APTEFF, 52, 1-273 (2021) UDC: 66.067.8.081.3:582.542.

1:667-12
DOI: https://doi.org/10.2298/APT2152033L BIBLID: 1450-7188 (2021) 52, 33-44
Original scientific paper

REMOVAL OF METHYLENE BLUE BY BIOSORPTION ONTO STIPA

TENACISSIMA L. (ALFA) PLANTS: KINETICS, EQUILIBRIUM AND
THERMODYNAMIC STUDIES

Samir LADJALI1,2*, Nadjib DAHDOUH1, Samira AMOKRANE1, El hadj MEKATEL1,

Djamel NIBOU1
1
Laboratory of Materials Technology, Faculty of Mechanic and Engineering Processes (USTHB) BP 32,
16111, Algiers, Algeria
2
Process Engineering Department, Faculty of Science and Technology,
Mustapha Stambouli University-Mascara, Mascara, Algeria

Received: 27 September 2020 Revised: 12 February 2021 Accepted: 17 February 2021

This study examines the ability of Stipa tenacissima L. (Alfa) to biosorb the Methylene Blue dye.
Biosorption tests were performed in aqueous solution based on certain essential parameters such as
solution’s pH (2-12), solid/liquid ratio (1-6 g/L), initial dye concentration (25-125 mg/L) and contact
time (0-300 min). The Langmuir, Freundlich, Temkin and Elovich models were applied. It was found
that the equilibrium data could be fitted to the Langmuir isotherm for MB biosorption with a
maximum capacity qmax 55, 95 mg/g. The kinetic study shows that the experimental data correspond to
the pseudo-second order kinetic model. The negative Gibbs values free energy ΔG° reveal the spon-
taneity of MB biosorption at the surface of Stipa tenacissima L. The positive value of ΔH° reveals the
endothermic nature of the process.

Keywords: Stipa tenacissima L (Alfa), methylene blue, biosorption, kinetic study and thermodyna-
mic.

INTRODUCTION

Nowadays, environmental protection has become a major concern in all countries.

Therefore, there is an urge for encouraging the development of processes for the impro-
vement of waste-water treatment methods focusing on the reduction of pollution sources.
However, industrial effluents from textile, tanning, or printing activities often have high
colored pollutant loads which are difficult to biodegrade. The discharge of highly colored
compounds such as dyes can block out sunlight penetration in surface waters, hence
decreasing both photosynthetic activity and dissolved oxygen concentration and affecting
aquatic life (1). Unfortunately, during the dyeing process, large fractions of reactive colors
(10-50 percent) are wasted and an estimation is that over 7105 tons of dyes are produced
each year (2). This is why many researchers within the water treatment field are interested
in the removal of reactive dyes.
Several conventional treatments have proven ineffective in removing supplements and
dyes due to their high-water solubility. Furthermore, various techniques have been used in
the process of eliminating some soluble pollutants from industrial or domestic effluents.
They are different from each other and can be cited for illustration purposes: adsorption (3),
electrolysis (4), combined Adsorption/Photocatalysis (5), liquid-liquid extraction (6), mem-

* Corresponding author: Samir Ladjali, Process Engineering Department, Faculty of Science and Technology,
Mustapha Stambouli University-Mascara, Algeria, e-mail: [email protected]

33
APTEFF, 52, 1-273 (2021) UDC: 66.067.8.081.3:582.542.1:667-12
DOI: https://doi.org/10.2298/APT2152033L BIBLID: 1450-7188 (2021) 52, 33-44
Original scientific paper

