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Methylene blue adsorption on magnetic alginate/rice husk bio-

composite

Erol Alver, Ayşegül Ülkü Metin, Francois Brouers

PII: S0141-8130(19)38425-9
DOI: https://doi.org/10.1016/j.ijbiomac.2020.02.330
Reference: BIOMAC 14947

To appear in: International Journal of Biological Macromolecules

Received date: 17 October 2019

Revised date: 28 February 2020
Accepted date: 29 February 2020

Please cite this article as: E. Alver, A.Ü. Metin and F. Brouers, Methylene blue adsorption
on magnetic alginate/rice husk bio-composite, International Journal of Biological
Macromolecules(2020), https://doi.org/10.1016/j.ijbiomac.2020.02.330

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© 2020 Published by Elsevier.

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Methylene Blue Adsorption on Magnetic Alginate/Rice Husk Bio-

composite

Erol Alvera*, Ayşegül Ülkü Metinb, Francois Brouersc

a
Department of Chemical Engineering, Faculty of Engineering, Hitit

University, 19030, Çorum, Turkey e-mail: erolalver@hotmail.com

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b
Department of Chemistry, Faculty of Science and Arts, Kırıkkale University,

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Yahşihan 71450, Kırıkkale, Turkey
c

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Faculty of Applied Sciences, Liège University, Belgium
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*
Corresponding author:

Dr. Erol Alver

Department of Chemical Engineering

Faculty of Engineering, Hitit University, Turkey

e-mail: erolalver@hotmail.com

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Abstract

Magnetic alginate/rice husk (m-ALG/RH) bio-composite beads prepared with

ionotropic gelation method and used for methylene blue (MB) removal.

Structural analysis of magnetic alginate/rice husk composite beads was

performed using FTIR, SEM-EDS and TGA techniques. The accomplishment

of magnetic alginate/rice husk composite beads as an adsorbent for the

removal methylene blue was investigated from aqueous solution. Maximum

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experimental adsorption capacity of the bio-composite beads was calculated

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as 274.9 mg/g. The various process parameters such as pH, temperature

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and initial MB concentration optimized. It was determined that pH no
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significant effect on dye removal efficiency of beads while temperature and
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ionic strength caused a decrease on removal efficiency. The various isotherm

models were applied for determine the adsorption mechanism and Freundlich
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isotherm model is more compatible with the experimental data. The kinetic
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studies showed that the adsorption of methylene blue can be well described
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by the fractal Brouers-Sotolongo kinetic model. The thermodynamic

calculations indicated that methylene blue adsorption was a spontaneous and

exothermic nature. The results showed that the magnetic alginate/rice husk

bio-composite as low-cost and eco-friendly adsorbent can be effectively used

for cationic dye removal steps in the environmental engineering applications.

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Keywords: Alginate, Rice Husk, bio-composite, Methylene Blue adsorption,

Brouers-Sotolongo Model

1. Introduction

Dyes are widely used in different industries such as textiles, paper, food,

cosmetics, pharmaceuticals and leather [1-4]. The waste dyes resulting from

industrial activities constitute significant environmental problems due to it

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has toxic and carcinogenic effect [3,5,6]. Dyes can be classified as anionic,

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cationic and non-ionic. Methylene blue, classified as cationic dye category, is

one of the dyes widely used in industry [3, 7,8]. Although MB is not
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considered to be highly toxic, it causes negative influence such as
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inflammation of leptomeninges, neuronal apoptosis, heart rate increasing,
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nausea and vomiting in human health as well as pollution in the water [7-9].
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To overcome dye pollution in the water, various methods such as membrane

separation, flocculation, coagulation, aerobic or anaerobic treatment, cloud

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point extraction, chemical oxidation, ion exchange and adsorption have been
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tested [5,10,11] . Among them, one of the simplest, cheap and effective

physical process is adsorption that has also simple design requirements for

the treatment of wastewater [1,5,11,12]. Alginate is one of the most

commonly used natural biopolymer to remove dyes and heavy metals from

aqueous solutions [13-19]. Alginate, which is a water-soluble a linear binary

copolymer consisting of -D-mannuronic acid and guluronic acid units, is a

natural anionic polysaccharide extracted mostly from Brown seaweed

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[13,20,21]. It widely utilizes in food and biomedical applications due to its

biocompatibility, biodegradability, nontoxicity, high gelation, viscosity and

stabilizing properties as well as economical and abundance [4-13,22-24].

