Desalination and Water Treatment 190 (2020) 322–330

June
www.deswater.com
doi: 10.5004/dwt.2020.25644

Biosorption of methylene blue dye by rice (Oryza sativa L.) straw:

adsorption and mechanism study

Ali H. Jawada,*, Nurul Nadiah Mohd Firdaus Huma, Ahlam M. Farhanb,

Mohd Sufri Mastulia,c
a
Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia, Tel. +60355211721;
emails: [email protected]/[email protected] (A.H. Jawad), Tel. +6035543 5737; email: [email protected] (N.N.M.F. Hum),
Tel. +03 5543 6594; email: [email protected] (M.S. Mastulia)
b
Chemistry Department, College of Sciences for Women, University of Baghdad, Baghdad, Iraq, Tel. (+964) 7702507225;
email: [email protected] (A.M. Farhan)
c
Centre for Nanomaterials Research, Institute of Science, Uviversiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia

Received 28 October 2018; Accepted 9 February 2020

abstract
In this work, rice (Oryza sativa L.) straw biosorbent (RSB) was evaluated as natural, renewable, and
low-cost biosorbent for removal of methylene blue (MB) dye from aqueous solution. The structural
characterization of the RSB was performed through pore structural analysis (Brunauer–Emmett–
Teller), scanning electron microscopy and energy dispersive X-ray analysis, X-ray diffraction, Fourier
transform infrared, point of zero charge method, and proximate analysis. Batch adsorption experi-
ments were conducted to study the influence of adsorbent dosage (0.05–0.30 g), solution pH (2–12),
initial dye concentration (20–100 mg/L), and contact time (0–240 min) on the adsorption of the MB.
The kinetic uptake results were well described by the pseudo-second-order kinetic. The experimen-
tal data at equilibrium fitted well with the Langmuir model at 303°K, and the maximum adsorp-
tion capacity of MB on the RSB surface was found to be 158 mg/g. The mechanism of adsorption
included mainly electrostatic attractions, n–π stacking interaction, and hydrogen bonding interac-
tion. The results indicate the potential use of RBS as natural, renewable, and low-cost biosorbent for
the removal of MB dye as a model of cationic dye.
Keywords: Adsorption; Agricultural waste; Rice straw; Low-cost adsorbent; Methylene blue

1. Introduction complications due to long term exposure to MB dye include

eye burns, breathing difficulties, nausea, allergy, vomiting,
Dyes are also known to be toxic and carcinogenic which
mental confusion, jaundice, and even dysfunction of brain,
could cause detrimental health effects. Nonetheless, the
liver, and central nervous system [3].
usages of synthetic dyes in various industries have increased
Various treatment methods are available for the removal
significantly over the years due to its simple applicability
of dyes from wastewater. These methods include biotreat-
and persistent dyeing effect [1]. Methylene blue (MB) dye,
ment [4], flocculation–coagulation [5], photocatalytic deg-
a cationic basic dye which forms face-to-face dimers, rep-
radation [6], Fenton chemical oxidation [7], cation exchange
resents one of the most widely utilized synthetic dyes not
membranes [8], and electrochemical degradation [9].
only in the dyeing industries but also in the field of chem-
Adsorption technique provides high performance and con-
istry, biology, and medical science [2]. Some of the health
venience of operation and selectivity as well as exhibits a
simple design and flexibility [10]. Activated carbon is one of
* Corresponding author.

1944-3994/1944-3986 © 2020 Desalination Publications. All rights reserved.