brane filtration (7), coagulation-flocculation (8), etc. The best prospect for dye removal
tends to be adsorption on activated carbon. This adsorbent is costly and hard to recycle after
use despite its efficiency. A wide variety of inexpensive adsorbent materials, such as clay
minerals, have been identified in recent years (9) and biomasses (10). Most of the materials
studied include wastes of aquatic and agro-industrial origin like seaweed, microbial bio-
mass, pine bark, cotton, beet pulp, pine sawdust, sugarcane bagasse, jute fibers, olive ker-
nel, coconut, and rice husks (11). The studies available in the scientific literature indicate
that the biosorbents can be an alternative to the activated carbons in water treatment pro-
cesses on an industrial scale (12). Thereby, this paper examines the treatment of water-con-
taining dye such as methylene blue (MB) by following the adsorption process that is based
on the retention of a pollutant by an adsorbent. In this case, it is a natural lignocellulosic
material whose stems were chosen as the biosorbent. This study aims first and foremost to
valorize this local resource which is abundant in Algeria and to determine its biosorption
capacities regarding the dye. The fundamental investigations, mainly, include the charac-
terization of biosorbents, biosorption equilibrium, kinetics and thermodynamics. Determi-
nation of biosorption kinetics is crucial in predicting the behavior of a biosorbent in prac-
tical applications (13).
Stipa tenacissima L. is also known as Alfa in the studied region (the Arabic name for
the plant) like belongs to the grass family. It is widespread in arid regions in northwest
Africa and southern Spain. This wild plant covers large areas of the Algerian highlands and
usually blooms in the period time from April to June. However, it is a permanent plant that
survives the winter. It grows up to approximately one-meter height in the form of a cylin-
drical rod. Like any lignocellulose/lingnocellulosic biomass, Alfa stems are hard, its Latin
name is (Stipa tenacissima L.), low density, abundant in nature, renewable and 100% bio-
degradable. The untreated plant, namely Stipa tenacissima L., is examined in this study.
Methylene blue, a cationic dye, was used as a molecular model to study the biosorption
properties for the removal of the typical dye (14).

EXPERIMENTAL

MATERIALS

Biosorbent preparation

The Alfa biomass stems were manually washed with tap water to remove debris, dust,
and sand, and then it was thoroughly rinsed with distilled water, dried in the open air for 24
hours, and then warmed up in an oven at 80 °C for 48 hours. To grind the biosorbent, the
biomass was immersed in liquid nitrogen for 15 minutes to harden and weaken the stems to
facilitate the grinding process. Afterwards, they were easily crushed with a domestic
mortar. Then, the ground powder was sieved (powder fraction <0.7mm). It is noteworthy to
mention that the material did not undergo any chemical or physical treatment.

Adsorbate

Methylene blue (MB) is a cationic dye that can be used in many applications such as the
textile industry. The aforementioned is one of the common pollutants in colored effluents.

34
APTEFF, 52, 1-273 (2021) UDC: 66.067.8.081.3:582.542.1:667-12
DOI: https://doi.org/10.2298/APT2152033L BIBLID: 1450-7188 (2021) 52, 33-44
Original scientific paper

Several types of research were published on the possibility of removing the MB using
different adsorbents (15).
Effect of pH: The effect of pH on the removal of MB dye was studied in the range from
2 to 12. The pH of the solution was adjusted to the desired value by micro-additions of HCl
(0.1 M) or NaOH (0.1 M). The other parameters were kept constant: C0 = 25 mg/L, contact
time 90 min, R (S/L) of 6 g/L and at a temperature of 25 ± 2 °C. After the mixture was
centrifuged and the adsorbate was analyzed by the spectrophotometer.
Effect of adsorbent dose: the mass of Stipa tenacissima L was determined by a series of
experiments that contributed to the optimal biosorption by methylene blue. Consequently, a
range from 1 to 6 g/L was selected.
Effect of initial methylene blue concentration: the MB concentrations were varied from
25 to 125 g/L while keeping the other operating conditions constant to determine the effect
of the initial concentration of MB on the removal percentage.
Effect of contact time: The equilibrium time is an important parameter, it is determined
following the achievement of a kinetic of MB biosorption at an initial concentration of 100
mg/L; R(S/L) of 6 g/L and the pH of the solution is 12. Several samples in time were taken,
such as t = 5, 15, 30, 50, 60, 90, 120 and 180 min to determine the optimum time corres-
ponding to the best MB biosorption yield. The removal percentage (%) of MB was deter-
mined using equation [1]:

% 100 [1]

The capacity qe (mg/g) was calculated by the following expression (Eq. 2):

[2]

where, C0 and Ce represent the initial and the equilibrium concentration (mg/L) of MB
respectively, m is the mass of the biosorbent used (g) and V is the volume of the dye solu-
tion (L).

