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Biosorption of Congo red dye by Aspergillus carbonarius M333 and

Penicillium glabrum Pg1: Kinetics, equilibrium and thermodynamic
studies
Hadj Daoud Bouras a,b,∗, Ahmed Réda Yeddou a,c, Noureddine Bouras d,e, Djamila Hellel b,f,
Michael D. Holtz g, Nasserdine Sabaou d, Abdelmalek Chergui a,h, Boubekeur Nadjemi a
a
Laboratoire d’Etude et de Développement des Techniques de Traitement et d’Epuration des Eaux et de Gestion Environnementale (LEDTEGE), Ecole Normale
Supérieure de Kouba, Vieux-Kouba, BP 92, 16308 Alger, Algeria
b
Département de Physique, Ecole Normale Supérieure de Laghouat, BP 4033, RP Rue des martyrs, Laghouat, Algeria
c
Département de Génie de l’Environnement, Université de Boumerdès, Avenue de l’Indépendance, 35000 Boumerdès, Algeria
d
Laboratoire de Biologie des Systèmes Microbiens (LBSM), Ecole Normale Supérieure de Kouba, Vieux-Kouba, BP 92, 16308 Alger, Algeria
e
Département de Biologie, Faculté des Sciences de la Nature et de la Vie et Sciences de la Terre, Université de Ghardaïa, BP 455, Ghardaïa 47000, Algeria
f
Laboratoire de Synthèse Organique et Biocatalyse (LSBO), Faculté des Sciences, Université Badji Mokhtar, Annaba, Algeria
g
Field Crop Development Centre, Alberta Agriculture and Forestry, 5030 – 50 Street, Lacombe, Alberta T4L1W8, Canada
h
Département Génie de l’Environnement, Ecole Nationale Polytechnique, 10 Avenue Hassen Badi, BP 182, El Harrach, Alger, Algeria

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

Article history: The biosorption of the anionic dye Congo red from aqueous solution onto the novel biosorbents As-
Received 6 February 2017 pergillus carbonarius and Penicillium glabrum was studied. Optimum sorption conditions were identified by
Revised 31 July 2017
varying solution pH, initial dye concentration, contact time and temperature. The obtained results showed
Accepted 1 August 2017
that BET surface area of Penicillium glabrum biosorbent (6.31 m2 /g) was larger than that of Aspergillus car-
Available online xxx
bonarius biomass (5.07 m2 /g). The microstructures of the fungi were observed with scanning electron
Keywords: micrographs. Chemical characterization of both micro-fungi was carried out by Fourier Transform In-
Aspergillus carbonarius frared Spectroscopy (FT-IR). The biosorption data have been analyzed using Langmuir, Freundlich, Temkin,
Penicillium glabrum Dubinin-Radushkevich and Sips isotherms. Based on R2 , the equilibrium sorption data was better fitted
Congo red to Langmuir isotherm model than any other model. The biosorption processes conformed to the pseudo-
Biosorption second-order rate kinetics. Maximum biosorption capacity was found to be 99.01 mg/g for Aspergillus car-
Kinetics
bonarius and 101.01 mg/g for Penicillium glabrum at pH 4.5, 0.33 g/L sorbent dosage, 180 min contact time
Thermodynamic study
and 303 K for dye initial concentration of 50 mg/L. Thermodynamic parameters of the biosorption (G°,
H° and S°) were also determined and it was found that the biosorption of dye by Aspergillus carbonar-
ius and Penicillium glabrum was a spontaneous process and endothermic in nature.
© 2017 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction annually [2]. Recently, a number of studies have highlighted the

For many years, contamination of water sources with synthetic
dyes by many industries has become a major environmental prob-
lem. Dye-containing wastewater discharged from several industrial
activities is a serious threat to the water bodies around indus-
trial areas, because these toxic, organic or synthetic, dyes can af-
fect plant life and thus destroy natural ecosystems [1]. More than
10 0,0 0 0 dyes are synthesized with 70 0,0 0 0 metric tons produced
∗
Corresponding author at: Laboratoire d’Etude et de Développement des Tech-
niques de Traitement et d’Epuration des Eaux et de Gestion Environnementale
(LEDTEGE), Ecole Normale Supérieure de Kouba, Vieux-Kouba, BP 92, 16308 Alger,
Algeria.
E-mail address: hajdaoud_bouras@yahoo.fr (H.D. Bouras).
toxicity (cytotoxic, genotoxic and mutagenic) of textile dye and
wastewater [3]. These colored textile effluents have untreated dyes
and their derivatives which not only contaminate the ecosystem
but also harm human and aquatic health [4]. Consequently, re-
moval of dyes from such wastewaters is an important environmen-
tal problem and complete dye removal is needed because dyes are
visible even at low concentration [5]. The methods used for dye
removal include chemical, physical and biological processes [6].
Chemical methods, such as electrochemical and catalytic oxidation,
are not used on a large scale because of their complicated opera-
tion, difficult subsequent disposal and high cost [7,8]. Conventional
biodegradation is ineffective for complete removal of many reac-
tive dyes due to complex aromatic structures in the dyes molec-
ular structure [9]. Currently, biosorption is regarded as one of the

