Journal of Water Resource and Protection, 2013, 5, 10-17
http://dx.doi.org/10.4236/jwarp.2013.57A003 Published Online July 2013 (http://www.scirp.org/journal/jwarp)
Application of Modified Bagasse as a Biosorbent for
Reactive Dyes Removal from Industrial Wastewater
Abd El-Aziz A. Said1*, Aref A. M. Aly1, Mohamed M. Abd El-Wahab1, Soliman A. Soliman1,
Aly A. Abd El-Hafez1, V. Helmey2, Mohamed N. Goda1
1Chemistry Department, Faculty of Science, Assiut University, Assiut, Egypt
2 Mechanical Engineering Department, Faculty of Engineering, Assiut University, Assiut, Egypt
Received April 15, 2013; revised May 18, 2013; accepted June 25, 2013
Copyright © 2013 Abd El-Aziz A. Said et al. This is an open access article distributed under the Creative Commons Attribution Li-
cense, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
Propionic acid modified bagasse was used for the removal of reactive yellow 2 and reactive blue 4. The effects of pH,
contact time, initial dye concentrations, adsorbent particle size and adsorbent dose on the adsorption of the two dyes
were investigated. Additionally, the desorption process and intra-particle diffusion were studied. Acidic pH values were
favorable for adsorption of both dyes. The equilibrium adsorption data were best fitted with the Freundlich isotherm for
reactive yellow 2 and the Langmiur isotherm for reactive blue 4. The values of their corresponding constants were de-
termined. The kinetic for dye adsorption is well described by a pseudo-first order kinetic model for the reactive yellow
2 and by pseudo-second order for the reactive blue 4. The investigation revealed that the hydroxyl groups of bagasse
and the carboxylic group of propionic acid play a great role in the removal of both reactive dyes.
Keywords: Modified Bagasse; Reactive Yellow 2; Reactive Blue 4; Adsorption; Kinetics
Dyes are widely used in many industries such as textile,
plastic, paper, food and cosmetic for coloring their prod-
ucts. These dyes are water pollutants and cause environ-
mental hazards. In addition, many dyes are difficult to be
biodegradable and tend to persist in the environment cre-
ating serious water quality and public health problems.
So, a conventional biological treatment process is not
very effective in treating dyes wastewater. There are
various methods for removing dyes including coagula-
tion and flocculation , oxidation or ozonation  and
membrane separation . However, these processes are
very expensive and cannot be effectively used to treat the
wide range of dyes waste. Alternative methods include
adsorption on natural biosorbents which are becoming
now of high interest for removal of dyes from waste ef-
fluents. In this way several studies have used natural ma-
terials locally available, renewable and of low costs [4-6].
Among these sorbents are banana, bagasse, coir pith,
palm-fruit bunch, apple-pomace, wheat straw, rice husk,
pine sawdust, peanut hull, coffee husk, maize cob, or-
ange peel, sugar cane dust and luffa fiber [7-9].
Recently, sugarcane bagasse was used as potential low-
cost adsorbent for removal of many dyes from wastewater
Reactive dyes are generally used for colouring cotton
and other cellulosic material, but are also applied to a
small extent on wool and nylon. In the present study re-
moval of reactive yellow 2 and reactive blue 4 from
aqueous solutions using bagasse pre-treated with propi-
onic acid was investigated. Several parameters have been
studied such as pH, contact time, biomass dosage, and
particle size and desorption process. The equilibrium
sorption capacity and the kinetic adsorption of both dyes
on the modified bagasse were studied. The selection of
bagasse for this study was based on low cost raw mate-
rial and environmental impact.
2. Materials and Methods
Reactive yellow 2 and reactive blue 4 dyes were pur-
chased from Sigma-Aldrish Chemical Co. The chemical
structures of the two dyes are presented in Figure 1.
2.1. Preparation of Adsorbent
Sugar cane bagasse modified with propionic acid was
previously described .
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A. E.-A. A. SAID ET AL. 11
Figure 1. Chemical structures of reactive yellow 2(a) and
reactive blue 4(b).
2.2. Preparation of Aqueous Dye Solution
Stock solutions of the two dyes were prepared by dis-
solving accurately a weighed amount of each dye in dis-
tilled water (1000 mg/L) and diluting these solutions
prior to performing the adsorption experiments.