BIOSORPTION ISOTHERMS

Biosorption isotherms play a major role in determining maximum capacities and iden-
tifying the type of isotherm. Therefore, the four classical isothermal models (Langmuir,
Freundlich, Temkin, and Elovich) were used to describe the removal mechanism of MB
from biomass to establish the relationship between the amount of MB adsorbed and its
equilibrium concentration in the solution. The Langmuir, Freundlich, Temkin and Elovich
linearized equations are as follows [3], [4], [5], and [6], respectively (5, 16-19):

1 1 1
[3]

1
[4]

35
APTEFF, 52, 1-273 (2021) UDC: 66.067.8.081.3:582.542.1:667-12
DOI: https://doi.org/10.2298/APT2152033L BIBLID: 1450-7188 (2021) 52, 33-44
Original scientific paper

[5]
1
[6]

where, Ce (mg/L) is the equilibrium concentration; qm (mg/g) is the maximum biosorption

capacity; KL (L/mg) is the Langmuir constant; KF (mg 1−1/n L1/n g-1) is the Freundlich
constant; n: the intensity of biosorption; KT (L/mg) is the Temkin isothermal constant; bT
Variation in biosorption energy (J/mol); KE (L/mg) represents the Elovich equilibrium
constant.

BIOSORPTION KINETICS

The biosorption data obtained by experimental methods were fitted for pseudo-first
order, pseudo-second order and intraparticle diffusion models (equations 7-9, respectively)
to describe and interpret the biosorption process of MB on biomass and to calculate the
various parameters that characterize the biosorption kinetics, as follows (16):

[7]

1 1
[8]

,
[9]

where, qe (mg/g) and qt (mg/g) are the adsorption capacities at equilibrium and at time t,
respectively, while k1(min-1), k2 (mg/g min) and Kint (mg/g min0.5) are the biosorption rate
constants of first-order, second-order kinetic and intraparticle diffusion models, and c is a
constant related to the thickness of the boundary layer.

THERMODYNAMIC STUDY

The thermodynamic parameters of the biosorption process, namely free enthalpy (∆G°),
enthalpy (∆H°), and entropy (∆S°) explain the mechanism of the biosorption process of the
cationic MB dye by Alfa biomass. The biosorption distribution coefficient (Kd) is given by
the equation [10] (21):

[10]

The variation of enthalpy (∆Ho) and entropy (∆So) can be obtained from the slope and
intercept of the ln Kd plot as a function of (1/T) equation [11]. The Gibbs free enthalpy of
biosorption is calculated by the equation [12] (22):
∆ ∆
[11]

36
APTEFF, 52, 1-273 (2021) UDC: 66.067.8.081.3:582.542.1:667-12
DOI: https://doi.org/10.2298/APT2152033L BIBLID: 1450-7188 (2021) 52, 33-44
Original scientific paper

∆ ∆ ∆ [12]

where, R (8.314 J /mol K) is the universal gas constant and T is the absolute temperature.

RESULTS AND DISCUSSION

EFFECT OF PH

Several studies have demonstrated that pH is an important factor to determine the

biosorption capacity of organic cationic and anionic compounds (22) since it can influence
both the adsorbent and adsorbate surface properties. In addition to the biosorption mecha-
nism, it is highly observable that the removal percentage of MB and the biosorption capa-
city increase with the increase of pH (Fig. 1).

Figure 1. Effect of initial pH on MB removal and biosorption capacity (Co= 25 mg/L,

R= 6 g/L, Time = 90 min and T= 298 ± 2 K).