http://dx.doi.org/10.1016/j.jtice.2017.08.002
1876-1070/© 2017 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Please cite this article as: H.D. Bouras et al., Biosorption of Congo red dye by Aspergillus carbonarius M333 and Penicillium glabrum
Pg1: Kinetics, equilibrium and thermodynamic studies, Journal of the Taiwan Institute of Chemical Engineers (2017),
http://dx.doi.org/10.1016/j.jtice.2017.08.002
JID: JTICE
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2 H.D. Bouras et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2017) 1–9
most popular and attractive technologies in terms of operation and
cost [10–14]. Low-cost and effective biomaterials used for dye re-
moval from wastewater have been of great interest for many en-
vironmental research programs [15,16]. Previous studies on biosor-
bents focused mainly on inactivated microorganisms which are not
affected by dye toxicity [17]. Several studies have been undertaken
to evaluate the adsorption capacities of bacteria, algae, fungi and
seaweeds as adsorbents [18]. Moreover, dead biomass has several
advantages compared with live biomass, as there is no need to pro-
vide nutrients [19]. Fungal mass can be used as a cheap source
of biosorbent as the amino, carboxyl, thiol and phosphate groups
present in the fungal cell wall are capable of binding dye molecules
[20]. Many different types of fungal materials have been used as
biosorbents for the removal of dye from polluted water, includ-
ing both macro- and micro-fungi, such as Trametes versicolor [21],
Ganoderma applanatum [22], Funalia trogii [23], Rhizopus stolonifera
[24] Aspergillus flavus [25], Aspergillus niger [26], Penicillium fel-
lutinum (composite with bentonite) [18].
In this study, the new fungal materials were chosen as biosor-
bent as it is natural, easily available, and thus a low-cost biomass
for the removal of dye from wastewater. Congo red (CR) dye has
been widely used in many industries [27–29]. Consequently, this
work aimed to optimize the biosorption of this azo dye by the
novel biosorbents Aspergillus carbonarius and Penicillium glabrum in
batch systems.
The effects of pH, temperature and contact time on biosorption
capacity were investigated. Biosorption kinetics were evaluated, us-
ing the pseudo-first order, pseudo-second order and intraparticle
diffusion models. Scanning electron microscopy (SEM) and Fourier
Transform Infrared Spectroscopy (FT-IR) were used to compare the
biosorption behavior of dye.
2. Materials and methods
2.1. Microorganisms (micro-fungi)
The biomass used in this study came from two filamentous
micro-fungi (molds): Aspergillus carbonarius M333 (AC) and Penicil-
lium glabrum Pg1 (PG). Both fungi were obtained from the fungal
collection of BioSym (Département Bioprocédés et Systèmes Micro-
biens), Université de Toulouse (France).
2.2. Preparation of inoculum (fungal spores)
Aspergillus carbonarius (AC) and Penicillium glabrum (PG) were
cultivated in Petri dishes containing 20 mL of PDA (Potato Dex-
trose Agar) medium. The pH of the medium was adjusted to 6.8–
7.0 before autoclaving at 120 °C for 20 min. After 7 days of incu-
bation at room temperature (25 ± 2 °C), the fungal colonies were
harvested. A suspension of spores was prepared in sterile distilled
water containing 0.1% Tween (Tween 80, Fisher). A Thoma chamber
was used to determine final spore concentration (approximately
106 spores/mL). Before use, fungal spores were carefully washed
with ultrapure water to remove any contaminants or inhibitors of
spore germination. Stock cultures were maintained at −18 °C in
25% glycerol.
2.3. Culture conditions
60 μL of the fungal spores were used to inoculate 250 mL Erlen-
meyer flasks containing 100 mL of liquid Sabouraud medium (10 g
sucrose, 7 g peptone in 1 L of distilled water). Prior to inoculation,
the pH of the medium was adjusted to 6.8–7.0 and autoclaved at
120 °C for 20 min. After 19 days of incubation (without shaking) at
room temperature (25 ± 2 °C), the mycelial biomass was harvested.
Please cite this article as: H.D. Bouras et al., Biosorption of Congo red dye by Aspergillus carbonarius M333 and Penicillium glabrum
Pg1: Kinetics, equilibrium and thermodynamic studies,
http://dx.doi.org/10.1016/j.jtice.2017.08.002
[m5G;August 31, 2017;15:42]
2.4. Preparation of the dead biomass
Both A. carbonarius, (AC) and P. glabrum (PG), were harvested
for biomass from the liquid growth medium, thoroughly washed
with ultrapure water and then oven-dried at 80 ± 5 °C for 24 h.
For the biosorption studies, the dried biomass was sieved through
ASTM standard size S (S ≤ 500 μm) sieves: to obtain AC and PG
biosorbent. The powdered biosorbent was finally stored at −18 °C
in an airtight container until use.
2.5. Dye solution preparation
The dye used in this study was Congo red (C.I.22120, FW =
696.7, λmax = 500 nm), an anionic disazo direct dye. CR was ob-
tained from Sigma Aldrich with 99.99% purity. The chemical struc-
ture of the dye is given in Fig. 1. A stock solution of concentra-
tion 100 mg/L was prepared in ultrapure water; other concentra-
tions were obtained by successive dilutions.
2.6. Batch biosorption studies
The batch biosorption studies were carried out at different
parameters such as pH (1.5–6.5), initial dye concentration (25–
125 mg/L), contact time (0–240 min), and temperature (293, 298
and 303 K) at pH 4.5. Biosorption experiments were conducted
in batch systems by adding 10 mg of powder of AC and PG into
glass tubes containing 30 mL of dye solution at the desired concen-
trations. The mixtures were shaken at 30 °C (303 K) and 250 rpm
on a rotary shaker (New Brunswick Scientific Company, New Jer-
sey, USA) to reach equilibrium, unless otherwise stated. After each
biosorption process, the dye solution was separated from the
biosorbent by centrifugation (Microlitre Centrifuges, Heraeus in-
struments, Biofuge) at 16,0 0 0 g (12,0 0 0 rpm) for 10 min. The super-
natants were taken and dye uptake was determined using a UV–vis
spectrophotometer (JENWAYUV–vis 6705) by monitoring the ab-
sorbance at wavelength of 500 nm. The amounts of CR taken up
by the unit weight of biosorbent qt (mg/g) were obtained by the
following Eq. (1).
(C0 − Ct ) V
qt = (1)
m
Where qt is the amount of CR adsorbed by AC and PG (mg/g), C0 is
the initial dye concentration put in contact with AC and PG (mg/L),
Ct is the dye concentration (mg/L) after the adsorption procedure
at the predetermined time t, m is AC and PG mass (g) and V is the
volume of the dye solution (L).
For adsorption isotherms determination, CR solutions of differ-
ent concentrations (25–125 mg/L) at pH 4.5 were agitated with
10 mg of AC and PG until the equilibrium was achieved. The equi-
librium adsorption capacities qe (mg/g) at different solute concen-
trations of CR adsorbed by AC and PG were calculated according to
Eq. (2).
(C0 − Ce ) V
qe = (2)
m
Where C0 and Ce are the initial and equilibrium concentrations of
CR, respectively (mg/L). V is the volume of CR solution (L) and m
is the mass of adsorbent used (g).
2.7. Characterization of the biosorbent
The surface area, pore volume and pore diameter of AC and PG
were measured by Brunauer–Emmett–Teller (BET) (Micromeritics
ASAP-2020). The points of zero charge (pHpzc ) of the two adsor-
bents were determined by mass titration as suggested by Wang
et al. [30]. The surface morphology of AC and PG was determined
using the hanging drop method by scanning electron microscopy
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H.D. Bouras et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2017) 1–9 3

Fig. 1. Chemical structure of Congo red.

Table 1
Characteristics of A. carbonarius and P. glabrum biomass.

Adsorbent AC PG

Surface area
Single point surface area (m2 /g) 3.87 4.64
BET surface area (m2 /g) 5.07 6.31
Pore volume
Single point adsorption total pore volume of pores (cm3 /g) 0.0046 0.0052
Pore size
Adsorption average pore diameter (Å) 36.66 32.98
Nanoparticle Size
Average Particle Size (Å) 11832.254 9509.172
pHPZC 5.76 6.40

(SEM) at 15.0 kV and 10 0 0X magnification. FT-IR spectra of biosor-

bents were obtained on a Perkin Elmer FTIR-1750 spectrophotome-
ter in the region of 40 0–40 0 0 cm−1 . 100 AC AC-RC

3. Results and discussion 95

3.1. Characterization A. carbonarius and P. glabrum surfaces

% Transmitance

90

The textural parameters of AC and PG biosorbents were summa-

rized in Table 1. It was found that the BET surface area of AC and 85 3269.43 cm-1

1413.84cm-1
3269.43 cm-1

PG was 5.0709 and 6.3097 m2 /g, respectively. Though the surface

1620.63cm-1
areas of AC and PG were relatively small [31,32], the biosorption 80
capability of AC and PG for CR is high. These results demonstrated
that the functional groups in AC and PG are more efficient than
75
surface area in biosorption process.
The total pore volume and average pore diameter for Aspergillus 1023.18 cm-1
carbonarius M333 were found to be 0.004648 cm3 /g and 36.6641 Å, 70
4000 3500 3000 2500 2000 1500 1000 500
respectively. While, 0.005203 cm3 /g and 32.9866 Å were obtained
for the total pore volume and average pore diameter for Penicillium Wavenumber (cm-1)
glabrum Pg1, respectively.
The points of zero charge (pHPZC ) for AC and PG were 5.76 and PG PG (RC)
100
6.40, respectively (Table 1). For pH values lower than pHPZC the
adsorbent presents a positive surface charge. The higher amount
697.92 cm -1

of CR dye adsorbed by the two adsorbents at pH values lower than

548.51 cm

95
-1

5.00 can be explained by the electrostatic interactions between the

% Transmitance

anionic dye molecule and the surface charge of the adsorbents,

-1

which became positively charged at pH < 5.76 and 6.40, for AC and
1236.44 cm
-1

90
-1 1742.74 cm

PG, respectively (pH < pHPZC ).

