LSST #808213, VOL 48, ISS 18

Application of Papaya Seeds as a Macro-/Mesoporous

Biosorbent for the Removal of Large Pollutant Molecule
from Aqueous Solution: Equilibrium, Kinetic, and
Mechanism Studies
Edson Luiz Foletto, Caroline Trevisan Weber, Daniel Assumpção Bertuol, and
Marcio Antonio Mazutti

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Application of Papaya Seeds as a Macro-=Mesoporous Biosorbent for the Removal of Large Pollutant Molecule from Aqueous Solution: Equilibrium,
Kinetic, and Mechanism Studies
Edson Luiz Foletto, Caroline Trevisan Weber, Daniel Assumpção Bertuol, and Marcio Antonio Mazutti
 3b2 Version Number : 7.51c/W (Jun 11 2001)
File path : P:/Santype/Journals/TandF_Production/LSST/v48n18/LSST808213/LSST808213.3d
Date and Time : 30/09/13 and 12:29
Separation Science and Technology, 48: 1–8, 2013
Copyright # Taylor & Francis Group, LLC
ISSN: 0149-6395 print=1520-5754 online
DOI: 10.1080/01496395.2013.808213
Application of Papaya Seeds as a Macro-/Mesoporous
Biosorbent for the Removal of Large Pollutant Molecule
from Aqueous Solution: Equilibrium, Kinetic, and
Mechanism Studies
5 Edson Luiz Foletto, Caroline Trevisan Weber, Daniel Assumpção Bertuol, and
Marcio Antonio Mazutti
Department of Chemical Engineering, Federal University of Santa Maria, Santa Maria, Brazil
The potential use of papaya seeds as biosorbent for the removal
of a large dye molecule, Procion Red, from aqueous solution was
10 investigated. Papaya seeds were characterized by nitrogen adsorp-
tion/desorption isotherms and scanning electron microscopy. The
results revealed that the papaya seeds exhibit a macro-/mesoporous
structure, which is desirable for applications in adsorption
processes. The models of Langmuir, Freundlich, and Temkin were
15 employed to fit the equilibrium data, where the Langmuir model
showed the most suitable fitting. The maximum adsorption capacity
for Procion red dye was found to be 73.26 mg g
1. Pseudo-
first-order, pseudo-second-order, Elovich, and intraparticle diffusion
models were used to analyze the kinetic data obtained at different
20 concentrations of dye. The adsorption process of Procion red dye
followed the pseudo-second-order and intraparticle diffusion models.
The results indicated that the adsorbent used in this work is
adequate for the treatment of large dye molecules containing in
aqueous solutions. This work highlights the potential application
25 of papaya seeds in the field of adsorption.
Keywords adsorption; dye; equilibrium; kinetics; papaya seed
INTRODUCTION
Dyes are used as coloring agents in many industries such
30 as textile and tanneries. When improperly discharged into
the environment, these dyes may affect aquatic life due to
their toxicity and the reduction of light penetration (1).
Some methods for dye removal from industrial wastewater
include adsorption (2), coagulation (3), flotation (4), and
35 photocatalysis (5,6). Among these chemical and physical
methods, the adsorption using activated carbon has been
found to be promising compared with other techniques in
terms of efficiency to remove a broad range of pollutant
molecules (7). However, activated carbon is still considered
40 expensive, which limits their use. Besides, in recent years
Received 5 August 2012; accepted 21 May 2013.
Address correspondence to Edson Luiz Foletto, Department
of Chemical Engineering, Federal University of Santa Maria,
97105-900, Santa Maria, Brazil. E-mail: efoletto@gmail.com
1
various kinds of low-cost materials have been used as alter-
native adsorbents to activated carbon, which are mainly
vegetable waste such as rice husk (8), orange peel (9), seed
shells of sesame (10), sugarcane bagasse pith (11), oil palm
shell (12), and wheat husk (13). Unfortunately, these 45
low-cost adsorbents usually present low adsorption capaci-
ties and, consequently, its applicability in an industrial
wastewater treatment is not attractive from the economic