 A.H. Jawad et al. / Desalination and Water Treatment 190 (2020) 322–330 323

the most common adsorbent used for removal of dyes, never- analysis was conducted in reflection mode (Cu Kα radia-
theless due to a high operational cost, and extremely difficult tion) on a PANalytical (UK), X’Pert Pro X-ray diffractometer.
for regeneration limits its application on huge scale [11]. Scans were recorded with a scanning rate of 0.59°/s. The dif-
Taking these criteria into consideration, there is an inter- fraction angle (2θ) was varied from 10° to 90°. Textural char-
est to search for economic and efficient techniques using acterization of RSB was carried out by N2 adsorption using
alternative materials such as agricultural waste as natural, Micromeritics ASAP 2060, USA. Fourier transform infrared
renewable, and low-cost biosorbent. In recent years, adsorp- (FTIR) spectral analysis of RSB was performed on a Perkin
tion process by biomass wastes has been regarded as the Elmer, Spectrum One in the 4,000–500 cm−1 wavenumber
most affordable and feasible option for removal of dyes. range. The surface physical morphology was examined
Therefore, many types of agricultural residue and biomass by using scanning electron microscopy–energy-dispersive
waste were successfully utilized as renewable and low-cost X-ray spectroscopy [(SEM–EDX (energy-dispersive X-ray),
biosorbent for removal of MB dye from aqueous such as Hitachi, TM3030Plus, Tabletop Microscope, Japan]). The
pomegranate [12], dragon fruit peel [13], watermelon rinds pH at the point of zero charge (pHpzc) was estimated using
[14], soft and hardwood wastes [15], rejected tea [16], tea a pH meter (Metrohm, Model 827 pH Lab, Switzerland), as
waste [17], and canola residues [18]. described by Lopez-Ramon et al. [26]. The surface charge
Rice (Oryza sativa L.) is a prime source of carbohydrates (pHpzc) was measured by using the pH drift method with
in Asia. As per the Food and Agriculture Organisation of the a pH meter, the solution pH was adjusted to a series of ini-
United Nations (FAO) statistics in 2014, worldwide rice pro- tial values between 2 and 12 by adding either HCl or NaOH
duction was about 740 million tons [19]. So far, rice straw and then RS (0.15 g) to the solution. These were then shaken
(RS) is considered as a waste, and consequently left or burnt for 24 h in an isothermal water bath shaker, a revolving
without any profit. Numerous ideas have been suggested for water bath to reach equilibrium, after each resulting pH was
exploiting RS as pulp and paper [20], construction materials measured and the initial pH (pH0) vs. the difference between
[21], compost [22], fuel [23], production of ethanol [24], and the initial and final pH values (ΔpH) was plotted. The pzc
precursor for activated carbon [25]. RS could be an excellent was taken as the point where ΔpH = 0.
choice from an economic and environmental perspective
due to its availability and zero value waste. To the best of 2.4. Batch adsorption experiments
our knowledge, RS so far never been applied as a biosorbent
for removal of cationic dyes from wastewater. Therefore, this The batch adsorption experiments were conducted in
research work assesses the potential application of RS as a order to determine the optimized conditions of adsorbent
low-cost and renewable biosorbent for MB dye removal from dosage (0.05−0.30 g), solution pH (2−12), initial dye con-
aqueous solution through batch mode adsorption studies. centration (20−100 mg/L), and contact time (0−240 min). All
experiments were performed in a series of conical flasks con-
2. Materials and methods taining 100 mL of MB dye solution of known concentrations
and the pH of MB solution was adjusted by adding either
2.1. Adsorbate (MB) 0.10 mol/L HCl or 0.10 mol/L NaOH. A known dosage of RSB
Methylene blue (MB, 98.5% Assay) as an adsorbate was was added into the MB dye solution, capped, and agitated in
bought from R&M Chemicals, Malaysia. All MB solutions a water bath shaker (Memmert, water bath, model WNB7−45,
were prepared and diluted with ultra-pure water. The used Germany) at a constant speed of 110 stroke/min and 303°K
MB has a chemical formula of C16H18Cl3S·xH2O with molecu- until equilibrium reached. The supernatant was separated
lar weight of 319.86 g/mol. using 0.20 μm Nylon syringe filter and the remaining dye
concentration was monitored at different time intervals
using a HACH DR 2800 direct reading spectrophotometer at
2.2. Preparation of adsorbent a maximum wavelength (λmax) of 661 nm. The blank test was
The RS was collected from rice mill in Perlis, Malaysia. carried out in order to account for color leached by the adsor-
The dried RS was converted to very small pieces and washed bent and adsorbed by the glass containers, blank runs with
several times with distilled water and then dried thor- the only RSB in 100 mL of doubly distilled water and 100 mL
oughly in sunlight for 48 h. The dried RS was ground and of MB solution without RSB were conducted simultaneously
sieved to the mesh size between 250 and 500 μm. Later, the at similar conditions. The adsorption capacity at equilib-
RS was washed several times with distilled water, and then rium, qe (mg/g) and the percent of color removal, CR (%) of
with ethanol technical grade to remove the dust and other MB dye were calculated using Eqs. (1) and (2), respectively:
water-soluble impurities and subsequently dried at 105°C
for 24 h inside an oven. The obtained sample was converted
qe =
(C 0
− Ce ) V
(1)
into powder form by a mixer grinder and sieved to constant W
mesh size (250–500 μm). The final product of rice straw bio-
sorbent (RSB) was stored in an airtight container for further
applications. CR% =
(C 0
− Ce )
× 100 (2)
C0
2.3. Characterization of RSB
where, C0 (mg/L) = initial dye concentration; Ce (mg/L) = dye
The physicochemical properties of RSB were investigated concentration at equilibrium; V (L) = volume of dye solution;
by using the following analyses. X-ray diffraction (XRD) W (g) = mass of adsorbent.
324 A.H. Jawad et al. / Desalination and Water Treatment 190 (2020) 322–330