-1
-1
1373.40 cm
1542.59 cm
-1

SEM is used to characterize the surface morphology of a biosor-

2854.09 cm
-1

bent [27]. The SEM images of AC and PG are illustrated in Fig. 3(a) 85
3271.05 cm

and (b), respectively. As seen in these figures, the surfaces of AC

-1

and PG particles have a porous structure.

1642.76 cm
2923.80 cm

Vibrational spectra of AC and PG biomass before and after dye 80

biosorption are illustrated in Fig. 2(a) and (b), respectively. The
changes in the FT-IR functional group bands, along with the band -1
1027.11 cm
positions, before and after dye loading are presented in Table 2. 75
The FT-IR spectrum of AC before the biosorption process showed 4000 3500 3000 2500 2000 1500 1000 500
several major intense bands, around 3269, 2924, 1620, 1413 and Wavenumber (cm-1)
1023 cm−1 (Fig. 2(a)). A shift in the wave number from 3269 cm−1
to 3278 cm−1 was noted after CR biosorption and this may be at- Fig. 2. (a). FTIR spectra of A. carbonarius before and after biosorption of Congo red.
(b). FTIR spectra of PG before and after biosorption of Congo red.
tributed to the change in –NH2 stretching vibration. The intensities
of the peaks at about 2924 and 1413 cm−1 on the FT-IR spectrum of

Please cite this article as: H.D. Bouras et al., Biosorption of Congo red dye by Aspergillus carbonarius M333 and Penicillium glabrum
Pg1: Kinetics, equilibrium and thermodynamic studies, Journal of the Taiwan Institute of Chemical Engineers (2017),
http://dx.doi.org/10.1016/j.jtice.2017.08.002
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Table 2
FT-IR spectral characteristics of A. carbonarius and P. glabrum before and after Congo red sorption.

AC PG
Band position (cm−1 ) Band position (cm−1 ) Suggested assignments
Before biosorption After biosorption Before biosorption After biosorption

3269.43 3278.48 – – –NH2 stretching vibration

– – 3271.05 3273.19 –N–H stretching vibration
1620.63 1619.43 – – N–H deformation vibration of amide I groups
1023.18 1030.29 – – C–N stretch of amide or amine
– – 2923.80 2923.32 –CH stretch aliphatic
– – 1742.74 1743.40 C=O stretching vibration of carboxylate (–COO–) / (–COOR–)
– – 1642.76 1643.37 C=O stretching vibration of N–H deformation vibration of amide I groups
– – 1027.11 1026.34 C–O stretching of carboxylic groups

80

60

qt (mg/g)
40

AC
20 PG

0
0 50 100 150 200 250
t (min)
(a) Fig. 4. Effect of contact time on the biosorption capacity of Congo red on A. car-
bonarius and P. glabrum. Conditions: Ci = 50 mg/L, dosage of 0.33 g/L, T = 303 K, pH
4.5.

deformation vibration of amide I groups. The scissor bending of a

NH2 group can be observed at 1542 cm−1 . The biosorption peak at
1378 cm−1 corresponds to –CH bending vibrations. Thus the band
observed at 1236 cm−1 may be attributed to stretching vibrations
of sulphonate groups [35]. The peak observed at 1027 cm−1 was
assigned to C–O stretching of carboxylic groups, while the peak
showed at 697 cm−1 correspond to the N–H out-of-plane bending.
The band between 611 and 520 cm−1 for the biosorbent represents
C–N–C scissoring that is only found in protein structures [36], and
this band disappeared after CR biosorption. In the spectra of PG
after treatment with CR, shifts of bands were observed at these
peaks, indicating possible involvement of these functional groups
in the adsorption process.

(b) 3.2. Effect of contact time

Fig. 3. (a) SEM micrographs of AC. (b). SEM micrographs of PG.
biomass AC, ascribed to –C–H stretching vibrations were stronger
than those of the modified biomass AC loaded with CR dye. The
sharp peak at 1620 cm−1 can be attributed to N–H deformation vi-
bration of amide I groups [33]. The band of 1023 cm−1 could be
attributed to a C–N stretch of amide or amine.
In Fig. 2(b) (CR biosorbed by PG) the peak 3271 cm−1 was
shifted to 3273 cm−1 , corresponding to N–H stretching vibrations.
The bands observed at about 2923 cm−1 and 2854 cm−1 could
be assigned to the –CH stretch. The band observed at 1742 cm−1
was assigned to a carbonyl band (C=O) of unionized carboxylate
stretching of carboxylic acid or their esters [34], whereas the peak
at 1642 cm−1 may be attributed to C=O stretching vibration of N–H
The effect of contact time (0–240 min) on biosorption capacities
of AC and PG at an initial dye concentration of 50 mg/L is shown
in Fig. 4. It can be seen from this figure that the biosorption capac-
ities increase with contact time and the adsorption reached equi-
librium after about 180 min for both AC and PG. At equilibrium CR
removal for AC was 53.4 mg/g compared to 66.6 mg/g for PG with
an initial CR concentration of 50 mg/L. Further increase in contact
time did not enhance the extent of biosorption and hence 180 min
was chosen as the contact time for further experiments.
3.3. Effect of pH on biosorption
The pH of the aqueous solution is an important factor on
the dye-binding capacity of each biosorbent. Therefore, CR dye
biosorption onto AC and PG was studied at 303 K in the pH range

Please cite this article as: H.D. Bouras et al., Biosorption of Congo red dye by Aspergillus carbonarius M333 and Penicillium glabrum
Pg1: Kinetics, equilibrium and thermodynamic studies, Journal of the Taiwan Institute of Chemical Engineers (2017),
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70 80

60 60

qe (mg/g)
qe (mg/g)

50 40

40
AC
20 PG
AC
PG
30
0
0 20 40 60 80 100 120 140
1 2 3 4 5 6 7 C0 (mg/L)
pH
Fig. 7. Effect of initial dye concentration on the biosorption capacity A. carbonarius
Fig. 5. Effect of pH on the equilibrium uptake capacity A. carbonarius and P. glabrum and P. glabrum. Conditions: dosage of 0.33 g/L, T = 303 K, pH 4.5.
for Congo red. Conditions: Ci = 50 mg/L, dosage of 0.33 g/L, T = 303 K.