Furthermore, alginate is used as adsorbent in the removal of basic dyes and

heavy metals from wastewater due to the presence of negatively charged

carboxyl groups [18,22,25,26].. Alginate forms the hydrogel in the so-called

“egg box” structure with the ionotropic gelation in the presence of cations

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usually divalent or trivalent [21,27]. One of the most used gelation agents is

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calcium ions for alginate [1,2].

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Rice Husk which is an agricultural waste consists of cellulose, hemicelluloses,
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lignin, silica and crude protein and has been reported in the literature to be a
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good adsorbent for removal of many metals and basic dyes [10,28-31]. Rice

husk, containing organic and inorganic substances, is chemically stable and

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has high mechanical strength [32]. In addition to, the rice husk, an
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agricultural waste material having no commercial significance, can be found

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as cheap and plentiful [33,34]. On the other hand, magnetic particles are

often added to the polymeric materials to increase the adsorbent properties

and to remove them easily in the solution medium after use [18,25,26].

From this point of view, in this study, the magnetic alginate/rice husk (m-

ALG/RH) bio-composite beads was synthesized by adding rice husk into the

alginate solution. Adding rice husk into alginate both improve its mechanical

strength and remove methylene blue more effectively with the synergistic

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effect. According to our research, no study on preparing magnetic

Alginate/Rice Husk composite beads used as an adsorbent for the removal of

organic or inorganic pollutants has been previously reported. The properties

of bio-composite were determined by FTIR, SEM-EDS and TGA techniques.

The effect of various process parameters such as pH, adsorbent amount and

ionic strength on methylene blue removal were studied in batch system and

the obtained data were evaluated using various isotherm and kinetic models.

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2.1. Chemicals and Reagents
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The cationic dye Methylene Blue (MB) and Na-Alginate were purchased from
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Sigma–Aldrich. All other reagents were analytic grade and were supplied by

Merck.
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2.2. Preparation of Magnetic Alginate/Rice Husk Bio Composite

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Beads
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For the preparation of the (m-ALG/RH) bio-composite beads, alginate

solution was prepared (2% w/v) in deionized water. Firstly, Rice husk (0.05

g, <45µm) was dispersed in alginate solution (10 mL, 2% w/v) for 30 min

and the alginate/rice husk composite solution was dropped slowly into 50mL

CaCl2 (2%w/v) and FeCl3 (0.05 M) solution by a syringe needle. To complete

crosslinking reaction, the alginate/rice husk beads were left in the CaCl2

solution for 24 h, and then filtered out and washed using distilled water.

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Then, the cross-linked alginate/rice husk beads were transferred into 25 mL

NH3 stock solution (25%w/w). For magnetization of beads, 5 mL 0.25 M

FeCl2 was added to the above solution and stirred for 30 min. The magnetic

bio-composite beads were magnetically separated from reaction medium and

washed with distilled water (Figure 1).

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Figure 1. Schematic presentation of the preparation of the magnetic

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alginate/rice husk bio-composite beads.

2.3. Characterization

The maximum absorbance wavelength and concentration of Methylene Blue

during adsorption studies were measured with a UV–vis spectrometer

(Thermo Scientific / Evolution-201).

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The functional groups of the bio-composite beads were identified using

Fourier transform infrared (FTIR)-Raman spectroscopy (Thermo Scientific /

Nicolet IS50).

The surface morphology of the bio-composite beads was examined by using

a scanning electron microscope (FEI / Quanta 450 FEG) coupled with energy

dispersive spectroscopy (EDS) spectrometer.

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The morphologic properties of the bio-composite beads was examined by

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using a scanning electron microscope (FEI / Quanta 450 FEG) coupled with

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energy dispersive spectroscopy (EDS) spectrometer.
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Thermogravimetric analysis (TGA) of bio-composite beads were carried out
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by Mettler – Toledo / TGA / DSC 1 HT TGA instrument.

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Magnetic hysteresis curve of alginate/rice husk bio-composite beads was

obtained by vibrating sample magnetometer (VSM, Cryogenic Limited PPMS).

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A Thermo Scientific ICE 3500 model Flame Atomic Absorption

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Spectrophotometer (AAS) was used to determine the amount of iron content

in bio-composite beads .

Free carboxyl groups on bio-composite beads has been analyzed by

potentiometric titration [REF]. For this purpose, the m-ALG/RH bio-

composite beads (0.2 g) was allowed soak into distilled water (10 mL) for

24.0 h. Then, the m-ALG/RH bio-composite beads was treated with NaOH

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solution (0.1 M,10.0 mL) for 2.0 h. At the end of this period, the bio-

composite beads removed and the residual solution was assayed by titration

with HCl solution (0.1 M). The amount of available free carboxylic acid was

calculated as mmol/g bio-composite beads [35].