3. Results and discussion 3.1.3. Point of zero charge analysis

3.1. Characterization of RSB The pHpzc analysis was studied to estimate the pH
at which the net charge of the surface of adsorbent is zero.
3.1.1. Physical properties of RSB The pHpzc of RSB was determined to find out the pH at
The results of physical and textural properties of RSB which the electrical charge of the surface of RSB was zero.
were recorded in Table 1. The results indicate that RSB has Fig. 3 shows that the pHpzc of RSB was at pH 6.1 which
low values of bulk density, ash content, and moisture con- reflected the acidity of RSB, this results in agreement with the
tent, along with a relatively high yield approximate carbon. aforementioned FTIR results (Fig. 2a) about the availability
The N2 adsorption/desorption isotherms for RSB is shown of acidic functional groups such as carboxylic acids, alco-
in Fig. 1, and the textural parameters of RSB are recorded in hols, phenols, or ester groups within the chemical structure
Table 1. As for textural properties, RSB has low Brunauer– of RSB. At solution pH above the pHpzc value, the surface
Emmett–Teller (BET) surface area of 4.42 m²/g. Pore sizes of RSB becomes negatively charged and thus, adsorption of
are classified in accordance with the IUPAC classification cations is preferred [24]. In this regard, it is predicted that the
system (USA), where pores may possess variable diameter adsorption of the cationic dye (MB dye) by RSB will be favor-
(d): micropores (d < 2.0 nm), mesopores (2.0 nm < d < 50 nm), able at solution pHs above 6.1 due to electrostatic interactions.
and macropores (d > 50 nm) [27]. From the textural proper-
ties recorded in Table 1, it can be concluded that RSB is a 3.1.4. X-ray diffraction spectral analysis
mesoporous material.
XRD analysis was performed to determine the degree of
crystalline or amorphous nature of the RSB. Fig. 4 shows the
3.1.2. Fourier transform infrared spectral analysis XRD pattern of the RSB. The curve was indexed based on a
FTIR spectral analysis elucidates the structural and standard diffraction reference pattern (PCPDF No: 898487).
compositional information on the active functional groups The X-ray diffractograms indicate the appearance of a broad
presented in the RSB. FTIR spectrum of RSB before adsorp- diffraction background and the absence of a sharp peak
tion (Fig. 2a) shows various functional groups, in agree- reveals a predominantly amorphous structure. XRD peak at
ment with their respective wavenumber (cm−1) position. 2θ = 24° in the spectrum assigned to the reflection from (002)
The broadband at 3,500 cm−1 is assigned to the overlapping relates to crystalline carbon with expanded lattice parame-
of the stretching vibrations of the hydroxyl (O−H) and ters (carbon with impurities).
amine (N−H) groups, while band around 3,000 cm−1 is due
to carboxylic acid O−H stretching. The band at 1,633 cm−1 3.1.5. SEM–EDX analysis
associated with C=O (ketones, aldehydes, lactones, or car-
boxyl groups) [28]. The asymmetric and symmetric vibra- The SEM and EDX results of RSB before and after MB
tions of –COO of the ionic carboxylic groups within RSB are dye adsorption are shown in Figs. 5a and b, respectively. As
represented by the band at 1,523 cm–1. The bands between seen in Fig. 5a, the external surface of RSB displays a rough
the 1,300 and 1,000 cm−1 regions are assigned to the C–O and texture distributed over the surface. Additionally, the corre-
C–O–C stretching vibrations in carboxylic acids, alcohols, sponding EDX spectrum (Fig. 5a) indicates that the RSB con-
phenols, or ester groups [12–14]. Thus, the FTIR spectrum sists of mainly C and O, and a detectable amount of Si and N.
of RSB before adsorption indicates that the external surface After MB adsorption (Fig. 5b), the RSB surface is transformed
of RSB is rich with various functional groups, containing to be more compact and smoother due to filling of MB dye
oxygen of carboxylic and carbonyl species. These active molecules on the RSB surface. It was also observed from EDX
groups on RSB surface are responsible for enhancing the results (Fig. 5b) that RSB consists of mainly C and O, and a
adsorption of MB dye molecules due to electrostatic inter- detectable amount of Si and N. The slight increment in the
action. After MB dye adsorption (Fig. 2b), the band shifted
and became more pronounced, and new bands assigned
to nitro (1,274–1219 cm–1) are attributed to MB dye loaded
onto RSB surface.

