,
83% at 100 mg/l, and 76% at 125 mg/l. Fig. 4 shows that
91% of DR80 was removed with an initial concentration
of 50 mg/l, 83% at 75 mg/l, 82% at 100 mg/l, and 67%
at 125 mg/l. These experiments were performed at pH 2.
For both dyes, the equilibrium capacity decreased with an
increase in the initial concentrations as shown in Figs. 3
and 4.
Fig. 3. The effect of time and concentration on DR23 removal in orange
peel. Conditions: pH 2, T 25 ◦ C, S 200 rpm, ms = 8 g/l.
Fig. 4. The effect of time and concentration on DR80 removal in orange
peel. Conditions: pH 2, T 25 ◦ C, S 200 rpm, ms = 4 g/l.
373
3.2. Adsorption isotherms
Adsorption is the accumulation of a mass transfer process
(1)
that can generally be defined as material at the interface
between solid and liquid phases. Equilibrium relationships
between sorbent and sorbate are described by sorption
isotherms, usually the ratio between the quantity sorbed and
that remaining in the solution at a fixed temperature at equi-
librium. Isotherm data should accurately fit into different
isotherm models to find a suitable model that can be used
for the design process [12].
Langmuir and Freundlich isotherm equations were tested
in this work. The Langmuir equation can be written
Q0 KL Ce
qe = , (2)
1 + KL Ce
where q e is the amount of dye adsorbed on the orange peel
at equilibrium, C e is the equilibrium concentration of dye
solution, K L is the equilibrium constant, and Q0 is the max-
imum adsorption capacity. This equation has been success-
fully applied to many adsorption processes [13–19]. The
applicability of the Langmuir isotherm suggests the mono-
layer coverage of the dye on the surface of the orange peel.
The essential characteristic of the Langmuir isotherm can be
expressed by the dimensionless constant called the equilib-
rium parameter, R L , defined by
RL = 1/(1 + KL C0 ), (3)
where K L is the Langmuir constant, C0 is the initial dye
concentration (mg/l), and R L values indicate the type of
isotherm to be irreversible (RL = 0), favorable (0 < RL < 1),
linear (RL = 1), or unfavorable (RL > 1) [20]. It has been
found that the adsorption of DR23 and DR80 dyes on the or-
ange peel is favorable and has an R L value between 0 and 1
(Table 1).
Also, isotherm data was studied with the Freundlich
isotherm, which can be expressed by [5,21,22]
qe = KF Ce ,
1/n
(4)
where K F is the adsorption capacity at unit concentration
and 1/n is the adsorption intensity.
The equilibrium isotherm for the adsorption of DR23 and
DR80 dyes on orange peel was determined with 250 ml of
dye solution (50 mg/l). The systems were agitated for 24 h
(200 rpm) in a constant temperature at pH 2. Fig. 5 shows
the adsorption isotherms of dyes (q e versus C e ) using orange
peel. The Q0 , K L , r12 (correlation coefficient for Langmuir
isotherm), K F , n, and r22 (correlation coefficient for Fre-
undlich isotherm) are given in Table 1.
Table 1
Linearized isotherm coefficients for dyes
Dye Q0 KL RL r12 KF n r22
DR23 10.718 0.308 0.0609 0.9762 4.431 4.189 0.8896
DR80 21.052 0.429 0.0445 0.9997 9.384 4.16 0.9549
374 M. Arami et al. / Journal of Colloid and Interface Science 288 (2005) 371–376

Table 2
The effect of initial pH of dye solutions on the maximum absorbance wave-
length (λmax (nm)) of DR23 and DR80
pH λmax (nm)
DR23 DR80
2 505 540
4 503 536
6 503 537
8 504 537
10 505 536
12 506 538

tant role in dye adsorption on orange peel. At pH 2, a high

Fig. 5. Adsorption isotherms of dyes using orange peel. Conditions:
C0 = 50 mg/l, pH 2, T 25 ◦ C, S 200 rpm.
electrostatic attraction exists between the positively charged
surface of the adsorbent and the anionic dye. As the pH of
the system increases, the number of negatively charged sites
increases. A negatively charged surface site on the adsorbent
does not favor the adsorption of dye anions due to the elec-
trostatic repulsion [23,24]. Also, lower adsorption of DR23
and DR80 at alkaline pH is due to the presence of excess
OH− ions competing with the dye anions for the adsorp-
tion sites. The effective pH was 2 and it was used in further
studies. A similar trend was observed for adsorption of Acid
Yellow 36 on sawdust carbon and rice-husk carbon [5] and
Congo Red on activated carbon [23].

3.4. SEM studies

Before and after the orange peel was allowed to adsorb

Fig. 6. Effect of pH on the adsorption of dyes on orange peel. Conditions:
C0 = 50 mg/l, pH 2, T 25 ◦ C, S 200 rpm, ms = 8 g/l (DR23) and 4 g/l
(DR80).
the dyes, the SEM images were taken and analyzed (Fig. 7).
Based on analysis of the images taken by SEM before and
after the adsorption process, highly heterogeneous pores
within orange peel particles were observed. After adsorp-
tion, the pores were packed with dyes.