2.3. Adsorption Experiment
In each adsorption experiment 50 mL of dye solution of
known concentration and pH was added to known weight
of adsorbent in 100 mL airtight volumetric flasks at room
temperature (27˚C ± 1˚C) and the mixture was stirred on
a rotary orbital Shaker at 150 rpm. The dye solution was
filtered from bagasse and determined spectrophotometri-
cally by recording the absorbance changes at maximum
absorption (405 nm for reactive yellow 2 and 595 nm for
reactive blue 4) using Thermofischer Scientific, aqua
mate, Evolution 166 Uv-visible spectrophotometer. All
pH measurements were carried out with a pH-meter
model number JENWAY 3450. The initial pH values
were adjusted with 0.1 M HCl or NaOH to form series of
pH’s. Effect of adsorbent dosage was studied with dif-
ferent adsorbent doses and 50 ml of the dye solution at
equilibrium time. For the desorption studies the adsorb-
ent used for the adsorption of the dye solution was thor-
oughly washed with distilled water to remove unad-
sorbed dye and desorption process was conducted at a
range of pH values. The amount of dye adsorbed onto the
bagasse, qe (mg/g) was calculated as the following equa-
where Ci and Ce are the initial and equilibrium time solu-
tion concentration of the dye (mg/L) , respectively, V the
volume of the solution (L) and W the dry weight of the
2.4. Kinetic Studies
To assess the applicability of the adsorption process it is
necessary to determine the kinetic parameters, using the
batch technique. A series of volumetric flasks containing
100 mL capacity, containing 50 mL dye solutions of
known concentrations at the appropriate pH and were
agitated by mechanical shaker at room temperature. After
a definite time interval, the solutions were filtered and
the filtrates thus obtained were then analyzed spectro-
photometrically. All the experiments were duplicated and
only the mean values are reported. The maximum devia-
tion observed was less than ±5%.
2.5. Thermal Studies
Thermogravimetric analysis TGA and differential ther-
mal analysis DTA techniques of original and treated with
propionic acid (5 wt%) were carried out using a Shima-
dzu Thermal Analyzer model (TG 60 H). Curves of TGA
and DTA were recorded upon heating up to 600˚C at
10˚C·min −1 and flow of air of 30 mL·min−1.
3. Results and Discussion
3.1. Characteristics of Dyes
Table 1 summarizes some important characteristics of
reactive yellow 2 and reactive blue 4 dyes.
3.2. Thermal Analysis
Figure 2(a) shows that the decomposition of untreated
bagasse proceeds in five stages. The first region of (36˚C -
124˚C) which accompanied with 5.3% weight loss with an
endothermic peak minimized at 77˚C is attributed to the
physically adsorbed water. The second stage of (125˚C -
208˚C) which accompanied with 8.1% weight loss is due
to the dehydration water. The major weight loss (53.2%)
takes place within (209˚C - 358˚C) range which exhibit
exothermic peak maximized at 316˚C. This peak is cor-
responded to the decomposition of cellulose and hemi-
celluloses in bagasse . The fourth stage of (359˚C -
459˚C) and with exothermic peak maximized at 426˚C
and the fifth region of (462˚C - 600˚C) which accompa-
nied with 4% weight loss with exothermic peak maxi-
mized at 480˚C are attributed to the decomposition of
lignin component of bagasse . The TGA and DTA
curves of treated bagasse with 5 wt% propionic acid was
carried out and presented in Figure 2(b) and the data are
cited in Table 2, it shows that the thermal decomposition
of treated bagses proceeds in similar behaviour of un-
treated bagasse i.e., takes place in five stages. It is clear
from the DTA curve and the data depicted in Table 2 that
the addition of propionic acid retards the third decompo-
Copyright © 2013 SciRes. JWARP
A. E.-A. A. SAID ET AL.
Table 1. Characteristics of the used reactive dyes.
No. of functional groups available for interaction
Dye λmax (nm) C(wt%)
No. of ionizable
groups −SO −C=O −NH −Cl −NH2
Reactive yellow 2 404 34.5 3 9 1 2 3 -
Reactive blue 4 595 35 2 6 2 2 2 1
Table 2. Data for thermal decomposition of untreated and treated bagasse.
Temperature range (˚C) and weight loss (%)
Adsorbent 1st stage 2nd stage 3rd stage 4th stage 5th stage
Total weight loss
36 - 124 125 - 208 209 - 358 359 - 459 462 - 600
Original bagasse 5.3 8.1 53.2 21.1 4.0
36 - 123 124 - 231 232 - 357 358 - 439 440 - 600
Treated bagasse 3.7 11.5 54.7 24.1 2.6
Copyright © 2013 SciRes.
sition step while enhances the fourth and fifth decompo-
sition stages. This reflects that the presence of propionic
acid strongly affected the structure of bagasse, i.e., a good
interaction between bagasse and propionic acid. So, the
results of thermal analysis indicated that propionic acid
should affect the physico-chemical properties of bagasse.