Table 1
Physicochemical characterization of RSB

Properties/characteristics Values
Bulk density (g/mL) 0.14
Ash content (wt.%) 9.44
Moisture content (wt.%) 3.15
Textural properties
BET surface area (m²/g) 4.42
Langmuir surface area (m²/g) 6.69
Average pore width (nm) 29.8
Fig. 1. Isotherms of N2 adsorption–desorption for RSB.
 A.H. Jawad et al. / Desalination and Water Treatment 190 (2020) 322–330 325

(a)

(b)

Fig. 4. XRD pattern of RSB.

Fig. 2. FTIR spectra of (a) RSB, and (b) RSB after MB dye
adsorption.
RSB dose of 0.1 g/100 mL with 84.05% removal and there-
after, further increase of dosage did not exert an apprecia-
ble increase in the MB removal percentage. This situation
can be explained by aggregate formation during adsorption,
which takes place at high adsorbent concentrations causing a
decrease in the effective adsorption areas [14]. Therefore, in
further experiments the adsorbent dosage was fixed at 0.1 g
for further investigations.

3.2.2. Effect of pH
The pH of solution was expected to influence the adsorp-
tion capacity of dyes as it has the ability to modify dyes
chemistry and also the surface charge of the adsorbent. Fig. 7
shows the effect of pH on the adsorption of MB dye by RSB.
The adsorption of MB dye by RSB increased steadily with
the increasing solution pH up to pH 7.0. After that, a further
increase in pH values demonstrated no obvious changes. At
acidic pH, lower adsorption capacity were reported due to an
additional concentration of H+ ions competing with the MB
Fig. 3. pHpzc of RSB suspensions. dye cations for adsorption sites. At solution pH < pHpzc = 6.1,
the surface of RSB was essentially positively charged and
thus, repulsion between the MB dye cations and the RSB
C, O, and N content of RSB after MB dye adsorption (Fig. 5b)
may have occurred and decreased the MB dye adsorption
can be attributed to the MB dye molecules loaded on the RSB
capacity. On the other hand, At solution pH > pHpzc = 6.1 as
surface.
the solution pH of the system increased, the surface of RSB
was likely to adopt negative surface charges and became
3.2. Batch Adsorption Experiments increasingly favorable for MB adsorption due to electrostatic
forces of attraction. In fact, at higher solution pH values, the
3.2.1. Effect of the adsorbent dosage
surface of RSB adopts a negative surface charge, which con-
The influence of adsorbent dosage on the removal of tributes to enhanced uptake of positively charged dye spe-
MB dye from aqueous solution was studied using variable cies via attractive electrostatic attraction, in accordance with
amounts of RSB ranging from 0.05 to 0.30 g at a fixed vol- an increase in the rate of adsorption. To continue this work,
ume, 100 mL and initial dye solution, C0 of 100 mg/L, while the effective solution pH for RSB was fixed at 7, and used in
other experimental parameters were kept constant at 303°K, further adsorption studies.
shaking speed of 110 stroke/min, a contact time of 60 min
and non-adjusted pH at 6.1 for the MB solution. The result
3.2.3. Effect of initial dye concentrations and contact time
for adsorptive removal of MB dye with respect to adsorbent
dosage is presented in Fig. 6. It is obvious that the removal The effect of concentrations and contact time is cru-
of MB dye increases rapidly with an increase of RSB dosage cial for determining the time required for the adsorbent to
due to the greater availability of the exchangeable active achieved equilibrium. Fig. 8 displays the amounts of MB
sites. The highest level of MB dye removal was achieved at dye adsorbed (qt) vs. time (min) at different initial MB dye
326 A.H. Jawad et al. / Desalination and Water Treatment 190 (2020) 322–330

