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INTERNATIONAL CONFERENCE ON SCIENCE AND TECHNOLOGY 2020 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 596 (2020) 012052 doi:10.1088/1755-1315/596/1/012052

Adsorption of Methylene Blue onto Iron Oxide Magnetic

Nanoparticles Coated with Sugarcane Bagasse

Siti Zuraida Razali1, Mohd Yusmaidie Aziz2*, Hisham Atan Edinur3, Ahmad
Razali Ishak1*
1
Center of Environmental Health & Safety, Faculty of Health Sciences, Universiti
Teknologi MARA, Puncak Alam 42300, Selangor, Malaysia
2
Integrative Medicine Cluster, Advanced Medical and Dental Institute, Universiti Sains
Malaysia, 13200 Bertam, Kepala Batas, Penang, Malaysia
3
School of Health Sciences, Universiti Sains Malaysia, Health Campus, 16150 Kubang
Kerian, Kelantan, Malaysia

Email: [email protected]; [email protected]

Abstract. The removal of dyes from coloured effluents, in particular from the textile
industry, is currently one of the major environmental concerns. Current methods for
removing dyes from wastewater are costly and cannot be used effectively to treat a wide
range of such wastewaters. Thus, we investigated the removal of methylene blue dye
from aqueous solution using iron oxide magnetic nanoparticles coated with sugarcane
bagasse. This newly and low-cost adsorbent was analysed with Fourier Transform
Infrared Spectrophotometer followed by optimisation of its physicochemical parameters
such as contact time, initial dye concentration, adsorbent dosage, and pH of dye
solution. The study showed that the adsorption of methylene blue was pH dependent
and the highest removal (98%) was obtained at pH 7. The optimum conditions were also
achieved by using 10 mg/L dye concentration, 0.6 gram dose of adsorbent and 60
minutes adsorption time. The results obtained followed the pseudo-second-order
kinetics and the adsorption was fitted well to the Langmuir isotherm model where the
maximum adsorption capacity (Qm) was 37.45 mg/g. It is suggested that iron oxide
magnetic nanoparticles coated with sugarcane bagasse is a potential low-cost adsorbent
for the dye removal from industrial wastewater.

1. Introduction

Water pollution has become critical environmental and economic problems worldwide due to
industrialisation processes. One of the environmental pollutants that contributes to water pollution is
synthetic dye. It is widely applied in textiles, leather, paper, fur, printed materials and cosmetics [1].
Synthetic dyes are relatively inexpensive and widely used in the textiles industry [2]. The presence of
dye in water is a threat to both marine and human life. Dyes are essential recalcitrant that, when they
stay in flowing water for a long time, they slow down photosynthetic process, inhibit the growth of

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INTERNATIONAL CONFERENCE ON SCIENCE AND TECHNOLOGY 2020 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 596 (2020) 012052 doi:10.1088/1755-1315/596/1/012052

marine organisms by hindering sunlight and depletion of dissolved oxygen, and also reduce the
recreation value of the stream [3].

It is very important to eliminate dye contaminants from wastewater effluents because even a little
amount of dye in water is harmful and highly visible [4]. Various chemical processes to treat dyed
wastewater can be applied such as ion exchange, membrane filtration, precipitation, flocculation,
electro-kinetic coagulation, electro-flotation, electrochemical destruction, irradiation etc. However,
these processes are not cost-effective, need to comply with a number of rules and are not available on
the market for small wastewater treatment industries. Taking these factors into account, the adsorption
process is more useful for wastewater treatment due to its lower cost, uncomplicated operation, less
energy, no side effects of toxic substances and the absorption process is normally designed for coloured
wastewater treatment [5].

Adsorption process is an effective method of removing dyes from the wastewater. Owing to its
sludge free clean operation and full elimination of dyes from the diluted solution, the adsorption process
has the advantage over the other processes. Thus, it is considered one of the best techniques for
wastewater treatment. Activated carbon (powdered or granular) has been widely used an adsorbent due
to outstanding adsorption performance. Commercially available activated carbon is however very
expensive and this has led to further studies of cheaper replacements [6]. One of the efforts is to produce
green adsorbents using agro-industrial waste. An excellent green adsorbent is low cost and has
acceptable adsorption properties and has the reuse opportunity. In the market nowadays, there are many
low costs commercially available green adsorbents for removing dyes. However, with limited ability to
remove pollutants and poor ability to separate, most of them are not fully effective [7]. On the other
hand, the removal of pollutants by magnetic nanoparticles as adsorbents is an emerging field of water
and wastewater treatment, particularly for the removal of magnetic contaminants [8]. Thus, in this study,
we proposed iron oxide (Fe3O4) magnetic nanoparticles coated with sugarcane bagasse as a potential
low-cost adsorbent.