2.4. Dye Removal Studies

Dye removal studies were performed in dye solution (50 mL) with m-ALG/RH

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bio-composite beads. The pH of the dye solution is adjusted between 3–10

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using diluted HCl or NaOH solutions. A known mass of m-ALG/RH bio-

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composite beads was then added to the dye solution and shaken at 150 rpm
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and 20 °C. The effect of process variables such as pH, temperature, and
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ionic strength on the removal efficiency of dye was investigated.

The amount of adsorbed dye using the bio-composite beads was determined
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to the following equations:

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q=(Co-Ce)*V/m (1)
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%R=(Co-Ce)/Co*100 (2)

where q is the amount of adsorbed dye on the bio-composite beads (mg/g),

Co and Ce are the initial and the equilibrium concentration of dye in

solution(mg/L), respectively. V (L) is the volume of the MB solution, and m

(g) is the mass of the dried bio-composite. After each adsorption process, m-

ALG/RH bio-composite beads were removed from the aqueous phase using a

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magnet, and the residual dye concentrations were measured using a UV−vis

spectrophotometer at 665 nm.

To explain the interaction mechanism between the adsorbent−adsorbate

system at equilibrium, several adsorption models are used. In this study,

the equilibrium data were analyzed using Langmuir, Freundlich and Dubinin-

Raduskevich isotherms presented in Table 1.

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To description of adsorption mechanism, the adsorption rate at the

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solid/solution interface was determined using several kinetic models such as

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pseudo-first-order and pseudo-second-order model [36,37 ]:.
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ln(qe−qt)= lnqe−k1t (3)
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t/qt = t/ qe + 1/k2 qe2 (4)

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where qe and qt are the adsorption uptake at equilibrium and at any time t

(mg/g), respectively.
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On the other hand, experimental data was also analyzed using fractal
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Brouers-Sotolongo model for sorption kinetic analysis that the details of this

model had been given as follows:

The BSF(n,a) Brouers-Sotolongo kinetic equation has been used now in a

number of recent papers [38,39]. It reads:

1
−
𝑡 𝑎 𝑛−1
𝐵𝑆𝑓(𝑛, 𝛼) ≡ 𝑞(𝑡) = 𝑞𝑚𝑎𝑥 [1 − 1 + (𝑛 − 1) 𝜏
] (5)

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Where 𝑞 (𝑡) is the time dependent adsorbed quantity (in convenient units or

percentage), and 𝑞𝑚𝑎𝑥 the maximum adsorbent capacity in appropriates

unit. 𝜏 is a characteristic time, a fractal time exponent, and n a fractional

reaction order. The half time 𝜏50% corresponding to 𝑞(𝑡) =0.5 𝑞𝑚𝑎𝑥 is given by:

[38-41].

(0.5)−𝑛+1 −1 1/𝛼
𝜏50% = 𝜏( ) (6)
𝑛−1

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As discuss in references [39,40] from the general equation BSf(n, 𝛼 )

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equation, one can derive some of the most used empirical sorption kinetics

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equations: BSf(1,1) is the pseudo -first order kinetics equation; BSf(1, 𝛼) is
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the fractal pseudo-first order or Weibull-Avrami equation; BSf(2,1) is the
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pseudo-second order kinetics equation; BSf(2, 𝛼) is the Hill (or log-logistic)

kinetics equation.
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The difference with classical kinetic models is the introduction of a fractal

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time which can better represent the time evolution of the system.
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In some of the previous papers on sorption in porous materials, we had to

introduce a time dependent fractal coefficient to account for the change of

sorption conditions with time. This improvement of the theory can be used in

this context too in order to achieve a better fit of the release curves. We

assumed a power law behavior which is common in complex systems in the

following form:

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𝛼(𝑡) = 𝛼0 + (𝛼𝑠 − 𝛼0 (𝑡/ 𝑡𝑠 )𝜈 ) (7)

where 𝜈 is a empirical parameter and 𝑡𝑠 a time corresponding to the

saturation of the release. In this paper we will use this expression Eq. 5 with

𝛼 replaced by 𝛼(𝑡) (Eq.7). The variation of the fractal coefficient with time is

a replaced by manifestation of the change of the interaction at the surface

occurring as the sorption process proceed in time.