3.3. Effect of pH
The pH of the dye solution has a great influence on the
adsorption of the dye on the biosorbent presumably due
to the effect on the surface properties of the adsorbent
and ionization or dissociation of the dye molecules. Fig-
ure 3 represents the effect of pH on the removal of both
dyes. The highest dye removal efficiency was observed
at pH = 1.9 and pH = 2.1 for reactive yellow 2 and reac-
tive blue 4, respectively.
These acidic pH values might correspond to the rate of
dissociation of the sulphonic acid groups located on the
dyes. Furthermore, it is assumed that under acidic condi-
tions the hydroxyl groups of bagasse and the carboxylic
group of propionic acid are protonated i.e., 2
50100 150 200 250 300 350 400 450 500 550 600
–COOH2+. Thus a significant electrostatic interaction
may occur between the positively charged sites of the
adsorbent and the negatively charged part of the two re-
active dyes (sulphonate groups) . The lower adsorp-
tion of both dyes at alkaline pH values may be due to the
presence of excess OH− ions competing with the dye
anions for the adsorption sites.
3.4. Effect of Agitation Time and Initial Dye
The relation between removal of both dyes and the contact
time was studied and the results are shown in Figure 4. It
appears that removal of both dyes was rapid in the initial
stages and then steadily increases with increasing time.
Temper ature (oC)
Weight loss (%)
Figure 2. TGA and DTA curves of (a) untreated bagasse and
(b) bagasse treated with 5 wt% propionic acid.
The rapid removal at the initial contact time may be as-
cribed to the availability of high positive charges on the
bagasse surface for adsorption of the anionic reactive dyes.
The subsequent slow adsorption of the two dyes is pre-
sumably correlated with the electrostatic repulsion be-
tween the adsorbed species onto the bagasse surface and
the negative charge adsorbate species existing in the so-
lution besides the slow pore diffusion of the dye into the
bulk of the adsorbent . Figure 5 shows the influence
of the initial concentration of both dye solutions on the
A. E.-A. A. SAID ET AL. 13
Figure 3. Effect of pH on dye removal, (1 g of 1 mm particle
Figure 4. Effect of agitation time on dye removal.
0100 200 300
Reactive blue 4
Reactive yellow 2
Adsorption capacity (mg/g)
Dye concentration (mg/L)
Figure 5. Effect of initial dye concentration on dye removal.
adsorption dynamics by bagasse treated with propionic
acid. Upon raising the initial dye concentration of the
reactive yellow 2 from 50 to 500 mg/L the adsorbent
capacity increased from 12.5 to 180 mg/g whereas for
reactive blue 4 the capacity increases from 20 to 200
mg/g when the initial dye concentration increased from
25 to 500 mg/L.
3.5. Effect of Sorbent Particle Size
The effect of particle size on the adsorption of the two
dyes onto the modified bagasse was studied (Figure 6),
using a fixed sorbent dose (25 mg/50 ml). Different par-
ticle sizes range i.e., 0.25, 0.5, 0.71 and 1 mm were
adopted. The results reveal that the percentage removal
of the dyes increases with the decrease in bagasse parti-
cle size. Clearly a decrease in particle size would in-
crease the surface area and consequently an increase in
dye adsorption onto the bagasse surface occurs. Various
factors are responsible for the low adsorption capacity of
the dyes on the sorbent large particles. Among them are
the diffusional path length or mass transfer resistance,
contact time and blockage sections of the particles (not
utilized for adsorption) .
3.6. Effect of Sorbent Dosage
The effect of adsorbent mass on the adsorption of the two
dyes was investigated on treated bagasse of 1 mm parti-
cle size at initial dye concentration of 500 mg/L. Figure
7 depicts the expected pattern for both dyes where the
percent removal of each dye increases as the adsorbent
dosage increases. This may be attributed to the increase
in surface area of bagasse and availability of adsorption
sites for the two reactive dyes. However, the adsorption
density, the amount adsorbed by unit mass, decreases.
This may be due to unsaturation of adsorption sites or
Figure 6. Effect of sorbent particle size on dye removal.
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A. E.-A. A. SAID ET AL.