2. Materials and Methods

2.1. Sugarcane Bagasse and methylene blue standard

Sugarcane bagasse was collected from a local night market in Klang, Selangor. The sugarcane bagasse
was dried under sunlight, followed by drying in an oven at 100°C for 24 hours. The dried sugarcane
bagasse was then crushed mechanically to provide a smaller particle to increase the surface area of the
size of the adsorbent and were sieved afterwards to obtain a particle size between 0.3-1.0mm. Methylene
blue standard was purchased from Merck (Darmstadt, Germany).

2.2. Synthesis Fe3O4 Magnetic Nanoparticles coated with Sugarcane Bagasse

Magnetic particles were synthesized by dissolving 4.58 g of FeCl 2.4H2O and 8.93 g of FeCl3.6H2O in
80mL distilled water with intense stirring (1000 rpm). Approximately 10mL (25%) of ammonium
hydroxide solution was applied to the solution as it was heated to 80°C. Then, 10g of sugarcane bagasse
powder was added to the solution, and the reaction was allowed to carry out for 30 minutes at 80°C
under constant stirring to ensure the maximum growth of nanoparticle crystals. The samples were cooled
down to room temperature after 30 minutes, and washed regularly with distilled water to eliminate
unreacted chemicals. The iron oxide nanoparticles coated with sugarcane bagasse (Fe3O4 MNP-SCB)
was then filtered and dried in an oven at 105°C before use.

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INTERNATIONAL CONFERENCE ON SCIENCE AND TECHNOLOGY 2020 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 596 (2020) 012052 doi:10.1088/1755-1315/596/1/012052

2.3. Characterization of Fe3O4 Magnetic Nanoparticles Sugarcane Bagasse

Fe3O4 MNP-SCB was characterized using Fourier Transform Infrared Spectroscopy (FTIR). The spectra
were recorded at ambient temperature using a KBr disc method on the Perkin Elmer spectrophotometer
(RX-IFTIR, USA). The disk was prepared from 0.001 g of the sample finely ground with 0.3g of fine
grade KBr and then scanned at the wavelength range of 400 - 4000 cm-1.

2.4. Batch Absorption Study

The batch experiment was carried out to determine the optimum experimental conditions (pH, dosage,
contact time and initial dye concentration) for removal of methylene blue. The known concentration of
dye was prepared by adding ultra-pure water from a stock solution. The dye solution pH was then
adjusted to the desired value for optimization. For a defined period the mixture has been stirred at
200rpm. The filtering method was applied after a certain amount of stirring to separate the solid from
liquid. Calculation of the adsorption potential and adsorption performance as follows:

Co − Ce
Adsorption Efficiency (%) = X 100 (1)
Co

Where Co and Ce are the initial and final concentration of methylene blue respectively (mg/L).

mg Co − Ce
Adsorption Capacity ( ) , qe = X V (2)
g W
Where W is the weight of adsorbent (g), and V is the volume of the solution (L).

The results from the study were also used to determine the type of kinetics and isotherm models which
fitted to the adsorption condition. Two type of kinetics models namely pseudo first-order and pseudo
second-order were tested meanwhile for isotherms, Langmuir and Freundlich models were used.

3. Results and Discussion

3.1 Fourier Transform Infrared (FTIR) characterization

FTIR analysis was carried out to determine the functional group present in magnetic nanoparticles
(MNP) and magnetic nanoparticles coated with sugarcane bagasse (MNP-SCB) and we can affirm the
binding between the other groups (Figure 3.1). The appearance of bands between 3000 to 3500 cm-1 and
the band around 2800- 2900 cm-1 for both compounds could be attributed to O-H group of cellulose and
the CH2 groups respectively. The band at 559 cm-1 and 538 cm-1 relate to Fe–O bond. The absorption
band at 1605 cm-1 contribute to the deformation vibration of O-H group. The presence of absorption
band at 1025 cm-1 for MNP-SCB is related to the C–OH stretching vibration. Results indicated that
sugarcane bagasse was coated to the magnetic Fe3O4 nanoparticles successfully.