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The time dependent rate R(t) [38,39] corresponding to the first order

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Equation (7) whose solution is Eq.5 with 𝛼 replaced by 𝛼(𝑡) (Eq.7) in the

definition of R(t) [41]. -p

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dq(t)
= −R(t)q(t) (8)
dt
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is given by
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t α(t) 1 1 t ν−1 t t
R(t) = ( t α(t) + t (αs − α0 ) ln(t )/(1 + (n − 1)(t )α(t) ) (9)
τ ts
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s s s
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3. RESULTS AND DISCUSSION

Preparation mechanism of magnetic biocomposite beads,

magnetic/alginate/rice husk, is showed in Figure 1. In brief, the mixed

solution of rice husk (RH) and alginate (ALG) was added to CaCl2 and FeCl3

solution and then ammonia and FeCl2 was added to form m-ALG/RH beads.

After synthesis, the amount of iron content and the available free carboxylic

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acid groups of m-ALG/RH bio-composite beads were determined as 214.2

mg/g by AAS and 14.28±0.55 mmol/g by potentiometric titration.

FTIR Study: The FTIR spectra of the m-ALG/RH and MB adsorbed-ALG/RH

bio-composite beads shown in Figure 2. A peak observed at 3200-3400 cm-1

is due to presence of –OH groups in both alginate and cellulose of the rice

husk. The peaks at around 1592 and 1412 cm−1 are asymmetric and

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symmetric stretching of –COO- groups vibrations, respectively which are

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characteristic bands of alginate (Figure 2a) [42,43]. The peaks at around

2914 cm-1, 2868 cm-1 and 1076 cm−1 are the asymmetric, symmetric
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stretching of –CH2 groups vibrations and the CO stretching vibrations,
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respectively. On the other hand, the peak observed at 1700 cm−1 in bio-
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composite beads is attributed to the ester acetyl groups in carboxylic acid

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groups of lignin or hemicellulose. At 800 cm-1 band is owing to the stretching

vibration of Si–O bond in rice husk structure, while the peak around at 550
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cm-1 is the vibration of the Fe–O bonds in the crystalline lattice of Fe3O4 [44-
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47]. These findings are compatible with SEM-EDS spectrum (Figure 3).

After MB adsorption, the wide peak which is observed at 3200 cm-1 shifted to

3400 cm-1 due to the H-bonding interaction between MB molecules and m-

ALG/RH bio-composite beads indicating adsorption of MB on bio-composite

beads (Figure 2b). On the other hand, the peak at 2924 cm-1 is referred the

stretching vibration of −CH3 methyl groups of MB and peaks are seen at

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1594 cm-1,1334 cm-1 and 1492 cm-1 shows -C=N, -C-N and C=S the

stretching vibration in the dye molecule, respectively [48].

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Figure 2. FTIR spectra of m-ALG/RH bio-composite beads (a); MB adsorbed

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m-ALG/RH bio-composite beads

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SEM Study: The surface morphologies of m-ALG, m-ALG/RH, and MB

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adsorbed m−ALG/RH bio-composite beads were obtained by SEM (Figure 3).

It is clearly seen from the Figure, morphological regularity and the

roughness of the surface of the m-ALG beads increased with rice husk

incorporated into the magnetic biopolymer. On the other hand, it was

observed from SEM images (Figure 3c-II) that the MB molecules were

conglomerated as layers on the bio-composite surface after adsorption. It

can be also seen clearly from EDX analysis of the m-ALG, the m-ALG/RH and

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MB adsorbed m-ALG/RH bio-composite beads, the presence of O and C in

alginate (Figure 3a) and the presence of Si was clearly observed with the

incorporation of rice husk (Figure 3b). In addition to this, the presence of Fe

verified the incorporation of magnetic particles into the m-ALG/RH bio-

composite beads (Figure 3a-c).

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Figure 3. SEM images and EDS spectra: (a) magnetic alginate beads (I, II,
III); (b) magnetic alginate/rice husk beads (I, II, III); 3c) MB adsorbed
magnetic alginate/rice husk beads (I, II, III).