70 1.4

65 1.2
60
Ce/qe (g/L) 1.0
55
0.8
qe (mg/g)

50
0.6
45
0.4
40 AC
AC PG
35 PG 0.2

30 0 20 40 60 80 100
291 294 297 300 303 306 309
Ce (mg/L)
Temperature (T)
Fig. 8. The Langmuir isotherm plot for the biosorption of Congo red onto A. car-
Fig. 6. Effect of temperature on the biosorption capacity of A. carbonarius and P. bonarius and P. glabrum.Conditions: Ci = 50 mg/L, dosage of 0.33 g/L, T = 303 K, pH
glabrum for Congo red. Conditions: Ci = 50 mg/L, dosage of 0.33 g/L, pH 4.5. 4.5.

of 1.5–6.5 using an initial dye concentration of 50 mg/L and a It was likely due to more diffusion of adsorbate molecules across
biosorbent dosage of 0.33 g/L. Fig. 5 shows the biosorption capacity the external boundary layer and internal pores of the adsorbent
of CR on AC and PG. It can be seen that the optimum pH for CR particle [39].
removal was observed in the pH range of 3.0–4.5, and dye uptake
slightly decreased at pH = 5. The lower biosorption of the CR in al-
3.5. The effect of initial concentration of Congo red dye
kaline medium may be attributed to the competition from excess
OH– ions with the anionic dye molecule for the biosorption sites
The biosorption process is greatly influenced by the initial con-
[37]. While, acidic conditions could be favorable for the biosorption
centration of the adsorbate [40]. The biosorption capacity for AC
between fungal biomass and the dye, because a significantly high
and PG at different initial CR concentration is shown in Fig. 7.
electrostatic attraction could exist between the positively charged
The uptake amounts increased with increasing initial dye con-
surface of the biosorbent under acidic conditions and the anionic
centrations up to 100 mg/L for CR and then did not change. This
dye [38]. At pH 4.5, the biosorption of the dye CR by AC and PG
may be due to the occupation of the sorption sites on the biosor-
was 53.4 ± 2.6 mg/g and 67.2 ± 1.7 mg/g, respectively.
bents as the concentration of the dye increased. The biosorption
amounts of CR dye on AC and PG increased from 30.2 ± 2.2 to
3.4. Effects of temperature on Congo red biosorption 75.0 ± 1.3 mg/g and from 44.6 ± 1.9 to 88.2 ± 1.5 mg/g, respectively,
with increasing initial dye concentration from 25 to 125 mg/L.
The effects of temperature on the biosorption capacity of AC
and PG were studied at 293, 298 and 303 K. As shown in Fig. 6 that
the removal of CR increased with temperatures from 293 to 303 K, 3.6. Biosorption kinetics study
suggesting that the sorption process is endothermic in nature. The
equilibrium adsorption capacity was affected by the temperature The Lagergren’s pseudo-first-order, pseudo-second-order and
and the amount of CR adsorbed by AC and PG increased from intraparticle diffusion model were used to study the biosorption
33.4 ± 0.7 to 53.4 ± 1.0 mg/g and from 34.0 ± 0.7 to 66.6 ± 1.4 mg/g, kinetics of CR onto AC and PG biomass, using the experimental
respectively, when the temperature was raised from 298 to 303 K. data at various initial concentrations.

Please cite this article as: H.D. Bouras et al., Biosorption of Congo red dye by Aspergillus carbonarius M333 and Penicillium glabrum
Pg1: Kinetics, equilibrium and thermodynamic studies, Journal of the Taiwan Institute of Chemical Engineers (2017),
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Table 3
Comparison of the first- and second-order sorption rate constants, calculated and experimental qe values for sorption of
Congo red with different initial concentrations onto A. carbonarius and P. glabrum.

Samples AC PG

C0 of CR (mg/L) 50 75 100 50 75 100

qeq (exp) (mg/g) 54.00 66.00 75.00 67.20 76.80 87.60
Pseudo-first order
K1 (min−1 ) 4.97 × 10−2 4.51 × 10−2 4.78 × 10−2 5.18 × 10−2 4.67 × 10−2 4.69 × 10−2
q1 (cal) (mg/g) 44.12 19.36 25.94 62.26 54.18 58.54
R2 0.949 0.943 0.993 0.918 0.986 0.946
Pseudo-second order
K2 (g/mg min) 7.89 × 10−4 2.87 × 10−3 2.14 × 10−3 5.32 × 10−4 6.26 × 10−4 7.51 × 10−4
q2 (cal) (mg/g) 58.14 67.11 76.34 72.99 81.97 91.74
R2 0.994 0.999 0.999 0.994 0.994 0.996
Intraparticle diffusion model
Kid1 (mg/g min1/2 ) 05.32 02.78 02.75 06.33 06.33 07.65
C1 02.96 38.83 45.33 02.70 11.33 16.86
R2 0.989 0.962 0.986 0.989 0.988 0.964
Kid2 (mg/g min1/2 ) 02.09 0.56 01.25 02.98 02.72 02.48
C2 25.14 57.32 58.41 25.85 39.19 53.26
R2 0.975 0.960 0.907 0.977 0.992 0.934

The linear form of the pseudo-first-order rate equation [41] is Table 4

Isotherm parameters and correlation coeffi-
given as:
cients for the biosorption of Congo red in
k1 aqueous solutions onto A. carbonarius and P.
ln (qe − qt ) = lnqe − t (3) glabrum.
2.303
Samples
Where qe and qt are the amounts of the CR dye sorbed at equilib- AC PG
rium time (mg/g) and t (min), respectively, and k1 is the first-order
Langmuir
rate constant (min−1 ). qm (mg/g) 99.01 101.01
The pseudo-second-order rate equation [42] is given by b (L/mg) 0.036 0.079
R2 0.988 0.998
t 1 1
= + t (4) Freundlich
qt k2 q22 q2 KF (mg/g) (mg/L)1/n 10.46 24.61
n 2.20 3.39
Where k2 (g/mg min) is the second-order rate constant, qt (mg/g) is R2 0.922 0.942
the amount of biosorption after time t (min) and qe is the amount Temkin
KT (L/g) 0.280 1.103
of biosorption equilibrium (mg/g). The intraparticle diffusion equa-
bT (kJ/mole) 0.105 0.128
tion is expressed as [43], R2 0.971 0.975
Dubinin–Radushkevich
qt = kid t 1/2 + Ci (5) qDR (mg/g) 72 80
KDR (mole2 /kJ2 ) 3E−05 1E−05
Where qt (mg/g) is the amount adsorbed at time t (min), kid E (kJ/mole) 0.129 0.224
(mg/g min1/2 ) is the rate constant of intraparticle diffusion. Ci R2 0.956 0.888
(mg/g) is a constant that gives an idea about the thickness of the Sips
qms (mg/g) 119.05 101.01
boundary layer.
Ks (L/mg)m 0.0026 0.0789
The parameters of the pseudo-first-, pseudo-second-order and ms 0.969 1.0 0 0
intraparticle diffusion kinetics at different initial dye concentra- R2 0.962 0.984
tions are summarized in Table 3. The low R2 values (< 0.993) and
the difference between qexp and qcal indicate that the pseudo-
first-order model was not well fitted to describe the biosorption
the linear plot of each biosorbent did not pass through the ori-
of CR by AC and PG. It may be explained that the pseudo-first-
gin [45]. Therefore, intraparticle diffusion was not the rate-limiting
order model does not fit well to the whole range of contact time
step [46]. The increase in the C values was due to the increase
and generally underestimate the qexp values [43,44]. On the other
in the thickness of the boundary layer. These results suggest that
side, the R2 values (R2 > 0.994) for the pseudo-second-order model
greater contribution of the surface adsorption is the rate control-
were relatively higher than those of the pseudo-first-order model.
ling step [47].
Moreover, the q2 values calculated by the pseudo-second-order
model were close to the experimental qe values. Thus, these results
suggest that the biosorption of CR on AC and PG can be described 3.7. Biosorption isotherms
well by pseudo-second-order kinetics.
The intraparticle diffusion model was also tested in order to The equilibrium isotherm studies are important for the under-
verify the possible influence of mass transfer resistance on bind- standing of the biosorption mechanism [35]. The equilibrium data
ing of CR dye onto both biosorbents. The plot of the intraparticle were analyzed using the most commonly used isotherms, Lang-
diffusion model for CR (data not shown) shows the same trend in muir, Freundlich, Temkin, Dubinnin–Radushkevich and Sips adsorp-
two steps. The initial portion of the plot indicates an external mass tion isotherm models. The linear form of the Langmuir model
transfer whereas the second linear portion is due to intraparticle [27] is given as:
or pore diffusion. The correlation coefficients of the intraparticle
diffusion model (Table 3) were found to be lower than that of Ce 1 Ce
= + (6)
the pseudo-second-order model (0.934 ≤ R2 ≤ 0.992). In addition, qe bqm qm

