Materials Today: Proceedings 22 (2020) 134–139

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Adsorption of Congo red dye from aqueous solutions using tunics of the
corm of the saffron
Abdellah Dbik ⇑, Safae Bentahar, Mohammed El Khomri, Noureddine El Messaoudi, Abdellah Lacherai
Ibn Zohr University, Faculty of Science, Department of Chemistry, Laboratory of Applied Chemistry and Environment, BP 8106, 80000 Agadir, Morocco

a r t i c l e i n f o a b s t r a c t

Article history: Adsorption of Congo red (CR) from aqueous solution using tunics of the corm of the saffron was studied.
Received 24 June 2019 Experimental results obtained showed that adsorption process was highly dependent on mass of adsor-
Accepted 9 August 2019 bent, contact time, initial dye concentration and temperature. The sorption equilibrium for Congo red dye
Available online 29 August 2019
by tunics of the corm of the saffron was reached within 60 min and adsorption efficiency of up to 68%
achieved. The sorption kinetics followed a pseudo-second-order kinetic model while Langmuir isotherm
Keywords: model was best applicable for obtaining the equilibrium parameters. These results demonstrate that
Saffron
tunics of the corm of the saffron are effective, environmentally friendly and low cost biomaterial for
Adsorption
Congo red
dye removal from aqueous dye solutions.
Kinetics Ó 2019 Elsevier Ltd. All rights reserved.
Anionic dye Selection and peer-review under responsibility of the scientific committee of the International Congress:
Applied Materials for the Environment CIMAE-2018.

1. Introduction
Synthetic dyestuffs are widely used in textile, paper, printing,
and cosmetic industries. Dyeing effluent has a serious environmen-
tal impact because disposal of such effluent into the receiving
water body causes damage to aquatic biota or humans by muta-
genic and carcinogenic effects [1]. Conventional treatment meth-
ods for removal of pollutants from aqueous solution, like
coagulation and flocculation [2], membrane separation [3], acti-
vated carbon adsorption [4] electrochemical removal [5], photo-
chemical degradation [6], biological degradation [7], and
adsorption [8] have been investigated with varying degree of
success.
Adsorption techniques have potential for removing organics
from water due to their high efficiency and ability to separate a
wide range of chemical compounds [9]. The most widely used
adsorbent is activated carbon [10], but its initial cost and the need
for a costly regeneration system make it less economically viable
as an adsorbent. This has led many researchers to search for cost
effective and efficient alternative materials such as date stone
[11], graphene oxide [12] and clay [13].
⇑ Corresponding author.
E-mail addresses: abdellah.dbik@edu.uiz.ac.ma (A. Dbik), safae.bentahar@edu.
uiz.ac.ma (S. Bentahar), mohammed.elkhomri@edu.uiz.ac.ma (M. El Khomri),
noureddine.elmessaoudi@edu.uiz.ac.ma (N. El Messaoudi), a.lacherai@uiz.ac.ma
(A. Lacherai).
In this research, the efficiency of the tunics of the corm of the
saffron (Crocus sativus L.) in adsorption of Congo red dye from
aqueous solution has been investigated. Batch experiments were
carried out for sorption kinetics and isotherms. Langmuir and Fre-
undlich isotherm model were used to analyze the experimental
data. The sorption kinetics was analyzed by pseudo-second-order
kinetic model. Effluent containing Congo red is largely produced
from textiles, printing, dyeing, paper, and plastic industries [14].
Congo red is toxic to many organisms and is a suspected
carcinogen and mutagen. This study explores the possibility of
utilizing tunics of the corm of the saffron as low cost biomaterials
for the adsorptive removal of Congo red dye from polluted
wastewater.
2. Materials and methods
2.1. Material
The tunics of the corm of the saffron (Crocus sativus L) (Fig. 1)
were collected from Taliouine (Morocco) region and extensively
washed with tap water to remove water soluble impurities and
other foreign particles. The biomass were dried in the sun for
two days, ground into fine material and then washed several times
with distilled water before drying in an oven at 90 °C for 24 h.
Stock solutions of the test reagents were made by dissolving Congo
red, in distilled water. The structure of this dye is shown in Fig. 2.