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Thermal Analysis:

Thermogravimetry is an important technique for examining the thermal

strength of polymers. The thermal behavior of the magnetic alginate and the

m-ALG/RH bio-composite beads were shown in Figure 4. The first weight loss

of both magnetic alginate and magnetic alginate/rice husk bio-composite

beads was about 15% between room temperatue and 200 oC due to the

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evaporation of adsorbed water on bio-composite beads. Thermal

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degradation both in the magnetic alginate and the m-ALG/RH bio-composite
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beads started after 200 C and the weight loss between 200-900 °C in
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magnetic alginate and m-ALG/RH bio-composite beads was 67% and 61%,
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respectively. According to obtained results, it can be said that the addition of
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rice husk into magnetic alginate beads increased the thermal stability of the
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beads.
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Figure 4. TG curves of magnetic alginate and magnetic alginate/rice husk
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beads.
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Magnetic Study: The magnetic hysteresis curve of the m-ALG/RH bio-

composite beads was obtained by Vibrating-sample magnetometer at room
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temperature (Figure 5). The hysteresis showed that the m-ALG/RH bio-
composite beads have superparamagnetic behavior and the specific
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saturation magnetization is 9.97 emu g−1 (magnetic field = ±1.0T). The m-

ALG/RH bio-composite beads can easily be accumulated using a magnet and
removed from adsorption medium (see Figure 1).

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Figure 5. Magnetization curve of the magnetic alginate/rice husk bio-
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composite.
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3.2. Dye Removal Studies

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3.2.1. Optimization of the adsorption conditions

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Adding Rice Husk (RH): In order to determine the effect of rice husk on

MB removal efficiency, the adsorption capacity of m-ALG/RH bio-composite

beads was compared with m-ALG beads. The results showed that the adding

the rice husk into magnetic alginate (0.5%w/v) increased to the MB

adsorption capacity from 58 mg/g to 62.5 mg/g in comparison of for m-

alginate. Therefore, the obtained the m-ALG/RH bio-composite beads

exhibited an enhanced adsorption of MB compare to magnetic alginate beads

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besides that mechanical properties of magnetic beads also increased with

adding rice husk consisted of mainly silica. Increase in adsorption uptake can

be attributed to the hydroxyl functional groups on the surface of silica from

rice husk addition to carboxyl groups of alginate chains. It can be also seen

from SEM images and EDS analysis of m-ALG/RH bio-composite beads

before and after MB adsorption, decreasing in roughness of the surface and

increasing of C and O peaks corresponds to MB molecules were adsorbed by

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m-ALG/RH bio-composite beads.

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pH: pH is an essential variable in the aqueous systems which effects the
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charge distribution of the adsorbent surface and thus the interactions
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between the adsorbent and the dye molecules can change. The adsorption
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uptake of bio-composite increased when the solution pH was increased in the

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range of 3-6. Therewithal, the pH had no significant effect in a wide pH

range of 6–10 and the adsorption capacity of MB changed between 59 and

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61.9 mg/g in this pH range providing an important advantage to use

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wastewater applications due to pH value of real waters usually is basic

(Figure 6). In this pH range, an increase of the negative surface charge of

the m-ALG/RH bio-composite beads due to deprotonation of carboxylic acid

groups occurs, thus, the available adsorption sites on bio-composite beads

increase. By means of electrostatic interaction between negatively charged

carboxyl groups and positively charged MB molecules, the adsorption

capacity increased. Conversely, the decrease in the adsorption capacity at

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lower pH solutions can be clarified by electrostatic repulsion between the MB

molecules and the adsorbent due to increasing in the hydrogen ion

concentration in the solution. Therefore, the interaction between the MB that

is a cationic dye MB and the more positive adsorbent is reduced [3]. Since

no significant change in adsorption capacity was achieved between pH 6-10,

further studies were performed at pH 6 (natural pH of the distilled water).

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Figure 6. Effect of initial solution pH on MB adsorption

Adsorbent Dosage: The effect of amount of bio-composite on the

efficiency of MB removal was investigated (Figure 7). The removal efficiency

of MB increased from 15% to 89% when the amount of adsorbent is

increased owing to the more reachable adsorbent surface can be interacted

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with MB. However, the adsorption capacity of bio-composite decreased from

338 mg/g to 145 mg/g with the increase in adsorbent dosage.

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Figure 7. Effect of adsorbent dosage on the adsorption of MB

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Ionic Strength: A decrease in adsorption capacity was observed when NaCl

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was added to the solution (Figure 8). This reduction may be owing to by the

preventing active sites of adsorbent surface with NaCl. Na+ ions may be

interfered with interactions between positively charged MB molecules and

the negatively charged of the m-ALG/RH bio-composite surface. While the

adsorption capacity of bio-composite beads in the salt-free dye solution was

79.7 mg/g, it decreased when the salt concentration increased and it was

7.8 mg/g in the 1% NaCl containing dye solution. However, at high salt

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concentrations, adsorption capacity of the m-ALG/RH bio-composite beads

decreased singing the break down the electrostatic interaction between dye

molecules and surface.

