68
Pol. J. Chem. Tech.,
Polish
Vol.
Journal
18, No.
of 2,
Chemical
2016 Technology, 18, 2, 68—77, 10.1515/pjct-2016-0031
Kinetic, isotherm and thermodynamics investigation on adsorption of
divalent copper using agro-waste biomaterials, Musa acuminata, Casuarina
equisetifolia L. and Sorghum bicolor
Ramya Prasanthi Mokkapati1, Jayasravanthi Mokkapati2, Venkata Nadh Ratnakaram3*
1
Acharya Nagarjuna University, Department of Chemistry, ANUCET, Guntur – 522510, India
Acharya Nagarjuna University, Department of Biotechnology, Guntur – 522510, India
3
GITAM University – Bengaluru, Karnataka – 561203, India
*
Corresponding author: e-mail: doctornadh@yahoo.co.in
2
Three novel and distinct agricultural waste materials, viz., Casuarinas fruit powder (CFP), sorghum stem powder
(SSP) and banana stem powder (BSP) were used as low cost adsorbents for the removal of toxic copper(II) from
aqueous solutions. Acid treated adsorbents were characterized by SEM, EDX and FTIR. Different factors effecting
adsorption capacity were analyzed and the efficiency order was BSP>SSP>CFP. Based on the extent of compatibility to Freundlich/Langmuir/D-R/Temkin adsorption isotherm and different models (pseudo-first and second order,
Boyd, Weber’s and Elovich), chemisorption primarily involved in the case of CFP and SSP, whereas, simultaneous
occurrence of chemisorption and physisorption was proposed in the case of BSP. Based on the observations, it was
proposed that three kinetic stages involve in adsorption process viz., diffusion of sorbate to sorbent, intra particle
diffusion and then establishment of equilibrium. These adsorbents have promising role towards removal of Cu(II)
from industrial wastewater to contribute environmental protection.
Keywords: banana bunch-stem powder, casuarinas fruit powder, sorghum stem powder, removal, copper,
adsorption.
INTRODUCTION
Technological advancements and improved industrialization in this modern era lead to the increased release of
heavy metal ions in to the water bodies like rivers, lakes
etc1. Copper is non-biodegradable and its accumulation
in ecological system can cause harmful effects to plants,
human and animals2. Even though trace amounts of copper is nutritious, the higher concentrations exceeding the
limit 1.5 mg L–1 can cause many severe diseases such as
liver and kidney damage, intestinal distress and stomach
ailments, cancer, nausea, vomiting, headache, diarrhea,
respiratory difficulties3. Excess of copper (II) leads to
different types of cancers since it can be deposited in
the brain, skin, liver and pancreas, and finally leading
to death4, 5. In addition, Cu(II) in acidic pH can cause
toxicological concerns to fish and other aquatic life even
in trace quantities6.
The conventional treatment techniques for copper
removal from aqueous solutions include chemical precipitation, ion exchange, membrane filtration, solvent
extraction, phyto extraction, ultra filtration, reverse
osmosis, adsorption etc. In addition, a number of non-conventional strategies involving the use of lignocellulosic
materials7, inorganic clay materials8, biopolymers9 and
synthetic polymeric hydrogels10 have also been reported
in the recent past. However, these processes used for
the separation of metal from contaminated water are
cumbersome and involve high cost consumption materials, for example, activated carbon for adsorption11.
Hence, among all water-treatment methods described,
biosorption is a highly preferred technique due to its
efficiency, easy handling and economic bulk availability
of adsorbents12–14. Particularly, the adsorbent materials
from agricultural origin have high affinity for Cu(II) due
to their various functional groups including carboxyl,
amide and hydroxyl group, etc. which are often ideal
because of their susceptibility to chemical modification
and mono to multilayer adsorption behavior for better
performance15.
Therefore, the present study is focusing on the use
of three novel chemically modified agricultural waste
materials viz., Musa acuminate (banana bunch stem
powder – BSP), Casuarina equisetifolia L. (casuarinas
fruit powder – CFP) and Sorghum bicolor (sorghum
stem powder – SSP) for effective removal of Cu(II) from
aqueous solutions. A comparative analysis throughout
the study using these three adsorbents can give better
understanding of the adsorption process in terms of
efficiency to remove copper metal ion from synthetic
aqueous solutions.