point of view.
Some recent studies are reporting that the use of papaya 50
(Carica papaya L.) seeds for the removal of dyes from
aqueous solutions has a high adsorption capacity. Hameed
(14) reported the use of papaya seeds to adsorb methylene
blue dye and obtained an adsorption capacity of about
555 mg g
1, while Unuabonah et al. (15) using the same 55
dye, reported values of 769 and 1250 mg g
1 for the undef-
fated and deffated papaya seeds, respectively. Recently,
papaya seeds have been used for the removal of tannery
dye in aqueous solution, which showed adsorption capacity
of 440 mg g
1(16). Despite its high adsorption capacity, the 60
use of papaya seeds in the adsorption of textile dye with
large size molecule has not been reported.
The use of papaya seeds as adsorbent to remove dyes
from aqueous solutions is particularly attractive in Brazil.
In the year of 2009 about 1.8 million of tons of papaya 65
fruits were harvested that corresponds to about 30% of
the world production (17). Also, India, Mexico, Nigeria,
and Indonesia are big papaya fruits producers. The portion
of seeds from papaya fruit is about 15 to 20% of its weight
and its final disposition in the environment must be done 70
carefully in order to avoid some serious pollution con-
ditions. Consequently, the use of papaya seeds as dye
adsorbent is very interesting from the environmental and
economic point of view, since it is an agricultural residue
that is available at low cost. 75
In this sense, the aim of the present study was to
evaluate the use of papaya seeds to remove textile dye that
 2 E. L. FOLETTO ET AL.
present large size molecule from aqueous solution. Kinetics
and equilibrium studies using a linear procedure were
80 carried out to evaluate the mechanism and equilibrium
isotherm of dye adsorption onto papaya seeds.
MATERIALS AND METHODS
Adsorbent, Characterization, and Adsorbate
Papaya fruits were collected at a local farm. The seeds
85 were removed from the fruit and dried at 90 C in an oven
for 24 h followed by crushing in a knife-mill. The resulting
material was sieved, and a portion with particle diameter
between 350 and 450 mm was used in the experiments. Analy-
sis of the surface area (BET) of the solid was performed
90 using the N2 adsorption-desorption isotherm at 77 K by
using Micrometrics ASAP 2020 equipment. The surface
physical morphology of the papaya seed was observed by
a scanning electron microscope (SEM, Shimadzu SSX-
550). Procion Red HE7B (CI Reactive Red 141; CAS num-
95 ber 61931-52-0; chemical formula is C52H34O26S8Cl12N14;
molecular weight ¼ 1,952 g mol
1), a dye extensively used
in the textile industry, was used as the model compound.
The chemical structure of the dye is given in Fig. 1.
Adsorption Studies
100 For the adsorption experiments, 50 mg of papaya seeds
were added to 100 mL of aqueous solution of dye at
FIG. 1. Three-dimensional chemical structure of Procion Red dye,
obtained by ChemBio 3D Ultra version 11.0 program. (Color figure
available online)
different initial concentrations (70 to 300 mg L
1). The
adsorption tests were carried out at various pH (2.5 to
9.0), which were adjusted using 0.1 M HCl or 0.1 M NaOH.
The resulting solution was continuously stirred using a 105
thermostatic orbital shaker (Tecnal, Brazil) under stirring
(100 rpm), at constant temperature (25 C). An aliquot of
the aqueous solution was taken at various time intervals
and filtered before analysis. The concentration of the dye
in aqueous solution was determined through the use of a 110
UV-vis spectrophotometer (Spectro vision, model
T6-UV). Absorbance values were recorded at the wave-
length of maximum absorbance of dye (kmáx ¼ 545 nm).
The amount of dye adsorbed per unit mass of adsorbent
at equilibrium (qe; mg  g
1) was determined from: 115
qe ¼ ½ðCo
Ce Þ  V =m ð1Þ
where Co is the initial dye concentration in liquid phase
(mg L
1), Ce is the dye concentration at equilibrium (mg L