https://doi.org/10.1016/j.matpr.2019.08.148
2214-7853/Ó 2019 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the International Congress: Applied Materials for the Environment CIMAE-2018.
 A. Dbik et al. / Materials Today: Proceedings 22 (2020) 134–139
Fig. 1. The corm of the saffron.
Fig. 2. The structure of Congo red.
2.2. Batch adsorption experiment
The adsorption experiments were conducted in 100 mL conical
flask on a magnetic shaker. All experiments were conducted in
duplicate and the average values reported. The effect of initial
dye concentration was performed by varying the initial Congo
red concentrations from 50 to 500 mg L
1. Tunics of the corm of
the saffron were added to 50 mL volume of Congo red solution.
After different interval times, aliquots from the reaction mixture
were analyzed for residual (CR) concentration using a spectropho-
tometer Ultraviolet–Visible double beam ‘‘UV-2005” at the 498 nm
wavelength determined before. The effect of contact time was
investigated using 0.5 g of tunics of saffron corm, and 50 mL Congo
red solution mixed in 100 mL flask. The adsorbent dose was inves-
tigated using 100 mg L
1 initial Congo red concentration with sor-
bent masses by varying from 80 to 2000 mg. The amount of dye
adsorbed at equilibrium onto the tunics of saffron corm was calcu-
lated by the following mass balance relationship:
ðC 0
C eq Þ
Q ads ¼ V
m ture above 500 °C may correspond to basic salt (Na2CO3) and ashes.
a b
Fig. 3. (a) and (b) Scanning electron microscopy of tunics of the corm of the saffron.
135
where Co and Ceq are the initial and the equilibrium dye concentra-
tions (mg L
1), V is the volume of solution (L) and m is the amount
of biomass used (mg). Percent dye removal (%) was calculated using
the following equation;
ðC 0
C eq Þ
Rð%Þ ¼  100 ð2Þ
C0
3. Results and discussion
3.1. Scanning electron microscopy (SEM)
Scanning electron microscope (SEM) was used to determine the
surface morphology and the local composition of our adsorbent.
SEM micrographs for samples were obtained with a SUPRA 40 VP
COLONNE GEMINI ZEISS using a maximum voltage of 20 kV; it
shows the presence of the elongated fibers and vessels which con-
tain the fibers. These forms would be very interesting for adsorp-
tion because of the amount of cavities and pores observed (see
Fig. 3).
3.2. The point of zero load pH
The pH point zero charges (pHzpc) corresponds to the pH value
at which the net charge of the adsorbing surface is zero. A quick
and easy way to determine this is to use the pH drift method
[15] of placing 50 mL of NaCl solution (0.01 M) in sealed vials
and adjust the pH of each of (values between 2 and10) by adding
NaOH or HCl solution (0, 1 M). I then added to each flask, 90 mg
of the support. The suspensions are kept in agitation at room tem-
perature for 48 h, and the final pH is then determined.
In Fig. 4, I plot the evolution the difference between the initial
and final pH adjusted according to initial pH. The point of intersec-
tion between the curve obtained and the abscissa axis corresponds
to pHzpc of our material. It is 5.8.
3.3. Thermal stability
The curves of TGA and DTA were carried out to investigate ther-
mal decomposition behavior of tunics of the corm of the saffron, as
shown in Fig. 5.
I observed first loss of mass which usually corresponds to the
surface water from 105 °C. The second loss from 200 to 330 °C,
which corresponds to thermal degradation of cellulose [16], is
exothermic. The third exothermic loss between 330 and 380 °C,
corresponds to degradation of hemicelluloses [16]. The fourth loss
between 380 °C and 500 °C, which corresponds to decomposition
ð1Þ of lignin [17], it is also exothermic. The rest mass at the tempera-
136 A. Dbik et al. / Materials Today: Proceedings 22 (2020) 134–139

3.5. Effect of the mass

The influence of the mass was studied at the pH of the solution

without adjustment, at room temperature, at a concentration of
100 mg L
1 of CR and with the mass between 50 and 1500 mg of
tunics of the corm of the saffron for 60 min (see Fig. 7).
The curve of the figure shows that a mass of 0.5 g of tunics of
the corm of the saffron is capable to fix a maximum of Congo red
of the order of 68%. The increase in the percentage of adsorption
to this mass can be explained by the increase in the number of
active sites added by the tunics. The percentage of adsorption
remains constant which can be explained by the saturation of all
the active sites.
Fig. 4. The pH point zero charges.