EXPERIMENTAL
Raw materials such as casuarinas fruit, sorghum stem
and banana bunch-stem for the preparation of adsorbents
are available abundantly in nature. They were cleaned
with distilled water. To reduce the organic leaching and
prevent mould growth during batch sorption the raw
materials were washed with 2% formaldehyde solution16
and completely air dried. The dried material was fine
powdered and sieved through standard sieves of particle
size 0.3 mm to 1.0 mm. In general, the adsorption capacity
is improved by modifying the nature of biosorbent by
different methods such as acid and alkali modification,
oxidation, and chemical graft17, 18. These techniques activate the sorbent by increasing active surface area and
improving chemical reactivity by formation of surface
functional groups which helps to chemically bond with
the heavy metals. Hence, the finest powders of casuarinas
fruit (CFP) and sorghum stem (SSP) were treated (soaked for 24 h at room temperature) with 1N H2SO4 and
banana bunch-stem (BSP) was treated with 1N HNO3.
The samples were washed with distilled water, oven dried
Pol. J. Chem. Tech., Vol. 18, No. 2, 2016
and cooled back to room temperature. The bio-sorbent
materials were stored in clean air tight containers and
used in the adsorption experiments. The preliminary
studies shows that the removal capacity of these treated
adsorbents is higher by about 30% compared to those
of untreated adsorbents. Hence, treated samples were
used throughout the study.
All the chemicals used were of analytical grade. The
standard copper stock solution of 1000 mg L–1 concentration certified for atomic absorption spectroscopy was
obtained from Loba Chemie Laboratory Reagents and
Fine Chemicals, India. Working copper solution was
prepared in bulk with deionised water and used for the
adsorption studies. The initial Cu (II) concentration of
the untreated sample was 36 mg L–1. The typical pH of
the experiments was about 5, and it was adjusted to the
desired value by the addition of few drops of 0.1 M HCl
or 0.1 M NaOH. Blank experiments were carried out
to study the adsorption of copper on the walls of batch
reactor and found negligible.
Instrumentation
The physical-chemical characterization of adsorbents
was performed by Scanning Electron Microscopy (SEM)
coupled to Energy-Dispersive X ray spectroscopy (EDX)
[FEI Quanta FEG 200 – High Resolution Scanning Electron Microscope] which also allows the identification and
quantification of the metal ions of the adsorbents. The
FT-IR spectra were performed using Bruker, ALPHA-T
to identify the active functional groups responsible for
the adsorption.
Batch adsorption studies
The experiments were performed in batch process
using BSP, CFP and SSP at room temperature in 250 ml
conical flask containing 50 ml of reaction mixture. While observing the effect of each parameter, the values
of other parameters were kept constant. The removal
efficiency of each adsorbent with respect to different
parameters like adsorbent dose [2, 4, 6, 8, 10, 15 and
20 g L–1], time [30, 60, 90, 120, 150, 180 and 210 min],
pH [2, 3, 4 and 5], temperature [30, 40, 50, 60 and 70oC]
and initial Cu(II) concentration [35, 50, 100, 150 and
200 mg L–1] was determined in individual experiments. In
each experiment, the metal ion solution equilibrated with
adsorbent were withdrawn, centrifuged and the final Cu
(II) concentration were measured by atomic absorption
spectroscopy19. The experiment was repeated thrice and
average results have been reported. The relative errors
in the experimental results were about 5%.
The adsorption capacity was determined by the following equation:
qe = [(Co-Ce)*V]/W
(1)
where, Co is the initial concentration of Cu(II) in solution, Ce is the final concentration of Cu(II) in solution
after adsorption, qe (mg g–1) is the adsorption capacity
of the adsorbent at equilibrium, V(L) is the volume of
suspension, and W(g) is the mass of adsorbent.