The pKa of MB is 0.04, therefore, methylene blue is completely ionized at a pH above

0.04 and exists in a cationic form (22, 23). The surface of the biosorbent is negatively
charged at pH values above pHZPC= 4.15 (14), which increases the electrostatic attraction of
the positively charged dye cations, and hence it increases the biosorption of methylene blue
(22, 24). A decrease of biosorption of methylene blue at low pH values was observed,
besides, the highest removal percentage (85.54 %) and adsorbed amount (52.45 mg/g) were
also obtained at pH=12.
That can be explained by the fact that the electrostatic repulsion between the cations and
the positively charged biosorbent surface is present at low pH values, Moreover, the me-
thylene blue cations can replace the ion on the surface of the biosorbent, resulting in an
increased biosorption by the ion exchange mechanism (24). The biosorption might be ex-
plained by pure electrostatic interactions between the biosorbent negatively charged and the
methylene blue positive charge (25). The dye's adsorption capacity depends on both the
adsorbent's surface properties and the dye’s structure (26-27).

37
APTEFF, 52, 1-273 (2021) UDC: 66.067.8.081.3:582.542.1:667-12
DOI: https://doi.org/10.2298/APT2152033L BIBLID: 1450-7188 (2021) 52, 33-44
Original scientific paper

EFFECT OF BIOSORBENT DOSE

Fig.2 shows the effect of the Alfa biomass dose on the removal percentage of methylene
blue and biosorption capacity. Therefore, it can be noted that the removal percentage of MB
increases with the increase of Alfa biomass dose, while the opposite trend is observed for
the biosorption capacity. The biosorption percentage of MB increased from 6.92 % to
92.25%, while the optimal dose of Alfa biomass is 6 g/L. The increase in the removal per-
centage of MB with an increasing ratio (S/L) is mainly due to the growing number of active
sites available on the biosorbent surface. According to this curve, it is clear that the dose
(S/L) of the biosorbent plays a very important role in the biosorption process.

Figure 2. Influence of biosorbent dose on MB removal and biosorption capacity

(Co= 25 mg/L, pH=12, R= 1-6 g/L, Time = 90 min and T= 298 ± 2 K).

Retrospectively, the adsorbed amount decreased from 55.27 to 22.43 mg/g. This can be
explained by a large number of available active sites that are free in the biosorption medium
making the MB cations difficult to approach the biosorption sites due to crowding. In
addition, a large dose of biosorbent generates agglomerations of particles.
Furthermore, small quantities of biosorbent could be dispersed in the aqueous phase,
facilitating the accessibility of the MB molecules to a large number of free sites of the ma-
terial. A similar phenomenon was observed by Somasekhara Reddy et al. (2012) (28) in
their study of Cango red adsorption on Jujube grains. Reddy attributed the decrease in the
amount adsorbed on the adsorbent surface by increasing the initial dose to the establish-
ment of adsorption sites during the process.

EFFECT OF INITIAL MB CONCENTRATION

Figure. 3 shows a rapid increase in biosorption for low concentrations, highest removal
(92%) was obtained at Co = 25 mg/L, and the best biosorption yields are 86.54 %, 81.6%,
75.25%, and 69.47 % for 50, 75, 100 and 125 mg/L respectively. Based on these results, it
can be concluded that the optimal concentration was 25 mg/L for the best MB removal
efficiency.

38
APTEFF, 52, 1-273 (2021) UDC: 66.067.8.081.3:582.542.1:667-12
DOI: https://doi.org/10.2298/APT2152033L BIBLID: 1450-7188 (2021) 52, 33-44
Original scientific paper

Figure 3. Effect of initial concentration on the removal of MB

(R= 6 g/L, pH ~ 12 and T= 298 ± 2 K).

The fixation of the MB cations on the active sites of the biosorbent was rapid due to
their low content at low concentration. The increase of the MB concentration can be ex-
plained by the rapid saturation of active sites resulting in a decrease in removal efficiency.

EFFECT OF CONTACT TIME

The analysis of the results observed in figure 4 shows that the biosorption kinetics of
MB occurring in two phases. The first phase is fast at the beginning of the process due to
the high availability of the biomass-free active sites, whereas the second phase becomes
slower overtime to reach equilibrium.

Figure 4. Effect of contact time on the removal of MB

(Co= 25 mg/L, R= 6 g/L, pH ~ 12 and T=298 ± 2 K).