1
), m is the mass of adsorbent (g), and V is the volume of
dye solution (L). All the adsorption experiments were carried 120
out in duplicate and only the mean values were reported. The
maximum deviation observed was about 4.5%.
Equilibrium and Kinetic Models
In this study, three equilibrium isotherm models were
investigated: Langmuir (9), Freundlich (9), and Temkin 125
(18). The respective equations are given in Table 1, where
qe, Ce and qmax are the equilibrium adsorption capacity
(mg g
1), equilibrium concentration (mg L
1) and the
maximum adsorption capacity (mg g
1), respectively; kF,
kL, and nF are the Freundlich adsorption constant 130
(mg g
1), Langmuir equilibrium constant (L mg
1), and
Freundlich constant related to adsorption intensity,
respectively; R, T, A, and B are the universal gas constant
(8.314 J mol
1 K
1), absolute temperature (K), equilibrium
binding constant (L mg
1), and a constant related to the 135
heat of adsorption, respectively. Also, four kinetic models
were tested: pseudo-first-order (8), pseudo-second-order
(8), Elovich (9), and intraparticle diffusion (1) models.
The respective kinetic equations are given in Table 2, where
TABLE 1
Isotherm models
Langmuir 1 1 1
¼ þ
qe kL qmax Ce qmax
Freundlich 1
logðqe Þ ¼ logðkF Þ þlogðCe Þ
nF


Temkin RT RT
qe ¼ lnðAÞ þ lnðCe Þ
B B
 PAPAYA SEED FOR THE REMOVAL OF LARGE POLLUTANT MOLECULE 3

TABLE 2
Kinetic adsorption models
Pseudo-first order lnðqe
qt Þ ¼ lnðqe Þ
k1 t

Pseudo-second order t 1 1
¼ þ t
qt k2 q2e qe

h ¼ k2 q2e

Elovich 1 1
qt ¼ lnðabÞ þ lnðtÞ
b b
pffiffi
Intraparticle diffusion qt ¼ kid t þ C
FIG. 3. SEM image of papaya seed.

predominant presence of mesopores (type IV) and some

140 qe and qt are the adsorption capacity at equilibrium and at
time t, respectively (mg g
1); k1, k2, kid, h are the rate con-
stant of pseudo-first-order adsorption (min
1), rate con-
stant of second-first-order adsorption (g mg
1 min
1),
intraparticle diffusion rate constant (mg g
1 min
0.5) and

1
1
145 initial sorption rate (mg g min ) (at t ! 0), respectively;
a, b, C are the initial adsorption rate (mg g
1 min
1),
desorption constant (g mg
1), and a parameter related to
the thickness of the boundary layer, respectively.
RESULTS AND DISCUSSION
150 Characteristics of the Adsorbent
Figure 2 shows the nitrogen adsorption-desorption
isotherms of the papaya seeds. According to the Brunauer-
Beming-Deming-Teller (BDDT) classification, the majority
of physisorption isotherms can be grouped into six types
155 (19). Typically, papaya seeds sample is a combination
of types II and IV, with a hysteresis loop, indicating the
macropores (type II). The pore size distribution calculated
from the adsorption blanch of the isotherm is presented
in Fig. 2 (see inset). It can be seen that papaya seeds sample 160
has a wide pore size distribution from mesopore (20 Å <
pore diameter < 500 Å) to macropore (pore diameter
500 > Å). From the BET characterization of the sample a
specific surface of 0.23 m2 g
1 was obtained and an average
pore diameter of 332 Å. 165
The SEM image (Fig. 3) shows a papaya seed particle
containing a heterogeneous, irregular, and rough surface.
This surface characteristic may enhance the adsorption of
large dye molecules onto papaya seed particles.
Influence of Physicochemical Parameters on the 170
Adsorption Process
One of the most important factors in adsorption studies
is the effect of the acidity of the medium (20). Procion red
dye removal by the papaya seeds at 25 C was found to be
pH dependent as shown in Fig. 4. Equilibrium adsorption 175
was favored by acidic pH and maximum adsorption by