3
INTERNATIONAL CONFERENCE ON SCIENCE AND TECHNOLOGY 2020 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 596 (2020) 012052 doi:10.1088/1755-1315/596/1/012052

Figure 1. FTIR spectra iron oxide magnetic nanoparticles (MNP) and iron oxide magnetic
nanoparticles coated with sugarcane bagasse (MNP-SCB)

3.2 Batch Adsorption Study - Effect of pH, dosage, contact time and initial concentration on dye
removal

The initial pH value of the solution has significant influence as the pH of the dye solution affects the
properties of the adsorbent such as the dye chemistry, surface charge and its degree of ionization. It
could be assumed that the electrostatic attraction, ionic properties and structure of adsorbent and dye
molecules under different pH values play important role in removal efficiency [9]. pH region between
5 and 9 was chosen because most of practical applications are within this range. As shown in Figure 2a,
the lowest percentage for dye concentration removal was 67% at pH 5.0 while highest percentage for
dye concentration removal was 98% at pH 7.0 with 0.5882 value of adsorption capacity. Increasing of
the solution pH increases the number of hydroxyl groups, thus increase the number of negative charges
and enlarges the attraction between dye and the adsorbent surface. It was attributed that the presence of
more negative charges adhering to positive charges of methylene blue which resulted to higher
methylene blue adsorption process [10].

The result from figure 2b shows that the removal efficiency is ranged between 92-96% regardless the
adsorbent dose. The adsorbent capacity was also in the range of 0.55-0.58 mg/g. The higher percentage
of dye removal with the adsorbent dose studied can be attributed to the availability of more adsorption
sites and the adsorbent surface area. The effect of contact time on the removal of dye concentrations
increased with increased contact time as shown in Figure 2c. At 60 minutes, the equilibrium had reached
where the methylene blue removal was the highest at 98.03%. Initially, the methylene blue molecules
reach the boundary of the layer during the first phase before being diffused to the adsorbent surface. At
the later stage, the molecules were diffused into the porous structure of the adsorbent. This phenomenon
will therefore take a relatively longer time [11].

Adsorption studies of Fe3O4 magnetic nanoparticles of sugarcane bagasse show that the percentage of
dye removal efficiency was higher at a higher concentration of methylene blue (Figure 2d). The
maximum removal efficiency was at 94.40 % at 10 mg/L of methylene blue solution. This removal
efficiency probably due to increased contact of adsorbate with available sites of adsorbent. This can be

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INTERNATIONAL CONFERENCE ON SCIENCE AND TECHNOLOGY 2020 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 596 (2020) 012052 doi:10.1088/1755-1315/596/1/012052

due to the fact that the increase of the initial adsorbent concentration is a driving force to resolve the
resistance of the dye to mass transfer between the aqueous and solid phases [12].

Figure 2. Effect of a) pH, b) absorbent dosage, c) contact time and d) initial concentration on dye
removal using Fe3O4 magnetic nanoparticles of sugarcane bagasse

3.3 Adsorption Kinetics and Isotherm

The adsorption kinetic models such as the pseudo-first-order and pseudo-second-order are useful for
determining behaviour of adsorption process; physical or chemical. In this study, the kinetics of removal
of methylene blue follows the pseudo-second order kinetics (R2= 0.99) which indicate the adsorption
process was more inclined towards chemisorption (Figure 3a).

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INTERNATIONAL CONFERENCE ON SCIENCE AND TECHNOLOGY 2020 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 596 (2020) 012052 doi:10.1088/1755-1315/596/1/012052

Figure 3. a) Pseudo second-order kinetic b) Langmuir sorption isotherm for removal of methylene
blue using Fe3O4 magnetic nanoparticles of sugarcane bagasse.

The pseudo second-order model is explicitly explained in equation 3 and 4.