39
APTEFF, 52, 1-273 (2021) UDC: 66.067.8.081.3:582.542.1:667-12
DOI: https://doi.org/10.2298/APT2152033L BIBLID: 1450-7188 (2021) 52, 33-44
Original scientific paper

The large number of free surface sites available is certainly responsible for the high
adsorption efficiency at the beginning, while the subsequent deceleration is likely due not
only to the decrease in available sites but also to repulsive forces among adsorbed dye
molecules and those present in the solution (5). The equilibrium biosorption time is reached
after 90 min and efficiency of 92%.

BIOSORPTION ISOTHERMS

The analyses of the results obtained from the biosorption of MB studied on the biomass
Alfa (Table 1) demonstrates that the correlation coefficient value (R2) of the Langmuir
isotherm (0.99) is higher than that of Freundlich, Temkin and Elovich. This implies that
Langmuir’s model is better for the description of the biosorption process of MB on Alfa
biomass. The dimensionless factor (RL) was calculated to confirm that Langmuir's model
corresponds to the experimental results and is presented in the form (29):

[13]

The RL factor was defined by Hall (1966) (29) as the separation factor whereK is the
Langmuir constant and C0 is the initial concentration of the MB cations (mg/L). The RL
value indicates the nature of the biosorption process:
- Unfavorable for RL>1.
- Favorable for 0 < RL < 1.
- Irreversible (RL = 0) and Linear (RL = 1).
The RL values of MB biosorption were 0.011<RL<0.055 (Table1), indicating that the
biosorption process is favorable. Comparing the current study with other investigations,
Table 2 demonstrates different adsorbent materials used in recent research that explains the
removal of methylene blue and their adsorption capacities.

Table 1. Isotherms models parameters for the biosorption of MB

by Stipa Tenacissima L. (Alfa)

Isotherm model Parameters Values

qm (mg/g) 55.95
b (L/mg) 0.68
Langmuir
R2 0.997
RL 0.011<RL<0.055 25<C0<125(mg/L)
KF (mg 1− 1/n L1/n g− 1) 22.87
Freundlich n 4.43
R2 0.842
KT (L/mg) 3.10
Temkin bT 315.61
R2 0.943
qm(mg/g) 28.23
Elovich KE (L/mg) 0.65
R2 0.873

40
APTEFF, 52, 1-273 (2021) UDC: 66.067.8.081.3:582.542.1:667-12
DOI: https://doi.org/10.2298/APT2152033L BIBLID: 1450-7188 (2021) 52, 33-44
Original scientific paper

Table 2. Comparison of adsorption capacities of some materials

with Stipa tenacissima L. in MB removal

Adsorbents Adsorption capacity (mg/g) Reference

SW PMMA 97.09 (30)
Kaolin 52.76 (31)
Raz luffa cylindrical 49.46 (32)
Lignite 41.49 (33)
Stipa tenacissima L. 55.95 This study
Prunuscerasefera (PRUN) 143 (22)

BIOSORPTION KINETIC

Based on the results in Table 3, it can be stated that the pseudo-second order model is
the best for describing the biosorption process of MB on the studied biomass since it pro-
vided a high value of correlation coefficient (R2 > 0.99).

Table 3. Kinetic parameters for the MB biosorption by Stipa tenacissima L. (Alfa).

Pseudo-first order Pseudo-second order Intraparticle diffusion

Kin *102
Co qe (exp) qe (cal) k1 qe(cal) k2
(mg/g.min0.5) R2
(mg/L) (mg/g) (mg/g) (1/min) R2 (mg/g) (g /mg.min) R2

25 48.49 8.26 0.054 0.815 27.26 0.072 0.997 5.22 12.47 0.799
50 34.27 10.25 0.048 0.824 34.89 0.039 0.994 7.36 31.51 0.825
75 41.58 28.25 0.031 0.789 41.38 0.028 0.997 8.47 58.25 0.902
100 49.89 22.95 0.044 0.799 49.58 0.010 0.998 11.03 76.58 0.858
125 54.25 1575 0.052 0.802 53.99 0.011 0.994 13.25 82.48 0.876