FIG. 2. N2 adsorption=desorption isotherms and (inset) pore diameter FIG. 4. Influence of initial pH on the adsorption of Procion Red dye by
distribution of the sample of papaya seeds. papaya seeds (Initial concentration of dye: 100 mg L
1; T ¼ 25 C).
 4 E. L. FOLETTO ET AL.

sample was observed at pH 2.5. When the pH of the dye repulsion between the adsorbed negatively charged sorbate
solution was increased from 2.5 to 5.5, the amount of the species onto the surface of the adsorbent and the available 215
dye adsorbed decreased from 37.58 to 17.72 mg g
1, anionic sorbate species in solution as well as the slow pore
180 respectively. A large decrease in adsorption capacity for diffusion of the solute ion into the bulk of the adsorbent
this dye was observed under basic conditions. A decrease (9). From Fig. 5, it was also observed that the contact time
from 16.20 to 7.10 mg g
1 was observed when the pH required to attain equilibrium was about 250 min for all the
increased from 7.0 to 9.0, respectively. Similar adsorption initial concentrations of dye used in this work. 220
behavior has been reported in the literature (21). The
185 adsorption of dye onto adsorbent is influenced by the pH
of the solution and also by the zero point charge (pHzpc) Adsorption Isotherms
of the adsorbent. The pHzpc of papaya seeds has been The analysis of the isotherm data indicates how the
found to occur at pH 6.25 (15). The surface of the papaya pollutant molecules are distributed among the aqueous sol-
seeds is positively charged below pH 6.25, while it acquires ution and solid phase when the adsorption process reaches
190 a negative charge above this pH. Procion Red is an anionic
dye that contains eight sulphonate groups (
SO
3 ) (see
Fig. 1). The adsorption of an anionic dye generally
decreases, increasing the pH. This phenomenon is associa-
ted with the negative charge on the adsorbent surface and
195 also with excess OH
ions in the solution that compete for
the adsorption sites (22). Therefore, at pH < 6.25 high elec-
trostatic attraction occurs among the positively charged
surface of the adsorbent and negatively charged dye. On
the other hand, at pH > 6.25, an electrostatic repulsion
200 occurs among the negatively charged surface on the
adsorbent and the negatively charged dye.
The influence of dye concentration and contact time on
adsorption kinetics using papaya seed as adsorbent at pH
2.5 and 25 C is presented in Fig. 5. As can be seen, the
205 amount of dye adsorbed per unit mass of papaya seed
increases with increasing initial dye concentration and con-
tact time. In addition, in the first minutes a fast adsorption
of dye into the papaya seed was verified, indicating a fast
adsorption process that is due to the availability of the
210 positively charged surface of the adsorbent, which led to
fast electrostatic adsorption of the anionic dye from the
solution at pH 2.5. After this period, a slow adsorption rate
of dye was verified that can be due to the electrostatic