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Figure 8. Effect of ionic strength on MB adsorption capacity of m-ALG/RH

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bio-composite beads

Effect of Methylene Blue concentration and isotherm studies

The influence of MB concentration on the removal percentage was

examined (Figure 9). As seen, when the MB concentration in the medium

increased from 25 to 500 mg/L, MB uptake capability of bio-composite

beads increased around 465.6 %. The maximum adsorption capacity of the

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m-ALG/RH bio-composite beads was determined as 274.9mg/g indicating

the initial dye concentration was a driving force in adsorption process.

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Figure 9. Effect of initial MB concentration on adsorption capacity

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Isotherm models are important tools for planning the real wastewater
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systems. In this study, Langmuir, Freundlich and Dubinin–Raduskevich

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equations have been used to evaluation of experimental data. Mathematical

equations of all used isotherm models were given in Table 1.

Where Ce (mg/L) is MB concentration of solution at equilibrium, qm and qD-R

are the maximum MB uptake (mg/g), KL is a constant for Langmuir

isotherm, KF and n are Freundlich constants, ε (kJ/mol) is Polanyi potential

for Dubinin-Raduskevich isotherm model.

Polanyi potential can be calculated as follow equation;

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ε = RT ln (1 + 1/Ce ) (10)

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

E = 1/(−2K)1/2 (11)

Table 1 shows the constants of the isotherm models calculated from

equations. It can be said that all isotherm models were seen to be

appropriate for the experimental data. Thus, the adsorption process might

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be a heterogeneous or multi-layer. In terms of regression coefficients (R2),

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conformity of adsorption data to isotherm models approximately followed

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the order: Freundlich ≥ Langmuir> D-R. It can be clearly seen from Figure
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10, experimental data especially obtained from lower MB concentrations
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fitted Freundlich and Langmuir models indicating both monolayer

adsorption and molecular interaction between dye molecules. At higher MB

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concentrations, experimental data fitted Freundlich more than others.

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Table 1. Isotherm model parameters for the removal of MB by magnetic

alginate/rice husk beads (pH: 6.0, sorbent dosage: 0.3 g initial dye
concentration: 25-500 mg/l)

Isotherm Expression formula Parameters m-ALG/RH

Langmiur 1/qe = 1/qm + (1/qm KL) 1/Ce KLx103 (L/mg) 4.43

qm (mg/g) 344

R2 0.994

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Freundlich lnqe=lnKF + 1/n Ce KF(mg/g(L/mg)1/n 7.41

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1/n 0.607

-p R2 0.999
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D-R lnqe=K 2+lnqe qD-R (mg/g) 315.92
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E(kJ/mol) 5.0

R2 0.984
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The KL is Langmuir constant indicating the relevancy of the MB to the

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adsorbent. High KL value for MB adsorption showed high affinity of MB

molecules to the m-ALG/RH bio-composite beads (Table 1). However, the

experimental adsorption capacity is lower than the calculated adsorption

uptake indicating incomplete adsorption process. Besides, the equilibrium

data were implemented to the D-R model to understand adsorption

behavior of MB is physical or chemical. The value of E shows the type of

adsorption process which is considered to be physical when the value of E is

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between 1 and 16 kJ/mol. Conversely, if the value of E is more than 16

kJ/mol, adsorption process occurs via chemical interactions [49]. It can be

clearly seen from Table 1, the value of E for the m-ALG/RH bio-composite

beads/MB system is obtained 5.0 kJ/mol indicating the adsorption of MB on

the m-ALG/RH bio-composite beads is physical.

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Figure 10. The conformity of adsorption data to isotherm models

The comparison of theoretical adsorption capacities of various adsorbents

used alginate and its composites for the removal of MB obtain from isotherm

models in the literature is given in Table 2. As seen, the different adsorption

capacities for MB removal have been reached in previously reported studies

using alginate and its composites. For example, while the adsorption

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capacity of the Alginate/ Polyvinyl Alcohol - Kaolin Composite is 17.33 mg/g

[50], it is 137.2 mg/g for MMTNS hydrogel beads [51]. On the other hand,

Boukhalfa et al. have been reported the MB adsorption capacity of

Maghemite/alginate/functionalized multiwalled carbon nanotubes as 905.5

mg/g [17]. On the other hand, Hassan et al. have been reported the

adsorption capacity of calcium alginate/activated carbon composite beads as

892 mg/g [7]. It is clearly seen that alginate prepared with activated carbon

of
and multiwalled carbon nanotubes have high adsorption capacities. However,

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these adsorbents have a significant disadvantage due to its considerable

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expensive. In our study, the adsorption capacity of the m-ALG/RH bio-
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composite beads which is a green, low-cost and easily accessible material
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was determined as 344 mg/g.