Please cite this article as: H.D. Bouras et al., Biosorption of Congo red dye by Aspergillus carbonarius M333 and Penicillium glabrum
Pg1: Kinetics, equilibrium and thermodynamic studies, Journal of the Taiwan Institute of Chemical Engineers (2017),
http://dx.doi.org/10.1016/j.jtice.2017.08.002
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H.D. Bouras et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2017) 1–9 7

Table 5 characterized by a uniform distribution of binding energies, up to

Comparison of biosorption capacities of various biosorbents for removal of
some maximum binding energy [49], which is expressed in the fol-
Congo red.
lowing equation:
Biosorbents pH qm (mg/g) References
RT RT
Pine cone 3.55 40.19 [10] qe = lnCe + ln KT (8)
Wheat bran 8.0 22.73 [13]
bT bT
Aspergillus niger 6.0 14.72 [26] Where KT (L/g) and bT (kJ/mol) are the Temkin constants. KT and
Aspergillus nidulans 6.8 357.14 [27]
bT constants were determined from the slope and intercepts of the
Cattail root 7.0 38.79 [28]
Sugarcane bagasse 7.0 38.2 [29] plots obtained by plotting plot of qe versus ln Ce .
Phoenix dactylifera seeds 2.0 61.72 [39] The D–R (Dubinnin–Radushkevich) isotherm equation used to
Macauba palm cake 6.5 32 [55] distinguish between physical and chemical adsorption is described
Jute stick powder 7.0 35.7 [56]
by Eq. (9) [50]:
Palm Kernel Seed Coat 6.7 66.23 [57]
Rice husk 6.0 14 [58] ln qe = K ε 2 + ln qDR (9)
Orange peel 5.0 22.4 [59]
Neem leaf powder 6.7 128.3 [60] Polanyi potential (ε ) is given as Eq. (10):
Trametes versicolor 7.0 51.81 [61]
Activated carbon (commercial grade) 2.0 0.635 [62] ε = RT ln(1 + 1/Ce ) (10)
Apricot stone 13 32.85 [63]
Penicillium sp. YW01 3.0 411.53 [64] Where qDR is the Dubinin–Radushkevich maximum adsorption ca-
Alternaria alternata 5 600 [65] pacity of dye (mg/g), K is the Dubinin–Radushkevich constant
Penicillium janthinellum 5 344.83 [66]
(mol2 /kJ2 ), R is the universal gas constant (8.314 J/mol K) and T is
Aspergillus carbonarius 4.5 99.01 Present work
Penicillium glabrum 4.5 101.01 Present work the absolute temperature (K). The plot of ln qe versus ε 2 gives a
straight line with a slope of K and an intercept of ln qDR . The
Dubinin–Radushkevich constant can give valuable information re-
4.6 garding the mean energy of adsorption by the following equation:

4.4 E = (−2 K )−1/2 (11)

4.2 The Sips model [51] incorporates the features of the Langmuir and
Freundlich models into a single equation and is represented as fol-
lows:
4.0
Ln qe

qms KsCems
qe = (12)
3.8 1 + KsCems
Where qe is the adsorbed amount at equilibrium (mg/g), Ce the
3.6 AC
equilibrium concentration of the adsorbate (mg/L), qmS the Sips
PG
maximum adsorption capacity (mg/g), KS the Sips equilibrium con-
3.4 stant (L/mg)m and mS is the Sips model exponent.
The parameter of isotherms adsorption and the R2 values are
2.0 2.5 3.0 3.5 4.0 4.5 5.0 listed in Table 4. Based on the analysis results, the biosorption
Ln Ce isotherm data were characterized perfectly by the Langmuir model
for both AC and PG. It is clear from the detailed analysis of the R2
Fig. 9. The Freundlich isotherm plot for the biosorption of Congo red onto A. car- values that the Langmuir model showed good fit of the behavior of
bonarius and P. glabrum.Conditions: Ci = 50 mg/L, dosage of 0.33 g/L, T = 303 K, pH experimental equilibrium data. The Langmuir isotherm gave max-
4.5. imum adsorption capacities of 99.01 and 101.01 mg/g for AC and
PG, respectively. It can be seen from Table 4 that, the numerical
Where Ce is the equilibrium concentration (mg/L) and qe is the values of the Freundlich constant n were 2.2 and 3.4 for AC and
amount adsorbed at equilibrium (mg/g). The Langmuir constants PG, respectively. Values of n greater than unity indicate that dye
qm (mg/g) represent the monolayer biosorption capacity and b anion was favorably biosorbed [52] by AC and PG. The applicabil-
(L/mg) relates to the heat of biosorption. A plot of Ce /qe versus Ce ity of both Langmuir and Freundlich isotherms to the dye implied
gives a straight line of slope 1/qm and intercepts 1/ qm b is shown that the biosorbents might exhibit monolayer adsorption and het-
in Fig. 8. erogeneous surface conditions. On the other hand, the values of KT
The Freundlich isotherm assumes a heterogeneous surface with and bT determined from Temkin for AC and PG model were 0.280,
a non-uniform distribution of biosorption heat over the surface 1.103 L/g and 0.105 and 0.128 kJ/mole, respectively. The higher KT
[48], which is expressed in the following equation: indicated a stronger interaction between the dye and the adsor-
1 bent surfaces. The Temkin model was capable of representing the
l nqe = l nK f + l nCe (7) equilibrium data more adequately (R2 > 0.97). The mean free en-
n ergy of adsorption (E), obtained from Dubinin–Radushkevich model
Where Kf (mg/g (L/mg) 1/n ), defined as the adsorption or distribu- gives information about biosorption mechanism, and more pre-
tion coefficient, is related to the adsorption capacity and whereof cisely its physical or chemical nature. If the value of E< 8 kJ/mole,
is a step of the affinity of the adsorbent for the adsorbate; n is a the process is governed by physical biosorption [53]. For AC and
measure of the adsorption intensity and gives indication on the fa- PG, the values of E were found to be 0.129 and 0.224 kJ/mol, re-
vorability of the adsorption. The linear plot of specific adsorption spectively. Hence, the present biosorption of CR seems to involve
(ln qe ) against the (ln Ce ) for Freundlich model is shown in Fig. 9. a physical mechanism. It was observed that Sips model described
The Temkin isotherm assumes that (i) the heat of adsorption the biosorption process successfully for CR dye with perfect statis-
of all the molecules in the layer decreases linearly with cover- tical results. The Sips model produced a good fit to the experimen-
age due to adsorbent–adsorbate interactions, and (ii) adsorption is tal data for PG as evidenced by high R2 (0.984). From this model,