Similarly, it can be noted that the qe values calculated by the pseudo-second order mo-
del are very close to those determined experimentally, which further justifies the fact that
the biosorption kinetics are of the pseudo-second order.
Table 4 summarizes the values of free Gibbs enthalpy (ΔGo), enthalpy (ΔHo), and en-
tropy (ΔSo). The analysis of these thermodynamic parameters reveals that the removal of
MB by Alfa biomass is a spontaneous reaction (ΔG°). The decrease of ΔG° with increasing
temperature shows that biosorption is more favorable at high temperature. The value of the
variation in the entropy of MB biosorption is positive, which means that the molecules in
the liquid phase are more organized than those in the solid-liquid interface (34). The posi-
tive value of ∆H° obtained shows that the biosorption process is endothermic.

Table 4. Thermodynamic parameters for the biosorption of MB

onto Stipa tenacissima L. (Alfa).

ΔH° (kJ/mol) ΔS° (J/mol K) ΔG° (kJ/mol)

T(K) 298 303 313 323
22.52 84.45 -25.73 -25.65 -26.41 -27.24

41
APTEFF, 52, 1-273 (2021) UDC: 66.067.8.081.3:582.542.1:667-12
DOI: https://doi.org/10.2298/APT2152033L BIBLID: 1450-7188 (2021) 52, 33-44
Original scientific paper

The value of ∆H° indicates that the biosorption of MB on Alfa biomass was controlled
by the physiosorption process, it is estimated below 40 kJ/mol. The biosorption process be-
comes chemical when ∆H° values are comprised between 40 and 120 kJ/mol (30).

CONCLUSION

Moreover, the natural biosorbent Stipa tenacissima L. was successfully used for the re-
covery of MB in an aqueous solution. In addition, optimal conditions for maximum MB re-
moval were determined as follows: pH = 12, biosorbent dose = 6 g/L and initial MB con-
centrations = 25 mg/L. Optimization of these parameters resulted in a satisfactory removal
efficiency and a 92% removal rate was achieved during 90 minutes. As a result, the Lang-
muir model provided a satisfactory correlation and proved to be the best for describing the
biosorption of MB on the surface of the biomass which suggests the formation of a mono-
layer of the MB dye on the biosorbent surface. The RL values for the biosorption of MB are
less than 1, demonstrating that the biosorption process is favorable. Moreover, the biosorp-
tion kinetics of MB generally follows a pseudo-second order law.
The thermodynamic study shows that the biosorption of MB on the biomass used is
spontaneous, endothermic and the biosorption process is physical. In summary, this work
proves that the available biomass Stipa tenacissima L. is a promising biological material for
the removal of cationic dyes like MB.

REFERENCES
1. Al-Degs, Y.S.; El-Barghouthi, M.I.; Khraisheh, M.A.; Ahmad, M.N.; Allen, S.J. Effect of surface
area, micropores, secondary micropores, and mesopores volumes of activated carbons on reactive
dyes adsorption from solution. Sep. Purifi. Technol. 2004, 39, 97-111.
2. Al-Duri, B.; Khader, K.; McKay, G. Prediction of binary compound isotherm for adsorption on
heterogeneous surfaces. J. Chem. Technol. Biotechnol. 1992, 53, 345-352.
3. Abdel-Ghani, N.T.; El-Chaghaby, G.A.; Helal, F.S. Preparation, characterization and phenol
adsorption capacity of activated carbons from African beech wood sawdust. Global. J. Environ.
Sci. Manag. 2016, 2(3), 209-222.
4. Rana, P.; Mohan, N.; Rajagopal, C. Electrochemical removal of chromium from wastewater by
using carbon aerogel electrodes. Water Res. 2004, 38 (12), 2811-2820.
5. Mekatel, E.; Amorkrane, S.; Trari, M.; Nibou, D.; Ladjali, S. Combined adsorption/photocata-
lysis process for the decolorization of Acid Orange 61. Arabian. J. Sci. Eng. 2019, 44(6), 5311-
5322.
6. Senol, A. Amine extraction of chromium (VI) from aqueous acidic solutions. Sep. Purif. Technol.
2004, 36 (1), 63-75.
7. Religa, P.; Kowalik-Klimczak, A.; Gieryc, P. Study on the behavior of nanofiltration membranes
using for chromium (III) recovery from salt mixture solution. Desalination. 2013, 315, 115-123.
8. Prakash, N.B.; Sockan, V.; Jayakaran, P. Wastewater treatment by coagulation and flocculation.
Int. J. Eng. Sci. Innov. Techn. 2014, 3(2), 479-484.
9. Toor, M.; Jin, b. isotherm, kinetics, and diffusion of modified natural bentonite for removing
diazo dye. Chem. Eng. J. 2012, 187, 79-88.
10. Kumar, R.; Ahmad, R. Biosorption of hazardous crystal violet dye from aqueous solution onto
treated ginger waste (TGW). Desalination. 2011, 265, 112-118.
11. Abramian, L.; El Rassy H. Adsorption kinetics and thermodynamics of azo-dye Orange II onto
highly, porous titania aerogel. Chem. Eng. J. 2009, 150, 403-410.