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Table 2. The comparison of studies using alginate and its composites for the
removal of MB.

Adsorbent q(mg/g) Ref.

Maghemite/alginate/functionalized multiwalled 905.5 [17]

carbon nanotubes
Graphene oxide/calcium alginate composites 181.81 [2]

Calcium alginate–bentonite–activated carbon 756.97 [1]

composite beads
Calcium alginate/activated carbon composite 892 [7]
beads

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Entrapping activated carbon powder derived 665.9 [23]
from spent coffee grounds into calcium-alginate
beads

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Frozen alginate–clay 181.8 [24]

Mesoporous activated carbon-alginate 230 [4]

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Alginate/ Polyvinyl Alcohol - Kaolin Composite 17.33 [50]
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Poly(vinyl alcohol)-sodium alginate-chitosan- 137.2 [51]
montmorillonite nanosheets hydrogel beads
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Fe3O4/activated carbon/sodium alginate 465.12 [52]

composite absorbent
m-ALG/RH 344 This
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study
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Thermodynamic study:
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From a thermodynamic viewpoint, the adsorption of MB on m-ALG/RH

beads were evaluated with respect to thermodynamic functions such as

ΔG0, ΔH0, and ΔS0 calculated by the following equations:

ΔG= −RT lnKd (12)

Kd is MB adsorption capacity (mg/g).

ΔGo= ΔHo−TΔSo (13)

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On combining Eqs. (10) and (11), we get linear Van't Hoff plot as follows:

lnKd=−ΔGo/RT=ΔSo/R−ΔH/RT (14)

ΔSo and ΔHo can be calculated from the intercept and the slope of the Van't

Hoff plot, i.e., as lnKd versus 1/T, respectively.

Among the thermodynamic functions, both free energy and entropy

functions show whether adsorption process will occur spontaneously or not.

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Especially, ΔGo is the essential parameter for spontaneity. The calculated

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thermodynamic parameters for the MB/m-ALG/RH system are summarized

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in Table 3. The negative ΔGo values showed that the adsorption process is
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spontaneous and MB molecules have high affinity to uptake on the m-
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ALG/RH bio-composite beads. Moreover, the negative value of ΔGo was high

at low temperature (20oC) which favors the adsorption process.

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Table 3. Calculated kinetic parameters for pseudo first-order and pseudo

second-order models for the removal of MB using m-ALG/RH bio-composite
beads; C: 50mg/L; sorbent dosage: 0.3 g).

T (K) Pseudo-first-order Pseudo-second-order Thermodynamic Parameters

qe,exp
(mg/g)
Ho So Go
2 -3 2
qe k1 R qe k2x10 R

-1 -1 -1
(mg/g) (min ) (mg/g) (g mg min ) (kJ/mol) (J/molK) (kJ/mol)

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293 84.6 69.18 0.012 0.918 90.91 0.34 0.928 -16.77 4.97 -15.31

313 53.4 54.18 0.029 0.985 58.82 1.73 0.995 -15.21

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333 36.9 20.27 0.041 0.928 38.46 9.90 0.999 -15.11

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On the other hand, negative value of ΔHo indicated that adsorption process
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was exothermic nature. So, the rise in the temperature will cause to

decrease in the adsorption capacity. The value of ΔHo predicts also the
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physisorption behavior of the m-ALG/RH. In addition, the positive value of

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ΔSo showed increase of randomness and facilitated the adsorption

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processes of MB onto the m-ALG/RH bio-composite beads.

Effect of adsorption time and determination of adsorption kinetics

Contact time is a very important parameter for adsorption process. Influence

of the time on dye adsorption at different temperature is shown in Figure 11.

The maximum uptake of MB was changed 84.6, 53.4 and 36.9 mg/g

increasing the temperature from 293 K to 333 K, respectively. On the other

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hand, it can be clearly seen that there was two-stage adsorption consisting

of an initial rapid stage (first 90 min) and then much slower stage.