Please cite this article as: H.D. Bouras et al., Biosorption of Congo red dye by Aspergillus carbonarius M333 and Penicillium glabrum
Pg1: Kinetics, equilibrium and thermodynamic studies, Journal of the Taiwan Institute of Chemical Engineers (2017),
http://dx.doi.org/10.1016/j.jtice.2017.08.002
JID: JTICE
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8 H.D. Bouras et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2017) 1–9

Table 6
Thermodynamic parameters for the biosorption of Congo red onto A. carbonarius and P.
glabrum at different temperatures.

Adsorbent Temperature (K) G° (kJ/mol) H° (kJ/mol) S° (kJ/ (mol K))
AC 293 −3.05 48.42 0.154
298 −2.61
303 −1.50
PG 293 −2.99 74.13 0.243
298 −1.31
303 −0.57

decreased with the rise in temperature. The negative value con-

-0.2 firms the feasibility of the process and the spontaneous nature of
sorption of CR on AC and PG.
-0.4 The calculated H° value was found to be 48.4 and 74.1 kJ/mol
for AC and PG, respectively. The positive H° values could lead
-0.6 to an endothermic nature of interaction between CR dye and the
both biomass AC and PG sorbent in the range of 293–303 K. It
Ln KL

-0.8 was also observed that S° values 0.154 kJ/mole K for AC and
0.243 kJ/mole K for PG indicate an increase in the degree of free-
-1.0 dom of the sorbed dye molecules.

-1.2 AC
4. Conclusion
PG

-1.4 0.00330
0.00333 0.00336 0.00339 0.00342
1/T K-1
Fig. 10. Plot of ln KL against 1/T for the removal of Congo red by A. carbonarius and
P. glabrum.
the maximum capacity (qm ) of AC and PG for the dye biosorp-
tion was estimated to be 119 and 101 mg/g, respectively. The values
of mS for AC and PG were found to be 1.0 0 0 and 0.969, respec-
tively, which implied that the model looked more like Freundlich
model than Langmuir model for the biosorption of CR onto the rel-
atively heterogeneous surface of biosorbent [54]. A comparison of
the maximum adsorption capacity with those of some other adsor-
bents reported in literature is given in Table 5. The AC and PG ad-
sorbents used in this work introduced very high adsorption capaci-
ties for CR when compared with other several adsorbents. From 19
different adsorbents, only five adsorbents presented higher sorp-
tion capacity than AC and PG [10, 13, 26–29, 39, 55–66], indicating
that AC and PG were intermediate adsorbents in relation to the ad-
sorption capacity for CR removal from aqueous solution. AC and PG
are not only excellent adsorbents for CR but also very cost effective
compared to activated carbon, one of the most popular commercial
adsorbents in use.
3.8. Thermodynamic analysis of biosorption process
In order to evaluate the thermodynamics of the dye removal
process by AC and PG biosorbent, the changes in the Gibbs free
energy (G°), enthalpy (H°) and entropy (S°), were analyzed.
KL is used as the equilibrium constant due to its dependence on
temperature. The following equations were used to estimate the
thermodynamic parameters.
G◦ = −RT lnKL (8)
H ◦ S ◦
lnKL = − + (9)
RT R [8] Hamzeh Y, Ashori A, Azadeh E, Abdulkhani A. Removal of acid orange 7 and
The values of H° and S° were determined from slope and inter-
cept of the plot of ln KL vs 1/T as shown in Fig. 10. The estimated
thermodynamic data are shown in Table 6. The magnitude of G°
For sorption of Congo red onto two micro-fungi (molds), A. car-
bonarius and P. glabrum, equilibrium, kinetic and thermodynamic
studies were presented in this study. The initial pH of the medium
significantly affected the sorption capacity of sorbent and the op-
timum value was found to be 4.5. Kinetic studies on sorption of
Congo red on A. carbonarius and P. glabrum revealed that a pseudo-
second order model showed the best fit to the experimental data
and film diffusion might be involved in the sorption process. The
surface area of the adsorbents was found to be 5.07 and 6.31 m2 /g
for AC and PG, respectively. The disappearances and shifts of some
functional groups in FT-IR spectra confirm the dye sorption onto
A. carbonarius and P. glabrum. The equilibrium models were used
to reveal the biosorption data. Langmuir model is capable of rep-
resenting the adsorption data satisfactorily than the other mod-
els. Furthermore, from the value of H° it was revealed that the
biosorption process is endothermic. Thus, A. carbonarius and P.
glabrum could be used as a biosorbent for the effective removal
of Congo red from dye wastewater in terms of high biosorption
capacity, available in natural and abundant with low cost.
References
[1] Wan Ngah WS, Teong LC, Hanafiah MAKM. Adsorption of dyes and heavy metal
ions by chitosan composites: a review. Carbohydr Polym 2011;83:1446–56.
[2] Shoukata S, Bhattia HN, Iqbal M, Noreen S. Mango stone biocomposite prepa-
ration and application for crystal violet adsorption: a mechanistic study. Mi-
croporous Mesoporous Mater 2017;239:180–9.
[3] Tahir N, Bhattia HN, Iqbal M, Noreen S. Bio-molecules composite with peanut
hull waste and application for crystal violet adsorption. Int J Biol Macromol
2017;94:210–20.
[4] Noreen S, Bhatti HN, Farrukh Z, Ilays S, Jamal MA. Continuous fixed bed re-
moval of novacron orange P-2R using sugarcane bagasse: prediction of break-
through curves. Desalin Water Treat 2016;57:12814–21.
[5] Ozer A, Akkaya G, Turabik M. The removal of acid red 274 from wastewater:
combined biosorption and biocoagulation with Spirogyra Rhizopus. Dyes Pig-
ment 2006;71:83–9.
[6] Yang Y, Jin D, Wang G, Liu D, Jia X, Zhao Y. Biosorption of acid blue 25 by un-
modified and CPC-modified biomass of Penicillium YW01: kinetic study, equi-
librium isotherm and FTIR analysis. Colloid Surf B 2011;88:521–6.
[7] Barka N, Abdennouri M, Makhfouk MEL. Removel of methylene blue and eri-
ochrome black T from aqueous solutions by biosorption on Scolymus hispan-
icus L.: kinetics, equilibrium and thermodynamics. J Taiwan Inst Chem Eng
2011;42:320–6.
remazol black 5 reactive dyes from aqueous solutions using a novel biosorbent.
Mater Sci Eng C 2012;32:1394–400.
[9] Jarusiripot C. Removal of reactive dye by adsorption over chemical pretreat-
ment coal based bottom ash. Procedia Chem 2014;9:121–30.