3.3. Effect of pH 3.5. Adsorption kinetics

The final dye concentration after adsorption varied signif- Kinetic data were analyzed with the Lagergren and Ho
icantly with the initial pH of the dye solution. The studies in equations [25]. A linear form of pseudo-first-order model
this report were carried out at a broad pH range of 2–10. The was described by Lagergren,
effect of pH on the adsorption of DR23 and DR80 dyes by K1
orange peel is shown in Fig. 6. The maximum dye adsorp- log(q1 − qt ) = log(q1 ) − t, (5)
2.303
tion occurred at pH 2; corresponding adsorption capacity
for DR23 and DR80 was 10.72 and 21.05 mg/g, respec- where q1 is the amount of dye adsorbed at equilibrium
tively. (mg/g), qt is the amount of dye adsorbed at time t (mg/g),
The results of blank studies indicated that the initial pH of and K1 is the equilibrium rate constant of pseudo-first-order
dye solutions has a negligible effect on the chemistry of both adsorption (min−1 ).
dyes. The maximum absorbance wavelength (λmax (nm)) of Also, a linear form of pseudo-second-order model
DR23 and DR80 at different pH values is shown in Table 2. (Eq. (6)), the Ho equation, is illustrated in Fig. 8,
DR23 and DR80 dyes are polar molecules (R-SO− 3 ) at t 1 1
low pH. Orange peel is composed of various functional = 2
+ t, (6)
qt Kqe qe
groups, such as amino and carboxyl, which could also be
affected by the pH of solutions. Therefore, the electrosta- where q e is amount of dye adsorbed at equilibrium (mg/g)
tic attraction, as well as the organic properties and structure and K2 is the pseudo-second-order equilibrium rate constant
of dye molecules and orange peel, could play a very impor- (g/mg min).
 M. Arami et al. / Journal of Colloid and Interface Science 288 (2005) 371–376 375

(a)

(b) (c)

(d) (e)

Fig. 7. SEM images for orange peel: (a) original orange peel; (b) after 15 min adsorption process (DR23); (c) after 1440 min adsorption process (DR23);
(d) after 15 min adsorption process (DR80); (e) after 1440 min adsorption process (DR80).

Table 3 3.6. Desorption studies

Kinetics constants for pseudo-first- and pseudo-second-order model
Dye K1 r32 K2 r42
Desorption studies help to elucidate the mechanism and
DR23 0.103 0.5827 0.374 0.998 recovery of the adsorbate and adsorbent. As the desorbing
DR80 0.066 0.2854 0.201 0.9996
pH was increased, the percent desorption increased from
37.5% (pH 2) to 97.7% (pH 12) for DR23 and from 2.2%
The values of K1 , K2 , r32 (correlation coefficient for (pH 2) to 93% (pH 12) for DR80 at dye concentration of
pseudo-first-order sorption kinetics), and r42 (correlation co- 50 mg/l (Fig. 9). As the pH of the system increases, the
efficient for pseudo-second-order sorption kinetics) were number of negatively charged sites increased. A negatively
calculated and are shown in Table 3. charged surface site on the adsorbent favors the desorption
376 M. Arami et al. / Journal of Colloid and Interface Science 288 (2005) 371–376
Fig. 8. Pseudo-second-order sorption kinetics of dyes on orange peel. Con-
ditions: C0 = 50 mg/l, pH 2, T 25 ◦ C, S 200 rpm, ms = 8 g/l (DR23) and
4 g/l (DR80).
Fig. 9. Effect of pH on desorption of dyes on orange peel. Conditions: pH 2,
T 25 ◦ C, S 200 rpm, ms = 8 g/l (DR23) and 4 g/l (DR80).
of dye anions due to the electrostatic repulsion. At pH 12, a
significantly high electrostatic repulsion exists between the
negatively charged surface of the adsorbent and anionic dye.
4. Conclusion
The results of this investigation show that orange peel
has a suitable adsorption capacity for the removal of DR23
and DR80 from aqueous solutions. The experimental results
were analyzed by using the Langmuir and Freundlich mod-
els and the correlation coefficients for Langmuir equation
fitted better than Freundlich equation. The initial equilibrium
time of adsorption was about 15 min at 25 ◦ C and pH 2 for
all concentrations of these dyes. The kinetic studies of two
dyes on orange peel were performed based on pseudo-first-
and pseudo-second-order rate mechanisms. The data indi-
cate that the adsorption kinetics of each dye on the orange
peel follow the pseudo-second-order rate expression. The
rapid adsorption kinetics of dyes on the orange peel suggests
a continuous flow process for the treatment of colored textile
wastewater. Desorption studies were conducted to elucidate
the mechanism and recovery of the adsorbate and adsorbent.
At alkaline pH a high electrostatic repulsion exists between
the negatively charged surface of the adsorbent and the an-
ionic dye.
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