3.6. Effect of initial dye pH

The influence of effect of solution pH was studied at room tem-

perature, at a concentration of 100 mg L
1 of CR, at a mass of 0.5 g
of tunics of the corm of the saffron, and with the pH between 3 and
10 for 60 min, as shown in Fig. 8.
There are several investigations of the effect of solution pH on
CR adsorption. However, there is no unique conclusion and the
results seem to contradict each other. In the present work, the
maximum adsorption of CR was recorded at pH 10. The dye
adsorption was nearly constant over the pH range of 4–10, and
the equilibrium adsorption was between 5.6 and 5.83 mg g
1.
The results obtained show that the variation of the residual con-
centration of Congo red is relatively small. The discoloration is
Fig. 5. TGA and DTA.
therefore little influenced by the pH.

3.4. Effect of contact time 3.7. Effect of temperature on the adsorption

This study aims to determine the time value from which the The influence of initial CR concentration at different tempera-
adsorption reaction reaches equilibrium. For this reason, the influ- ture on CR adsorption was investigated at 50–500 mg L
1 with
ence of the time was studied at the pH of the solution without
adjustment, at room temperature, at a concentration of 100 mg L
1
of CR and with a mass of 100 mg of tunics of the corm of the saf-
fron. The effect of the time was studied by varying the time
between 10 and 230 min (see Fig. 6).
The results show that adsorption process reached equilibrium
within 60 min and percentage dye removal increased with increase
in contact time. The high removal rate at the start of the contact
time was due to the large amount of surface area available for
adsorption of the dye during the initial stage and the capacity of
the adsorbent became gradually exhausted with time since the
few remaining vacant surface sites became difficult to be occupied
due to repulsive forces between the solute molecules on the solid
and bulk phases. Similar results have been previously reported in
the literature for dye removal [14].
Fig. 7. Effect of mass on the adsorption performance.

Fig. 6. Effect of contact time on adsorption. Fig. 8. Effect of pH of the solution on adsorption.
 A. Dbik et al. / Materials Today: Proceedings 22 (2020) 134–139 137

where K2 (g mg
1 min
1) is the constant of the pseudo-second-

order rate.
Table 1 lists the results of kinetic parameters of both models. As
can be seen, the values of R2 (0.9998) for the pseudo-second order
kinetic model were higher than that of the pseudo-first order
kinetic mode. In addition, the calculated value of adsorption capac-
ity, qe (6.66 mg g
1) is matched well with the experimental ones
(see Table 2).