Please cite this article as: H.D. Bouras et al., Biosorption of Congo red dye by Aspergillus carbonarius M333 and Penicillium glabrum
Pg1: Kinetics, equilibrium and thermodynamic studies, Journal of the Taiwan Institute of Chemical Engineers (2017),
http://dx.doi.org/10.1016/j.jtice.2017.08.002
JID: JTICE
ARTICLE IN PRESS
H.D. Bouras et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2017) 1–9
[10] Dawood S, Sen TK. Removal of anionic dye Congo red from aqueous solu-
tion by raw pine and acid-treated pine cone powder as adsorbent: equilib-
rium, thermodynamic, kinetics, mechanism and process design. Water Res
2012;46:1933–46.
[11] Chakraborty S, Chowdhury S, Saha PD. Adsorption of crystal Violet
from aqueous solution onto NaOH-modified rice husk. Carbohydr Polym
2011;86:1533–41.
[12] Chowdhury S, Saha P. Sea shell powder as a new adsorbent to remove ba-
sic green 4 (malachite green) from aqueous solutions: equilibrium, kinetic and
thermodynamic studies. Chem Eng J 2010;164:168–77.
[13] Wang XS, Chen JP. Biosorption of Congo red from aqueous solution using
wheat bran and rice bran–batch studies. Separ Sci Technol 2009;44:1452–66.
[14] Barka N, Ouzaouit K, Abdennouri M, Makhfouk ME. Dreid prickly pear cac-
tus (Opuntia ficus india) cladodes as a low-cast and eco-friendly biosorbent for
dyes removal from aqueous solutions. J Taiwan Inst Chem Eng 2013;44:52–60.
[15] Gupta VK, Suhas. Application of low-cost adsorbents for dye removal: a review.
J. Environ. Manag 2009;90:2313–42.
[16] Gupta N, Kushwaha AK, Chattopadhyaya MC. Adsorption studies of cationic
dyes onto Ashoka (Saraca asoca) leaf powder. J Taiwan Inst Chem Eng
2012;43:604–13.
[17] Aksu Z, Dönmez G. Combined effects of molasses sucrose and reactive dye on
the growth and dye bioaccumulation properties of Candida tropicalis. Process
Biochem 2005;40:2443–54.
[18] Rashid A, Bhatti HN, Iqbal M, Noreen S. Fungal biomass composite with ben-
tonite efficiency for nickel and zinc adsorption: a mechanistic study. Ecol Eng
2016;91:459–71.
[19] Mathialagan T, Viraraghavan T. Biosorption of pentachlorophenol from aqueous
solutions by a fungal biomass. Bioresour Technol 20 09;10 0:549–58.
[20] Fan H, Yang JS, Gao TG, Yuan HL. Removal of a low-molecular basic dye (azure
blue) from aqueous solutions by a native biomass of a newly isolated Cladospo-
rium sp.: kinetics, equilibrium and biosorption simulation. J Taiwan Inst Chem
Eng 2012;43:386–92.
[21] Bayramoğlu G, Çelik G, Arica MY. Biosorption of reactive blue 4 dye by native
and treated fungus Phanerocheate chrysosporium: batch and continuous flow
system studies. J Hazard Mater 2006;137:1689–97.
[22] Matos A, Bezerra R, Dias AA. Screening of fungal isolates and properties of
Ganoderma applanatum intended for olive mill wastewater decolorization and
dephenolization. Lett Appl Microbiol 2007;45:270–5.
[23] Yesilada O, Cing S, Asma D. Decolourisation of the textile dye astrazon red FBL
by Funalia trogii pellets. Bioresour Technol 2002;81:155–7.
[24] Zeroual Y, Kim BS, Kim CS, Blaghen M, Lee KM. Biosorption of bromophenol
blue from aqueous solutions by Rhizopus Stolonifer biomass. Water Air Soil Pol-
lut 2006;177:135–46.
[25] Gajera HP, Bambharolia RP, Darshna HG, Patel SV, Golakiya BA. Molecular iden-
tification and characterization of novel Hypocrea koningii associated with azo
dyes decolorization and biodegradation of textile dye effluents. Process Saf En-
viron 2015;98:406–16.
[26] Fu Y, Viraraghavan T. Decolorization and detoxification of Synozol red
HF-6BN azo dye, by Aspergillus niger and Nigrospora sp. Adv. Environ Res
2002;7:239–47.
[27] Xi Y, Shen YF, Yang F, Yang G, Liu C, Zhang Z, et al. Removal of azo dye from
aqueous solution by a new biosorbent prepared with Aspergillus nidulans cul-
tured in tobacco waste-water. J Taiwan Inst Chem Eng 2013;44:815–20.
[28] Hu Z, Chen H, Ji F, Yuan S. Removal of Congo red from aqueous solution by
cattail root. J Hazard Mater 2010;173:292–7.
[29] Zhang Z, Moghaddam L, O’Hara IM, Doherty WOS. Congo red adsorption by
ball-milled sugarcane bagasse. Chem Eng J 2011;178:122–8.
[30] Wang S, Zhu ZH, Coomes A, Haghseresht F, Lu GQ. The physical and surface
chemical characteristics of activated carbons and the adsorption of methylene
blue from wastewater. J Colloid Interface Sci 2005;284:440–6.
[31] Panda GC, Das SK, Guha AK. Jute stick powder as a potential biomass for the
removal of Congo red and rhodamine B from their aqueous solution. J Hazard
Mater 2009;164:374–9.
[32] Vieira SS, Magriotis ZM, Santos NAV, Cardoso MG, Saczk AA. Macauba
palm(Acrocomia aculeata) cake from biodiesel processing: an efficient and low
cost substrate for the adsorption of dyes. Chem Eng J 2012;183:152–61.
[33] Mona S, Kaushik A, Kaushik CP. Biosorption of reactive dye by waste biomass
of Nostoc linckia. Ecol Eng 2011;37:1589–94.
[34] Li F.T., Yang H., Zhao Y., Xu R. Novel modified pectin for heavy metal adsorption
Chin Chem Lett 2007; 18: 325–8.
[35] Akar T, Divriklioglu M. Biosorption applications of modified fungal biomass for
decolorization of reactive red 2 contaminated solutions: batch and dynamic
flow mode studies. Bioresour Technol 2010;101:7271–7.
[36] Wu Y, Jiang L, Wen YJ, Xin J, Feng ZS. Biosorption of basic violet 5BN and
basic green by waste brewer’s yeast from single and multicomponent systems.
Environ Sci Pollut Res 2012;19:512–21.
[37] Kumar PS, Ramalingam S, Senthamarai C, Niranjanaa M, Vijayalakshmi P,
Sivanesan S. Adsorption of dye from aqueous solution by cashew nut shell:
studies on equilibrium isotherm, kinetics and thermodynamics of interactions.
Desalination 2010;261:52–60.
[38] Daneshvar E, Sohrabi MS, Kousha M, Bhatnagar A, Aliakbarian B, Converti A,
et al. Shrimp shell as an efficient bioadsorbent for acid blue 25 dye removal