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Figure 11. Effect of contact time on MB adsorption at different temperatures

(Co = 100 mg/L) and fitted data to pseudo-second-order kinetic model
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Kinetic evaluation of adsorption process was performed the pseudo-first-

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order and the pseudo-second-order models and the calculated constants

were given in Table 3. The high correlation coefficients were calculated for

the pseudo-second-order kinetic model indicating adsorption behavior of MB

onto the m-ALG/RH beads is more appropriate than first order equation.

Moreover, the theoretical qe values are compatible with the experimental

data except obtained from 293 K, indicating this adsorption process is

controlled the pseudo-second-order kinetics (Figure 11).

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Adsorption is a complex process, it generally contains three stage such as

the first is the external diffusion, the second and the third stages are internal

diffusion. For this reason, it is not appropriate the analyzing adsorption

behavior using only one or two kind of kinetic models. Therefore, the

obtained kinetic data was also analyzed Brouers-Sotolongo kinetic equations

was shown in Section 2.3 and obtained data given in Figure 12 which are

presented in form as it is produced from the Mathematica program.

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Figure 12. Fit of experimental data to Brouers-Sotolongo Model at different

temperatures

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Figure 13. Rate curve according to Brouers-Sotolongo Model
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Experimental data were applied for various values of n (Table 4). Although
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the R2 values of all used models were very high, the best nonlinear fits for

MB adsorption at all studied temperatures seemed to be accurately described

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by the BSf model. On the other hand, the results of Table 4 when compared
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with those of Table 3 shows how important is the introduction of a fractal

coefficient, the R2 value reaching a value very close to 1 when this coefficient

is assumed to vary with time. The last line of Table 4 emphasizes the great

variation of this coefficient varying from a value smaller than 1 (anomalous

diffusion) to a multi-site sorption higher than 2. In Figure 13 we show the

corresponding curve for the Rate (Eq.9) which confirms the large variation

with time of the fractal coefficient and the nature of the sorption. The

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variation from a value smaller than 1 to a value largely higher than 1 yields

a so-called bathtub behavior of the rate characteristic of this type of

adsorption.

Table 4. Kinetic modeling results related to the MB adsorption onto the m-

ALG/RH bio-composite beads

Kinetic Model n 𝛼 𝑞𝑚𝑎𝑥 𝜐 𝑡𝑠 𝜏50% 𝑅2

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T=293 K (Figure 12)

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Weibull 1 0.93 94.7 48.7 0.984530

Hill

BSf(n,𝛼 (𝑡 𝜐 ))
2 1.05
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100.7 75.3 0.994070
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1.05 0.34-2.3 84.5 2 100 0.999956

T=313 K (Figure 12)

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Weibull 1 0.87 53.7 18.7 0.999934

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Hill 2 1.53 55.5 21.3 0.999864

BSf(n,𝛼 (𝑡 𝜐 )) 1.2 0.79-1.12 53.2 2 100 0.999984

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T=323 K (Figure 12)

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Weibull 1 0.50 37.2 3.79 0.999875

Hill 2 1.07 37.8 6.62 0.999858

BSf(n,𝛼 (𝑡 𝜐 )) 1.01 0.42-0.52 37.2 0.22 100 0.999877

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Conclusion

Results indicated that the magnetic alginate/rice husk bio-composite beads

can be successfully used as a low cost and efficient adsorbent for removal of

MB. Maximum adsorption capacity of magnetic alginate/rice husk beads was

calculated as 274.9

mg/g. The MB removal efficiency of magnetic alginate/rice husk bio-

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composite beads was independent of solution of pH; having no significant

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effect pH range 6–10. The kinetic studies indicated that the adsorption of MB

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is well described by the fractal Brouers-Sotolongo formalism. The variation of
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the fractal coefficient with time allows to follow the variation of the kinetic
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rate from diffusion to molecular sorption. We thought that the m-ALG/RH

bio-composite beads is favorable material for MB removal due to its high

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removal capacity, low cost and green constituent parts.

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Credit Author Statement

Erol Alver: Conceptualization, Methodology, Investigation , Resources,

Writing - Original Draft, Writing - Review & Editing. Ayşegül Ülkü Metin:

Conceptualization, Methodology, Formal analysis, Writing - Original Draft,

Writing - Review & Editing. Francois Brouers: Methodology, Formal

analysis

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Highlights

An eco-friendly and low-cost bio-composite was used to adsorb Methylene

Blue dye.

Rice Husk is agriculture waste material and has no commercial significance.

Rice Husk increased both mechanical strength of alginate and adsorption

capacity.

Results indicated that optimum removal of dye depends on process

parameters.

of
Brouers–Sotolongo model was the best fitted kinetic model for MB.

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