3.9. Adsorption isotherms

In order to determine the applicability of adsorption as a means

Fig. 9. Effect of concentration and temperature on the adsorption.
the initial dye solution pH at different temperature 22, 30, 40 and
50 °C for 60 min.
According to bibliographic searches, the adsorption process is
highly dependent on the initial concentration of the dye [18]. As
shown in Fig. 9, for the temperature 21 °C with increasing initial
CR concentration from 50 to 500 mg L
1, the amount of dye
adsorbed by tunics of the corm of the saffron increases sharply
from 3.3 to 5 mg g
1. It can be ascribed that an increase in adsor-
bate concentration leads to an increase in mass gradient between
the aqueous and solid phases, which acts as a driving force for
the transfer of dye molecules from bulk solution to the particle sur-
face [19]. Regarding the effect of temperature, it is evident that the
adsorption capacity increased with increase in the temperature
from 21 to 60 °C. This could be attributed to the increasing temper-
ature may lead to create a swelling effect inside the internal struc-
ture of adsorbent, penetrating the big Congo red molecule further
[20].
3.8. Study of adsorption kinetic
I applied two kinetic models, pseudo first order [21], and
pseudo second order [22]. The linearized pseudo-first order and
pseudo-second order kinetic equations were:
K1
logðqe
qt Þ ¼ logðqe Þ
t ð3Þ
2:303
where k1 (min
1) is the constant of pseudo-first gear.
The equation of the second order kinetic model of the form:
t
¼
1 1
þ t
qt K 2 q2e qe
of removing CR dye from aqueous solutions using the tunics of the
corm of the saffron, Langmuir and Freundlich isotherms models
were used. Langmuir isotherm model [23] assumes that the
adsorptions occur at specific homogeneous sites on the adsorbent
and is used successfully in many monolayer adsorption processes.
The nonlinear and linearized forms of Langmuir isotherm equation
is as follows:
Ce 1 Ce
¼ þ ð5Þ
qe qm K L qm
where KL (L mg
1) is the Langmuir constant and qm (mg g
1) is the
maximum amount of adsorbate retained on the support used. The
essential characteristics of the Langmuir isotherm can be expressed
in terms of an equilibrium dimensionless parameter (RL), which is
defined by:
1
RL ¼ ð6Þ
1 þ K LC0
C0 is the initial concentration of the adsorbate (mg L
1).
The Freundlich isotherm is used based on the assumption that
the sorption process has been implicated in a heterogeneous layer
[13]. The linearized form Freundlich equation is (see Fig. 10 and
Fig. 11):
1
lnqe ¼ lnK F þ ln C e ð7Þ
n
Where KF (mg g
1) is the Freundlich constant and 1/n is the inten-
sity of adsorption.
Analysis of the correlation coefficients obtained for these iso-
therms showed that the Langmuir isotherm describes better the
adsorption with respect to the Freundlich isotherm with a maxi-
ð4Þ mum capacity of monolayer adsorption of 6.2 mg g
1 of Congo
red at room temperature, the favorable adsorption because the RL
balance setting is always between 0 and 1.

Table 1
Kinetic parameters for the adsorption. 3.10. Comparison of different biosorbent low cost

Pseudo first-order kinetic model

The maximum adsorption capacity (qm) for the removal of CR
qe cal [mg g
1] K1 [g mg
1 min
1] R2 onto Tunics of the corm of the saffron as well as the other adsor-
4.22 0.033 0.9911 bents reported in the literature are listed in Table 3.
According to the herein obtained (qm) in comparison to the
Pseudo second-order kinetic model other reported adsorbents of CR it can be revealed that this new
qe cal [mg g
1] K2 [g mg
1 min
1] R2 biomass is an effective adsorbent within the eliminating of CR from
6.66 0.015 0.9999 aqueous solutions, being as alternative about removing the CR dye
from industrial wastewaters. The importance of the present study

Table 2
The characteristic parameters of adsorption models.

Langmuir Freundlich
KL qm RL R2 KF 1/n R2
0.1646 6.2 0.012–0.11 0.9985 2.454 0.165 0.737
138 A. Dbik et al. / Materials Today: Proceedings 22 (2020) 134–139

a. b.

Fig. 10. (a) Pseudo-first-order model and (b) Pseudo-second-order model.

a. b.

Fig. 11. (a) Langmuir adsorption isotherm and (b) Freundlich adsorption isotherm.

Table 3 kinetics with high correlation coefficient (R2 = 0.99) for all studied
Comparison of maximum monolayer biosorption capacity of Congo red by some concentrations. Consequently, it can be concluded that the tunics
biosorbents. of the corm of the saffron can be used as a cost effective alternative
Biosorbent qm [mg .g
1] Reference material for CR dye removal in wastewater treatment processes
without any laborious pre-treatment.
Kaolin 5.94 [24]
Roots of Eichhornia crassipes 5.28 [14]
Tea Waste 23.26 [25]
Tunics of the corm of the saffron 6.2 This study
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