Fig. 5. SEM–EDX profiles for (a) RSB and (b) RSB after MB dye adsorption at magnification power (1,000 K).

concentrations. The time variation plot pointed out that the overcome all mass transfer resistances between the aqueous
adsorption of MB dye was fast at initial stage. However, once and solid phases, but also determines a higher probability of
equilibrium was nearly approached, the adsorption process collision between MB dye ions and RSB surface. At higher
slows down gradually. This situation may due to the avail- MB dye concentrations, longer time was required for adsorp-
ability of unfilled active sites during the beginning stage of tion to complete, since there is a probability for MB dye mol-
adsorption, and after a certain period of time, vacant sites ecules to penetrate deeper within the interior surface of the
get occupied by MB dye molecules, creating a repulsive force RSB and be adsorbed at active pore sites.
between MB dye, and RSB surface in the bulk phase. The
amount of MB adsorbed by the RSB at equilibrium increases 3.3. Adsorption isotherm
from 22.7 to 99.4 mg/g as the initial MB dye concentration
increased from 20 to 100 mg/L. In batch adsorption experi- The adsorption isotherm is the most meaningful infor-
ments, the removal rate of the dyes from aqueous solutions mation which describes how the adsorbate molecules dis-
is controlled by the transport of dyes molecules from the sur- tribute between the solid-liquid phases when the adsorption
rounding sites to the interior sites of the adsorbent. High MB process reaches an equilibrium state [29]. Three isotherm
dye concentration not only provides a large driving force to models, namely Langmuir [30], Freundlich [31], and Te
 A.H. Jawad et al. / Desalination and Water Treatment 190 (2020) 322–330 327

mkin [32] were tested in this work. The Langmuir iso- Freundlich model is based on the assumption that mul-
therm model Langmuir describes the monolayer adsorp- tilayer adsorption process takes place on heterogeneous
tion process on uniform adsorption sites and is expressed adsorption sites. Linear equation of Freundlich model is
by Eq. (3): presented in Eq. (4):

qe =
qmax K aC e qe = K FC e1/ n (4)
(3)
1 + KaC e
where, Ce (mg/L) = equilibrium adsorbate concentration;
where, Ce (mg/L) = equilibrium adsorbate concentration; qe (mg/g) = amount of adsorbate adsorbed per unit mass of
qe (mg/g) = amount of adsorbed species per specified amount adsorbent; KF [(mg/g (L/mg)1/n] = Freundlich affinity constant.
of adsorbent; kL (L/mg) = Langmuir affinity constant; qmax Temkin model assumes that the heat of adsorption of all
(mg/g) = amount of adsorbate required to form an adsorbed the molecules in the layer decreases linearly with coverage
monolayer. due to adsorbent/adsorbate interactions, and adsorption is
characterized by a uniform distribution of binding energies,
up to some maximum binding energy. Temkin isotherm can
be expressed in its linear form is presented in Eq. (5):

RT
qe = ln ( KT C e ) (5)
bT

where, Ce (mg/L) = equilibrium adsorbate concentration;

qe (mg/g) = amount of adsorbate adsorbed per unit mass
of adsorbent; KT (L/mg) = equilibrium binding constant;
bT = adsorption heat.
A non-linear plot of Langmuir, Feundlich, and Temkin
models are shown in Fig. 9. The isotherm related param-
eters were calculated, and the results are shown in Table
2. Based on calculated data, Langmuir model shows best
fit with the highest correlation coefficients, R2 compared to
Freundlich and Temkin models. The results show that the
formations of a surface monolayer of MB dye molecules for
RSB. Moreover, the monolayer adsorption capacity, qm for
RSB towards MB dye was compared with other types of
Fig. 6. Effect of RSB dosage on MB dye removal (%) at biomass wastes as reported in Table 3. Therefore, the RSB
[MB]0 = 40 mg/L, V = 100 mL, pH = 5.6, T = 303 K, shaking utilized in this study can be considered as an effective bio-
speed = 110 stroke/min, and contact time = 60 min.
sorbent for removal of cationic dye like MB dye from aque-
ous solution.