42
APTEFF, 52, 1-273 (2021) UDC: 66.067.8.081.3:582.542.1:667-12
DOI: https://doi.org/10.2298/APT2152033L BIBLID: 1450-7188 (2021) 52, 33-44
Original scientific paper

12. Yacoumi, S.; Tien, C. Kinetics of Metal Ion Adsorption from Aqueous Solutions. Kluwer
Academic Publisher. 1995.
13. Brdar, M. M.; Kukić, D. V.; Šćíban, M. B.; Vasić, V. M.; Prodanović, J. M. Comparison of the
generalized and preset-order kinetic equations for description of biosorption data. Acta Period.
Technol. 2018, 49, 11-20.
14. Ladjali, S.; Amokrane, S.; Mekatel, E.; Nibou,D. Adsorption of Cr (VI) on Stipa tenacissima L
(Alfa): Characteristics, kinetics and thermodynamic studies. Sep. Sci. Technol. 2019, 54(6), 876-
887.
15. Kannan, N.; Sundaram, M.M. Kinetics and mechanism of removal of methylene blue by ad-
sorption on various carbons - comparative study. Dye.Pigment. 2001, 51, 25-40.
16. Rangabhashiyam, S.; Anu, N.; Nandagopal, M. G.; Selvaraju.; Environ. N. J. Relevance of iso-
therm models in biosorption of pollutants by agricultural byproducts. Chem. Eng. 2014, 2 (1),
398-414.
17. Papegowda, P.K.; Syed, A.A. Isotherm, kinetic and thermodynamic studies on the removal of
methylene blue dye from aqueous solution using Saw Palmetto spent. Int. J. Environ. Res. 2017,
11(1), 91-98.
18. Ratnamala, G.M.; Deshannavar, U.B.; Munyal, S.; Tashildar, K.; Patil, S.; Shinde, A. Adsorption
of reactive blue dye from aqueous solutions using sawdust as adsorbent: optimization, kinetic, and
Equilibrium studies. Arab. J. Sci. Eng. 2016, 41(2), 333-344
19. Elovich, S.Y.; Larinov, O.G. Theory of adsorption from solutions of non electrolytes on solid (I)
equation adsorption from solutions and the analysis of its simplest form (II) verification of the
equation of adsorption isotherm from solutions. Izv. Akad. Nauk. SSSR Otd. Khim. Nauk. 1962,
2(2), 209-216.
20. Gürses, A.; Hassani, A.; KıranYan, M.; AçıYlı, Ö. Karaca, S. Removal of methylene blue from
aqueous solution using by untreated lignite as potential low cost adsorbent: Kinetic, thermo-
dynamic and equilibrium approach. J. Water Process Eng. 2014, 2, 10-21.
21. Aid, A.; Amokrane, S.; Nibou, D.; Mekatel, E.; Trari, M.; Hulea, V. Modeling biosorption of
Cr(VI) onto Ulvacompressa L. from Aqueous solution. Water Sci. Technol. 2017, 77(1), 60-69.
22. Ouldmoumna, A.; Reinert, L.; Benderdouche, N.; Bestani, B.; Duclaux, L. Characterization and
application of three novel biosorbents “Eucalyptus globulus, Cynaracardunculus, and Prunus
cerasefera” to dye removal. Desalin. Water. Treat. 2013, 51(16-18), 3527-3538.
23. Weng, C. H.; Lin, Y. T.; Tzeng, T. W. Removal of methylene blue from aqueous solution by