FIG. 5. Influence of initial dye concentration and contact time on the FIG. 6. The plots of (a) Langmuir, (b) Freundlich, and (c) Temkin
adsorption of Procion Red by papaya seeds (T ¼ 25 C; pH ¼ 2.5). isotherm models for the Procion Red adsorption onto papaya seeds.
 PAPAYA SEED FOR THE REMOVAL OF LARGE POLLUTANT MOLECULE
225 the equilibrium state, and also is an important step in find-
ing a suitable model that can be used for design purposes.
The data were fitted using the Langmuir, Freundlich, and
Temkin isotherms, which are shown in Fig. 6. These equi-
librium models provide important information concerning
230 the adsorption mechanism, the surface properties, and
affinity of the adsorbent. The Langmuir model is appli-
cable to homogeneous adsorption systems when there is
no interaction among the sorbate molecules, whereas the
Freundlich model is an empirical equation used to describe
235 heterogeneous systems and it is not restricted to the forma-
tion of the monolayer (20). The Temkin isotherm model
assumes that the adsorption heat of all molecules in the
layer decreases linearly with the coverage due to
adsorbate-adsorbate interactions (9).
240 The adsorption parameters obtained from the plots
showed in Fig. 6 are listed in Table 3. The Langmuir iso-
therm (Fig. 6a) presented the best fitting of experimental
data, since the correlation coefficient was higher than
0.98, whereas the other linear models (Figs. 6b and 6c)
245 showed a lower correlation coefficient. These results
strongly suggest that there was monolayer coverage of
dye molecule on the activated carbon surface. The essential
characteristics of the Langmuir isotherm can be expressed
in terms of a dimensionless equilibrium parameter (RL)
250 (12). The parameter is defined by: RL ¼ 1=(1 þ kLCo),
where Co is the highest dye concentration in liquid phase
(mg L
1) and kL is the Langmuir adsorption constant
(L mg
1). The value of RL implies the adsorption to
be unfavorable (RL > 1), linear (RL ¼ 1), favorable
255 (0 < RL < 1), or irreversible (RL ¼ 0). The value of RL was
found to be 0.17 and confirmed that the Langmuir iso-
therm was favorable for adsorption of Procion red dye
onto the papaya seed under the conditions used in this
study. The maximum capacity (qmax) obtained using the
260 Langmuir isotherm for the adsorption of Procion red dye
was 73.26 mg g
1. This result is higher than the adsorption
TABLE 3
Isotherm parameters for Procion red adsorption onto
papaya seeds. Conditions: pH ¼ 2.5, T ¼ 25 C; Adsorbent
mass ¼ 50 mg
Langmuir
qmax (mg g
1) kL (L mg
1) R2
73.26 0.016 0.982
Freundlich
KF (mg g
1) nF R2
2.88 0.346 0.867
Temkin
A (L mg
1) B R2
16.77 51.86 0.906
5
capacities of various low-cost adsorbents and activated
carbons for different dyes reported in the literature. A qmax
value of 63.53 mg g
1 was observed by Önal (23) for
adsorption of Crystal Violet on activated carbon prepared 265
from waste apricot. Gupta et al. (24) reported that the qmax
values for adsorption of Vertigo Blue and Orange DNA 13
from aqueous solution were 11.57 and 4.54 mg g
1, respect-
ively, on carbon slurry developed from a waste material.
Bulut and Aydin (25) obtained a qmax value of 270
21.50 mg g
1 for the adsorption of methylene blue on
wheat shells. Cardoso et al. (26) found qmax values of 66
and 38.8 mg g
1 for adsorption of the textile dyes Reactive
Red 194 and Direct Blue 53, respectively, on cupuassu
shell. These results mentioned above indicate that the 275
papaya seed has a good ability to remove dye molecules
from aqueous solution, which may be attributed to its
macro-=mesoporous structure. These physical characteris-
tics are of great importance for adsorption purposes
because it allows for a greater accessibility of pollutant 280
molecules to the adsorbent. As mentioned in the Introduc-
tion, Hameed (14) found a qmax of 555 mg  g
1 for the
methylene blue dye onto papaya seeds. However, the size
of methylene blue molecule is lower (maximum length of
14.2 Å) (27) than the Procion red (maximum length of 285
23 Å; see Fig. 1), which may explain the greater qmax for
the methylene blue dye onto papaya seed. The adsorption
capacity depends greatly on the porosity of the adsorbent
material in relation to the size=volume of the adsorbate
molecules. The ratios between the average pore diameter 290
of the adsorbent (332 Å) and the maximum lengths of
Procion red and methylene blue dye molecules are 15
and 24, respectively. This implies that each pore of the
papaya seed particle could accommodate up to fifteen
Procion red dye molecules, and twenty-four methylene 295
blue molecules.
Adsorption Kinetics and Mechanism
Adsorption kinetic study is important because it pro-
vides valuable information concerning the mechanism of
dye adsorption in liquid solution. The prediction of 300
adsorption kinetics is necessary for the design of industrial
adsorption system. In this work, four kinetic models were
fitted (Fig. 7) and the kinetic parameters are presented in
Table 4. Only the pseudo-second-order kinetic model
(Fig. 7b) presented satisfactory fitting of the experimental 305
data, as can be seen by its high correlation coefficient
(R2). This indicates that the adsorption of Procion red
dye on papaya seed follows a pseudo-second-order kinetic
model. Similar phenomenon has also been observed in the
adsorption of basic blue 3 on activated carbon derived 310
from hevea brasiliensis seed coat (28), adsorption of
Bismark brown on activated carbon prepared from rubber-
wood sawdust (29), and the adsorption of reactive orange
dye on activated carbon prepared from sugarcane bagasse
 6 E. L. FOLETTO ET AL.