Fig. 7. Effect of pH on the adsorption capacity of MB dye

by RSB at [MB]0 = 140 mg/L, V = 100 mL, T = 303 K, shaking Fig. 8. Effect of initial concentration and contact time on the
speed = 110 stroke/min, contact time = 60 min, and RSB dos- adsorption of MB dye by RSB at V = 100 mL, T = 303 K, pH = 7,
age = 0.1 g. shaking speed = 110 stroke/min, and RSB dosage = 0.1 g.
328 A.H. Jawad et al. / Desalination and Water Treatment 190 (2020) 322–330

120 120

100
100
Co= 20 mg/L
80 Co= 40 mg/L
80 Co= 60 mg/L

qt (mg/g)
Co= 80 mg/L
qe (mg/g)

60
Co= 100 mg/L
60 PFO
PSO
40
Experimental data
40 Langmuir model
Freundlich model 20

20 Temkin model
0
0 50 100 150 200 250 300
0 Time (min)
0 2 4 6 8
Ce (mg/L) Fig. 10. Non-linear plots of the pseudo-first- and pseudo-second-
order kinetic models for MB adsorption on RSB surface.
Fig. 9. Adsorption isotherm plots of the Langmuir, Freundlich,
and Temkin models for MB dye adsorption by RSB at 303 K.
where, qe (mg/g) = amount of adsorbate adsorbed per unit
mass of adsorbent; qt (mg/g) = amount of adsorbate adsorbed
Table 2 at any time; k2 [mg/(min g)] = PSO rate constant.
Isotherm parameters for adsorption of MB dye by RSB at 303°K The obtained results of these two kinetic models were
shown in Fig. 10 and also reported in Table 4. As can be
Isotherm Parameters Values observed from the data, the value of correlation coefficient
Langmuir qmax (mg/g) 158 of the PSO kinetic model (R2 ≥ 0.99) was higher compared
KL (L/mg) 0.25 to the PFO kinetic model (R2 ≤ 0.96). Also, the quantity of
theoretical qe (qe,cal) determined from the PSO was closer to
R2 0.99
the quantity of experimental qe (qe,exp). The results indicate
Freundlich KF [(mg/g) (L/mg)1/n] 35.5 that PSO has better fit than PFO for the process of MB dye
1/n 0.55 adsorption by RSB. This result infers that the rate of MB
R2 0.96 dye adsorption onto RSB seems to be governed by chemi-
Temkin bT 77.4 cal process that involved sharing of electrons or by covalent
kT (L/mg) 3.50 forces through exchanging of electrons between adsorbent
R2 0.98 and adsorbate. Similar finding was obtained for the adsorp-
tion of MB dye onto pomegranate peels [12], dragon fruit
peels [13], and watermelon rinds [14].

3.4. Adsorption kinetic

3.5. Adsorption mechanism
Adsorption kinetic was studied in order to understand
the controlling mechanism of adsorption process, such as The proposed adsorption mechanism of MB dye on the
mass transfer and chemical reactions. Two types of kinetic surface of RSB is presented in Fig. 11. Based on the various
models namely pseudo-first-order (PFO) and pseudo-sec- functional groups available on the surface of RSB as dis-
ond-order (PSO) models were used to test the fit of experi- cussed previously in FTIR spectral analysis, the adsorption
mental data of MB dye uptake by RSB. PFO was proposed by mechanism of MB dye can be attributed to the various inter-
Lagergren [33] as given by Eq. (6): actions, for example, electrostatic attractions between nega-
tively charged functional groups on the surface of RSB and
positively charged species of the hydrolyzed cationic MB+
(
qt = qe 1 − exp− k1t ) (6) which strongly attracted from solution onto RSB surface
[35], as sketched in Fig. 11a. Another important factor for
MB dye adsorption by the RSB surface is the n–π stacking
where, qe (mg/g) = amount of adsorbate adsorbed per unit
interaction (Fig. 9b). In fact, the n–π interaction generally
mass of adsorbent; qt (mg/g) = amount of adsorbate adsorbed
occurs where the lone pair electrons on an oxygen atom are
at any time; k1 = PFO rate constant; qe and k1 values at different
delocalized into the π orbital of an aromatic ring of dyes [36].
initial MB concentrations were calculated from the plots of
Another possibility of interaction is hydrogen bonding inter-
ln(qe – qt) against t.
action between the surface hydrogen bonds of the functional
The linear form of the PSO model is given by Eq. (7) [34]:
groups available on the RSB surface and nitrogen atoms of
the MB dye [35], as shown in Fig. 11c. Similar observations
qe2 k2t were reported by other researchers for the adsorption on MB
qt = (7)
1 + qe k2t dye on the surface of chemically treated carbon microspheres
 A.H. Jawad et al. / Desalination and Water Treatment 190 (2020) 322–330 329