from aqueous solutions. J Taiwan Inst Chem Eng 2014;45:2926–34.
Please cite this article as: H.D. Bouras et al., Biosorption of Congo red dye by Aspergillus carbonarius M333 and Penicillium glabrum
Pg1: Kinetics, equilibrium and thermodynamic studies, Journal
http://dx.doi.org/10.1016/j.jtice.2017.08.002
[m5G;August 31, 2017;15:42]
9
[39] Pathania D, Sharma A, Siddiqi ZM. Removal of Congo red dye from aqueous
system using Phoenix dactylifera seeds. J Mol Liq 2016;219:359–67.
[40] Saha PD, Chowdhury S, Mondal M, Sinha K. Biosorption of direct red 28 (Congo
red) from aqueous solutions by eggshells: batch and column studies. Separ Sci
Technol 2012;47:112–23.
[41] Bouras HD, Benturki O, Bouras N, Attou M, Donnot A, Merlin A, et al. The use
of an agricultural waste material from Ziziphus jujuba as a novel adsorbent for
humic acid removal from aqueous solutions. J Mol Liq 2015;211:1039–46.
[42] Subbaiah MV, Yuvaraja G, Vijaya Y, Krishnaiah A. Equilibrium, kinetic and
thermodynamic studies on biosorption of Pb (II) and Cd (II) from aqueous
solution by fungus (Trametes versicolor) biomass. J Taiwan Inst Chem Eng
2011;42:965–71.
[43] Kim MH, Wang CHH, Kang SB, Kim S, Park SW, Yun YS, et al. Removal of
hydrolyzed reactive black 5 from aqueous solution using a polyethylenimine
polyvinyl chloride composite fiber. Chem Eng J 2015;280:18–25.
[44] Thangamani KS, Sathishkumar M, Sameena Y, Vennilamani N, Kadirvelu K, Pat-
tabhi S, et al. Utilization of modified silk cotton hull waste as an adsorbent for
the removal of textile dye (reactive blue MR) from aqueous solution. Bioresour
Technol 2007;98:1265–9.
[45] Argun ME, Dursun S, Ozdemir C, Karatas M. Heavy metal adsorption
by modified oak sawdust: thermodynamics and kinetics. J Hazard Mater
2007;141:77–85.
[46] Depci T, Kul AR, Onal Y. Competitive adsorption of lead and zinc from aqueous
solution on activated carbon prepared from van apple pulp: study in single-
and multi-solute systems. Chem Eng J 2012;200:224–36.
[47] Salima A, Benaouda B, Noureddine B, Duclaux L. Application of ulva lactuca
and systoceira stricta algae-based activated carbons to hazardous cationic dyes
removal from industrial effluents. Water Res 2013;47:3375–88.
[48] Mittal A, Kaur D, Malviya A, Mittal J, Gupta VK. Adsorption studies on the re-
moval of coloring agent phenol red from wastewater using waste materials as
adsorbents. J Colloid Interface Sci 2009;337:345–54.
[49] Temkin MJ, Pyzhe V. Kinetics of ammonia synthesis on promoted iron cataly-
sis. Acta Physiochim URSS 1940;12:327–56.
[50] Ramnani SP, Sabharwal S. Adsorption behavior of Cr(VI) onto radiation
crosslinked chitosan and its possible application for the treatment of wastew-
ater containing Cr(VI). React Funct Polym 2006;66:902–9.
[51] Sips R. Structure of a catalyst surface. J Chem Phys 1918;16:490–5.
[52] Hameed BH. Equilibrium and kinetic studies of methyl violet sorption by agri-
cultural waste. J Hazard Mater 2008;154:204–12.
[53] Sharma P, Saikia BK, Das MR. Removal of methyl green dye molecule from
aqueous system using reduced graphene oxide as an efficient adsorbent: ki-
netics, isotherm and thermodynamic parameters. Colloids Surf A Physicochem
Eng Asp 2014;457:125–33.
[54] Amirnia S, Ray MB, Margaritis A. Copper ion removal by acer saccharum leaves
in a regenerable continuous-flow column. Chem Eng J 2016;287:755–64.
[55] Vieira SS, Magriotis ZM, Santos NAV, Cardoso MG, Saczk AA. Macauba palm
(Acrocomia aculeata) cake from biodiesel processing: an efficient and low cost
substrate for the adsorption of dyes. Chem Eng J 2012;183:152–61.
[56] Panda GC, Das SK, Guha AK. Jute stick powder as a potential biomass for the
removal of Congo red and rhodamine B from their aqueous solution. J Hazard
Mater 2009;164:374–9.
[57] Oladoja NA, Akinlabi AK. Congo red biosorption on palm kernel seed coat. Ind
Eng Chem Res 2009;48:6188–96.
[58] Han R, Ding D, Xu Y, Zou W, Wang Y, Li Y, et al. Use of rice husk for the
adsorption of Congo red from aqueous solution in column mode. Bioresour
Technol 2008;99:2938–46.
[59] Namasivayam C, Muniasamy N, Gayatri K, Rani M, Ranganathan K. Removal of
dyes from aqueous solutions by cellulosic waste orange peel. Bioresour Technol
1996;57:37–43.
[60] Bhattacharyya KG, Sharma A. Azadirachta indica leaf powder as an effective
biosorbent for dyes: a case study with aqueous Congo red solutions. J Envi-
ron Manage 2004;71:217–29.
[61] Binupriya A, Sathishkumar M, Swaminathan K, Kuz C, Yun S. Compara-
tive studies on removal of Congo red by native and modified mycelial
pellets of Trametes versicolor in various reactor modes. Bioresour Technol
2008;99:1080–8.
[62] Khambhaty Y, Mody K, Basha S. Efficient removal of brilliant blue G (BBG)
from aqueous solutions by marine Aspergillus wentii: kinetics, equilibrium and
process design. Ecol Eng 2012;41:74–83.
[63] Abbas M, Trari M. Kinetic, equilibrium and thermodynamic study on the re-
moval of Congo red from aqueous solutions by adsorption onto apricot stone.
Process Saf Environ Prot 2015;98:424–36.
[64] Yang Y, Wang G, Wang B, Li Z, Jia X, Zhou Q, et al. Biosorption of acid black 172
and Congo red from aqueous solution by nonviable Penicillium YW 01: kinetic
study, equilibrium isotherm and artificial neural network modeling. Bioresour
Technol 2011;102:828–34.
[65] Chakraborty S, Basak B, Dutta S, Bhunia B, Dey A. Decolorization and biodegra-
dation of Congo red dye by a novel white rot fungus Alternaria alternata CMERI
F6. Bioresour Technol 2013;147:662–6.
[66] Wang MX, Zhang QL, Yao SJ. A novel biosorbent formed of marine-derived
Penicillium janthinellum mycelial pellets for removing dyes from dye-contain-
ing wastewater. Chem Eng J 2015;259:837–44.
of the Taiwan Institute of Chemical Engineers (2017),