Figure 7. Effect of bagasse dosage on dye removal.
due to some sort of particle interaction such as aggrega-
tion which will decrease the total surface area of adsorb-
ent and consequently an increase in the diffusion path
length . It is clear from the obtained results that the
removal of reactive blue 4 is more pronounced relative to
that of reactive yellow 2 upon increasing of the bagasse
weight above 1 gm.
3.7. Adsorption Isotherms
The adsorption isotherms are important to optimize the
design of an adsorption system to remove the dye. The
parameters obtained from the different isotherms provide
important information about the adsorption mechanisms
and surface properties. The most widely accepted surface
adsorption models are those of Freundlich and Langmuir.
3.7.1. Freundlic h Isotherm
Freundlich isotherm is expressed as.
where qe (mg/g) is the amount of dye adsorbed at equi-
librium, Ce (mg/L) is the equilibrium liquid-phase con-
centration of the dye and KF is a constant related to the
bonding energy and adsorption capacity. 1/n indicates the
adsorption intensity of dye onto the adsorbent and the type
of isotherm to be irreversible (1/n = 0), favorable (0 < 1/n
< 1) and unfavorable (1/n < 1).
Equation (2) can be arranged to a linear form:
1.5 1.6 1.7 1.8 1.9 2.0 2.12.2 2.3
To study the applicability of the Freundlich equation
for dye absorption onto bagasse a linear plot of log qe
versus log Ce is plotted and presented in Figure 8 and the
calculated parameters for Freundlich linear equation are
shown in Table 3. The reactive yellow 2 adsorption by
Figure 8. Freundlich isotherm for the sorption of reactive
yellow 2 at pH 1.9.
Table 3. Langmiur and Freundlic h isotherm parameters for
reactive yellow 2 and reactive blue 4 on modified bagasse.
R2 KF 1/n
Reactive yellow 20.9916 0.0045 1.5439
Reactive blue 4- - -
R2 Qm(mg/g) a(L/mg)
Reactive yellow 2- - -
Reactive blue 40.9956 13.2 0.052
modified bagasse fitted the Freundlich model well with R2
= 0.9916. The linear plot suggests the applicability of the
Freundlich equation. The 1/n is lower than 1.0, indicating
that reactive yellow 2 is favorably adsorbed by the pre-
treated bagasse. On the other hand the linear plot of the
Freundlich equation is not valid for reactive blue 4.
3.7.2. Langmiur Isotherm
The Langmiur equation is expressed as follows:
qaQC aC (4)
where qe and Ce are defined as in Freundlich equation, Qm
is the maximum adsorption capacity and a is the Langmiur
constant. Its linear form is expressed as:
CqaQ CQ (5)
The Qm and a values can be obtained from the slope
(1/Qm) and the intercept (1/a Qm) of the linear plot Ce/qe
versus Ce. Figure 8 illustrates the linear form of Langmuir
isotherm of the reactive blue 4 and the calculated pa-
Copyright © 2013 SciRes. JWARP
A. E.-A. A. SAID ET AL. 15
rameters are included in Table 3. It is clear from Figure 9
that the adsorption of the reactive blue 4 fits very well the
Langmuir equation with R2 = 0.9956 while the data do not
fit with the Freundlich equation .
3.8. Adsorption Kinetics
In order to investigate the adsorption process of the reac-
tive dyes by pretreated bagasse, pseudo-first order (Equa-
tion (6)) and pseudo-second order (Equation (7)) kinetic
models were used.
where qe is the amount of dye sorbed at equilibrium (mg/
g), qt is the amount of dye sorbed at time t (mg/g), k1 is the
rate constant of the pseudo-first order sorption (min−1), h
2e is the initial adsorption rate (mg/g·min) and k2 is
the rate constant of pseudo-second order kinetics (mg/g
min). Fi gure 10 shows that the pseudo first order equation
fits well for the adsorption of reactive yellow 2 whereas
the pseudo-second order equation is not valid. Moreover,
the correlation coefficient R2 and K1 were calculated from
the intercept and slope respectively and presented in Ta-
ble 4. The linear plot of t/qt versus t for reactive blue 4
shows a good linear relationship, Figure 11. On the other
hand the applicability of the pseudo-first order equation
on the adsorption of reactive blue 4 was found not appli-
cable. The correlation coefficient R2 and K2 were calcu-
lated from the intercept and the slope respectively and
recorded in Table 4.