Table 3
Adsorption capacities for MB dye by different biomass waste materials

Biomass waste Adsorbent dosage (g) pH Temp. (K) qmax (mg/g) References
Rice straw 0.1 g/100 mL 7.0 303 158 This Study
Softwood waste (Cedar) 0.8 6 298 217.3 [15]
Pomegranate peels 0.08/100 mL 5.6 303 200 [12]
Watermelon rinds 0.06 g/100 mL 5.6 303 188.6 [14]
Hardwood waste (Mahogany) 0.12 6 298 149.2 [15]
303 147
Rejected tea 0.25 g/100 mL 4.0 313 154 [16]
323 156
Tea waste 0.1 g/100 mL 8.0 303 85.1 [17]
Canola residues 0.35 g/100 mL 7.0 293 7.11 [18]

Table 4
Parameters of the PFO and PSO kinetic models for MB adsorp-
(a) tion by RSB at different initial MB dye concentration

Concentration, C0 (mg/L)
Parameter
20 40 60 80 100
qe,exp (mg/g) 22.7 51.4 67.4 83.0 99.4
PFO
qe,cal (mg/g) 46.1 65.9 88.5 103.1 142.2
k1 × 10–2 3.16 3.58 3.57 5.31 1.93
R2 0.94 0.96 0.95 0.96 0.87
PSO
(b) qe,cal (mg/g) 23.4 53.5 69.4 85.5 104.2
k2 × 10–3 7.00 3.00 2.00 2.00 1.00
R2 0.98 0.99 0.98 0.98 0.96

[37], multi-wall carbon nanotube [38], wrapping carbon

nanotube [39], and coal activated carbon [35].

4. Conclusion
The research work clearly indicates that RSB provides
a low-cost, renewable, and promising biosorbent for the
removal of MB dye from aqueous solutions. The adsorp-
tion experiments indicated that the PSO model provided
(c) the best description of the kinetic uptake properties, while
adsorption results at equilibrium are described by the
Langmuir model where the maximum adsorption capacity,
qmax is 158 mg/g. The mechanism of MB dye adsorption
on RSB included mainly electrostatic attractions, hydro-
gen bonding interaction, and π–π stacking interaction.
The results reveal that RSB a successful candidate for
the removal of cationic dyes from aqueous solutions.
The potential application of this material can be further
extended toward removal of heavy metals, pesticides, and
other colorless organic water pollutants.

Acknowledgments
Fig. 11. Illustration of the possible interaction between RSB sur-
face and MB dye: (a) electrostatic attraction, (b) n–π stacking The authors would like to thank the Universiti Teknologi
interactions, and (c) hydrogen bonding interactions. MARA, Institute of Research Management, and Innovation
330 A.H. Jawad et al. / Desalination and Water Treatment 190 (2020) 322–330

(Institut Pengurusan Penyelidikan and Inovasi) for support- [18] D. Balarak, J. Jaafari, G. Hassani, Y. Mahdavi, I. Tyagi,
ing this project under LESTARI grant [600-IRMI 5/3/LESTARI S. Agarwal, V.K. Gupta, The use of low – cost adsorbent (canola
residues) for the adsorption of methylene blue from aqueous
(037/2019)].
solution: isotherm, kinetic and thermodynamic studies, Colloid
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