𝐷𝑞𝑡
= 𝐾2(𝑞𝑒 − 𝑞𝑡)2 (3)
𝑑𝑡

Where K2 (min-1) is the rate constant of pseudo-second order adsorption, qe and qt denote the amount
of methylene blue adsorption (mg/g) and the amount of methylene blue adsorption (mg/g) at equilibrium
and at time (t) in minutes respectively. Integrating equation 3 and applying initial condition gives:

𝑡 1 𝑡
= 2
+ (4)
𝑞 𝐾2𝑞𝑒 𝑞𝑒

The isotherm model was simulated to describe the mechanisms of interaction between the adsorbent and
the adsorbate. Modelling of the equilibrium data is a very important way to predict the adsorption
mechanisms of various adsorption systems. In this study, the adsorption isotherm of methylene blue was
better fitted into Langmuir model as shown in Figure 3b (R2 = 0.99). The Langmuir isotherm assumes
monolayer adsorption to a surface containing a finite number of adsorption sites with no transmigration
of adsorbent in the surface of the plane. If a site has been filled up, there can be no further sorption at
that site. This means that the surface reaches a point of saturation at which the optimum surface
adsorption is achieved [13]. The linear form of the Langmuir equation is expressed as follow:

𝐶𝑒 1 𝐶𝑒
= + (5)
𝑞𝑒 𝑏𝑄𝑚 𝑄𝑚

Where Qm is the maximum adsorption capacity (maximum quantity of adsorbate required to form a
single monolayer on unit mass of adsorbent), b is adsorption equilibrium constant, qe is the amount
adsorbed on unit mass of the adsorbent and Ce, is the concentration of adsorbate at equilibrium. In this
study, the maximum adsorption capacity Qm for Fe3O4 magnetic nanoparticles material coated with
sugarcane bagasse was 37.45 mg/g.

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INTERNATIONAL CONFERENCE ON SCIENCE AND TECHNOLOGY 2020 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 596 (2020) 012052 doi:10.1088/1755-1315/596/1/012052

4 Conclusion

This study revealed that Fe3O4 magnetic nanoparticles material coated with sugarcane bagasse
prepared through chemical co-precipitation method could be successfully employed as an alternative
low-cost adsorbent for the removal of methylene blue dye. The effects of pH, initial concentration,
contact time and dosage of magnetic field intensity on the methylene blue dye adsorption were optimised
and confirmed by pseudo-second order adsorption kinetics and Langmuir adsorption isotherm models.
To recommend, this newly Fe3O4 magnetic nanoparticles – sugarcane bagasse adsorbent shall be applied
for dye removal in real wastewater samples. However, before testing in the real samples, we propose
for further characterization study to confirm the nano-composite materials using Ultraviolet-visible
spectroscopy (UV-VIS), X-ray fluorescence (XRF), X-ray diffraction (XRD), Scanning electron
microscopy (SEM) and Thermo gravimetric analysis (TGA).

References

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[2] Yaseen D and Scholz M 2019 Textile dye wastewater characteristics and constituents of
synthetic effluents: a critical review International journal of environmental science and
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[3] Tkaczyk A, Mitrowska K and Posyniak A 2020 Synthetic organic dyes as contaminants of the
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[4] Ismail M, Akhtar K, Khan M, Kamal T, Khan M A, M Asiri A, Seo J and Khan S B 2019
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[5] Leal T W, Lourenço L A, Scheibe A S, de Souza S M G U and de Souza A A U 2018 Textile
wastewater treatment using low-cost adsorbent aiming the water reuse in dyeing process
Journal of Environmental Chemical Engineering 6 2705-12
[6] Razi M A M, Hishammudin M N A M and Hamdan R 2017 Factor affecting textile dye removal
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[7] Rajabi A A, Yamini Y, Faraji M and Nourmohammadian F 2016 Modified magnetite
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of the disperse dyes from wastewater of textile companies Nanochemistry Research 1 49-56
[8] Mahmoodi N M, Abdi J and Bastani D 2014 Direct dyes removal using modified magnetic
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[10] Albroomi H, Elsayed M, Baraka A and Abdelmaged M 2015 Factors affecting the removal of a
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[12] El-Wakil A, El-Maaty A W and Oudah A A A-R 2015 Methylene blue dye removal from
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INTERNATIONAL CONFERENCE ON SCIENCE AND TECHNOLOGY 2020 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 596 (2020) 012052 doi:10.1088/1755-1315/596/1/012052

[13] Desta M B 2013 Batch sorption experiments: Langmuir and Freundlich isotherm studies for the
adsorption of textile metal ions onto teff straw (Eragrostis tef) agricultural waste Journal of
thermodynamics 2013