From Table 4, the correlation coefficients for the first
and second order kinetic models are greater than 0.99
which led to believe that the first and second order equa-
020 40 60 80100120
Figure 9. Linear f orm o f th e Langmuir is oth erm for re a ctive
blue 4 at pH 2.1.
Figure 10. Pseudo-first order plot for the desorption of re-
active yellow 2 at pH 1.9.
t (min g/mg)
Figure 11. Pseudo-second order plot for adsorption of reac-
tive blue 4 at pH 2.1.
Table 4. Comparison of the first and second order adsorp-
tion rate constants and the correlation coefficients.
Pseudo-first order Pseudo-second
1 (min−1) R2 K2
4 - - 0.9950 0.0106
tions provided good correlations for the biosorption of
reactive yellow 2 and reactive blue 4 respectively, on
3.9. Intra-Particle Diffusion
The intra-particle diffusion model was applied to test the
Copyright © 2013 SciRes. JWARP
A. E.-A. A. SAID ET AL.
possibility of intra-particle diffusion of reactive yellow 2
and reactive blue 4 into pre-treated bagasse. The adsorp-
tion process involves a transport of solute from the
aqueous phase to the surface of the solid particles with a
subsequent diffusion of the dye molecules into the inte-
rior pores which is a slow process and is therefore, a rate
determining step. The particle diffusion model is ex-
pressed by the following equation :
where C (mg/g) is the intercept and Kd is the intra-parti-
cle diffusion rate constant (mg/g·min−1/2). Two intersect-
ing linear plots are obtained for both dyes indicating dif-
fusion of the dye molecules into macro- and micropores
of bagasse. If the mechanism of adsorption follows on
intra-particle diffusion process, the plot of qt versus t1/2
should be straight line and pass through origin. Figure
12 shows that there are two separate regions that repre-
sent the steps involved during the process of adsorption.
The initial straight line is due to the bulk diffusion while
the second straight line corresponds to the intra-particle
diffusion for both dyes. The plots were not best-fit
straight lines passing through the origin. This phenome-
non indicates that there is a boundary layer resistance.
One of the possible reasons for the deviation of the
straight line from the origin is that there is a difference in
the rate of mass transfer in the initial and final stages of
dye adsorption. The results of the experiment suggest
that the intra-particle diffusion is not the only step con-
trolling adsorption of the two dyes .
3.10. Desorption and Reuse
A further goal of any adsorbent used is reuse potential.
So, before the investigation of reuse, the adsorption ex-
periments were carried out to find the optimum pH-de-
sorption conditions. Figure 13 shows the effect of pH
values on the desorption process of the two dyes. It
shows that the two dyes are stable at lower pHs whereas
increasing pH higher than 10 results in a rapid desorption
of both dyes from bagasse surface. It is thus to be con-
cluded that the two reactive dyes are stable in the pH
range 3 - 10 for reactive yellow 2 and 6 - 10 for reactive
blue 4 while they may be completely recovered from the
treated bagasse surface at pH = 12 and higher. It is of
interest to mention here that these results are in agree-
ment with the results presented in Figure 2 which show
that the remarkable dye removal of both dyes on modi-
fied bagasse was at lower pH values.
Modified bagasse by propionic acid is an effective bio-
sorbent for the removal of both reactive yellow 2 and
reactive blue 4 dyes from wastewater. The maximum
R eactive blue 4
R eactive yellow 2
Figure 12. Intra-particle diffusion model for reactive yellow
2 at pH 1.9 and reactive blue 4 at pH 2.1.
100 Reactve blue 4
Reactive yellow 2
D esorption %
Figure 13. Effect of pH on the desorption process of the two
removal was observed at pH = 1.9 and pH = 2.1 for reac-
tive yellow 2 and reactive blue 4, respectively. Moreover,
the decrease of particle size of adsorbent was accompa-
nied with a pronounced removal of both dyes. The equi-
librium adsorption was best fitted with the Frundlich
isotherm for reactive yellow 2 and with the Langmuir
isotherm for reactive blue 4. Adsorption kinetics revealed
Copyright © 2013 SciRes. JWARP
A. E.-A. A. SAID ET AL.
Copyright © 2013 SciRes. JWARP
that reactive yellow 2 is well described by a pseudo-first
order whereas reactive blue 4 fits good for pseudo-second
order. Modified bagasse can be reused by desorption of
both dyes in the pH = 12 and higher. The hydroxyl and
carboxylic groups from bagasse and propionic acid re-
spectively enhance the removal of both reactive dyes.
The authors would like to thank the financial supports
from the Science and Technology for Development Fund,
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