FIG. 7. Kinetic models for the adsorption of Procion Red dye: (a) Pseudo-first order, (b) Pseudo-second order, (c) Elovich, and d) Intraparticle
diffusion.

315 pith (11). The pseudo-first-order kinetic (Fig. 7a) and Adsorption kinetic data also were treated in this work
Elovich (Fig. 7c) models presented no satisfactory fitting using the intraparticle diffusion model. The model is 320
of the experimental data, as indicated by the low values represented in Fig. 7d. According to Fig. 7d, a plot of qt
of correlation coefficient obtained. versus t0.5 should be a straight line when the adsorption

TABLE 4
Kinetic parameters for the dye adsorption onto papaya seeds. Experimental conditions: pH ¼ 2.5,
T ¼ 25 C; Adsorbent mass ¼ 50 mg
Co (mg L
1)
Kinetic models 70 100 150 200 300
Pseudo-first order
k1 (min
1) 0.0112 0.0085 0.0054 0.0060 0.0064
R2 0.728 0.727 0.870 0.907 0.771
Pseudo-second order
k2  10
3 (g mg
1 min
1) 4.031 5.37 2.03 1.25 2.11
h (mg g
1 min
1) 4.65 7.35 5.07 3.806 7.35
R2 0.992 0.995 0.997 0.998 0.995
Elovich
a (mg g
1 min
1) 283.87 11.30  103 102.10 21.59 694.81
b (g mg
1) 0.297 0.375 0.171 0.124 0.187
R2 0.914 0.903 0.913 0.910 0.870
Intraparticle diffusion
kid (mg g
1 min
0.5) 0.786 0.797 1.506 1.554 1.574
C 20.79 25.11 25.99 27.89 36.01
 PAPAYA SEED FOR THE REMOVAL OF LARGE POLLUTANT MOLECULE
mechanism follows the intraparticle diffusion process. Such
types of plots may present multilinearity, implying that two
325 or more steps occur (30). The sharp first-stage portion is
the external surface adsorption stage. The second portion
is the gradual adsorption stage, where the intraparticle dif-
fusion is rate-limited. From Fig. 7d it was observed that
there were two linear steps, indicating that the adsorption
330 process of the Procion red dye on the papaya seed tends
to be controlled by both surface adsorption and intraparti-
cle diffusion. Vadivelan and Kumar (30) observed a similar
behavior, with two linear portions for the adsorption of
methylene blue on rice hulls. Two linear steps also were
335 found for the adsorption of Basic violet 3 and Acid black
1 dyes on unburned carbon from coal combustion residue
(31). Thus, several factors can affect the kinetics of dye
adsorption onto the adsorbent. These factors include the
chemical and physical structure of the dye molecule, the
340 physical properties of the adsorbent, and the experimental
solution conditions.
CONCLUSIONS
The present study showed that the presence of mesopores
together with macropores in the papaya seed make it a good
345 alternative as biosorbent to remove large molecule as Pro-
cion red from aqueous solution. The Langmuir isotherm
was the most suitable to fit the equilibrium data, indicating
a monolayer adsorption of Procion red dye onto papaya
seed particles with a maximum capacity of 73.26 mg g
1.
350 Four kinetic models were used to evaluate the adsorption
mechanism and the best fit was using the pseudo-second-
order kinetic model. The adsorption process was found to
be controlled by both surface and pore diffusion.
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