adsorption onto pineapple leaf powder. J. Haz. Mater. 2009, 170 (1) 417-424.
24. Seco, A.; Marzal, P.; Gabaldon, C. Study of the adsorption of Cd and Zn onto an activated
carbon: influence of pH, cation concentration, and adsorbent concentration. Sep. Sci. Technol.
1999, 34(8), 1577-1593.
25. Rey-Castro, C.; Lodeiro, P.; Herrero, R.; Sastre de Vicente; Environ, M. E. Acid-base properties
of brown seaweed biomass considered as a Donnan gel. A model reflecting electrostatic effects
and chemical heterogeneity. Sci. Technol. 2003, 37(22), 5159-5167.
26. Lin, J. X.; Zhan, S. L.; Fang, M. H.; Qian, X. Q.; Yang, H. Adsorption of basic dye from aqueous
solution onto fly ash. J. Environ. Manage. 2008, 87(1), 193-200.
27. Khattria, S. D.; Singh, M. K. Removal of malachite green from dye wastewater using neem
sawdust by adsorption. J. Hazard. Mater. 2009, 167(1-3), 1089-1094.
28. Somasekhara Reddy, M.C.; Sivaramakrishna, L.; Varada Reddy, A. The use of an Agricultural
waste material, Jujuba seeds for the removal of anionic dye (Congo red) from aqueous medium. J.
Hazar Mater. 2012, 203, 118-127.
29. Hall, K.R.; Eagleton, L.C.; Acrivos, A.; Vermeule, T. Pore-and solid-diffusion kinetics in fixed-
bed adsorption under constant-pattern conditions. Ind. Eng Chemi Fundam. 1966, 5 (2), 212-223.
30. Dahdouh, N.; Amokrane, S.; Murillo, R.; Mekatel, E.; Nibou, D. Removal of Methylene Blue
and Basic Yellow 28 Dyes from Aqueous Solutions Using Sulphonated Waste Poly Methyl
Methacrylate. J. Polym. Environ. 2020, 28(1), 271-283.

43
APTEFF, 52, 1-273 (2021) UDC: 66.067.8.081.3:582.542.1:667-12
DOI: https://doi.org/10.2298/APT2152033L BIBLID: 1450-7188 (2021) 52, 33-44
Original scientific paper

31. Mouni, L.; Belkhiri, L.; Bollinger, J. C.; Bouzaza, A.; Assadi, A.; Tirri, A.; Dahmoune, F.; Ma-
dani, K.; Remini, H. Removal of Methylene Blue from aqueous solutions by adsorption on
Kaolin: Kinetic and equilibrium studies. Appl. Clay. Sci. 2018, 153, 38-45.
32. Boudechiche, N.; Mokaddem, H.; Sadaoui, Z.; Trari, M. Biosorption of cationic dye from aqueo-
us solutions onto lignocellulosic biomass (Luffa cylindrica): characterization, equilibrium, kinetic
and thermodynamic studies. Int. J. Ind. Chem. 2016, 7, 167-180.
33. Gürses, A.; Hassani, A.; KıranYan, M.; AçıYlı, Ö.; Karaca, S. Removal of methylene blue from
aqueous solution using by untreated lignite as potential low cost adsorbent: Kinetic, ther-
modynamic and equilibrium approach. J. Water Process Eng. 2014, 2, 10-21.
34. Ho, Y.S. Review of second-order models for adsorption systems. J. Hazard. Mater. 2006, 136,
681-689.

44