69
RESULTS AND DISCUSSION
SEM, EDX and FT-IR studies
The visible observation of the surface texture and
porosity of the samples using scanning electron microscopy (SEM) gives better understanding of the nature of
adsorption process and was given in Figure 1. Rough
surface with some pore formation were visualized before
adsorption as an indication of large surface areas (Fig. 1a)
capable of high adsorption, whereas, a smooth surface
covering of the pores can be observed after adsorption
(Fig. 1b). EDX studies were carried out to determine the
chemical composition of adsorbents (wt% of elements).
Before adsorption: BSP: C–58.19, O–41.40, Fe–0.11,
Cu–0.00; SSP: C–55.46, O–38.33, Fe–0.13, Zn–0.02,
Cu–0.02; CFP: C–62.70, O–36.23, Fe–0.17, Cu–0.00; After
adsorption: BSP: C–54.21, O–42.87, Fe–0.17, Cu–0.92;
SSP: C–46.69, O–37.60, Fe–02.17, Zn–0.15, Cu–0.28; CFP:
C–62.95, O–34.98, Fe–0.17, Cu–0.23. Successful loading
of copper on the surface of sorbents was confirmed with
EDX spectra of biosorbents, both prior and after batch
process. In all the adsorbents, presence of stretching for
C-O, C=O and aliphatic C-H can be confirmed from
peaks in the range of 1023–1039 cm–1, 1614–1689 cm–1
and 2917–2920 cm–1 respectively. But, additional peaks in
CFP above 3000 cm–1 indicate the =C-H stretching and
further C=C stretching can be observed from peaks in
the range of 1450–1550 cm–1. Broad peaks in the range
of 3305–3320 cm–1 indicate the presence of carboxylic
acid groups in SSP and BSP, whereas, dominant sharp
peak at 3737 cm–1 indicates phenolic groups in CFP
(Fig. 2). Based on the FTIR bands, adsorption of copper
ions can be partly attributed to electrostatic attraction20.
Figure 1. SEM images of BSP, SSP and CFP (a) Before adsorption and (b) After adsorption of Cu(II) respectively
EDX and FT-IR observations correlate with the compositions of BSP [holocellulose, cellulose, lignin, pectin]21,
SSP [cellulose, hemicelluloses, lignin, cutin, silica]22, and
CFP [α-pinene, benzaldehyde, 1,8 cineole, furanoid,
α-campholenal, 4-terpineol, α-terpineol, α-terpinyl acetate, spathulenol, caryophyllene-oxide, guaiol]23. The
presence of functional groups like acid, alcohol and
amine are evident from these studies. Protons of phenols/
alcohols and carboxylic acid groups in these biosorbent
facilitate them for ions getting exchanged during the
adsorption process. Hydroxyl groups in these biopolymers
may function as donors. Hence the de-protonation of
hydroxyl groups can be involved in the co-ordination
70
Pol. J. Chem. Tech., Vol. 18, No. 2, 2016
Figure 2. FTIR spectra of acid treated biosorbents (a) BSP, (b) SSP and (c) CFP before adsorption
with metal ions24. Moreover, presence of more number
of peaks in CFP compared to SSP can be explained
based on presence of good number of phytochemicals
as mentioned above.
Studies on effect of contact time and adsorption kinetics
To better understand the Cu(II) sorption characteristics by the three adsorbents (BSP, SSP and CFP), both
kinetic and equilibrium models were used to describe
the data. Change in Cu(II) concentrations over time was
investigated at each 30 min interval in contact time till
Pol. J. Chem. Tech., Vol. 18, No. 2, 2016
210 mins, while other parameters were kept constant
(Fig. 3). An increase in contact period between adsorbent and Cu(II) ions increases the adsorption of metal
ion as because more time familiarizes the metal ion to
bond with the adsorbent25, 26. The results revealed that
the equilibrium was established at a point of 180 min
in case of BSP and 120 min in case of SSP and CFP
as adsorbents. The better performance of these adsorbents compared to the earlier used adsorbents in terms
of optimum time required is manifested in the present
case because it is 6 h using garden grass13, 25 h using
fish bones27, 36 h using porous geo polymeric spheres28.
From Figure 3, it is clear that metal sorption follow
three step sorption mechanism. During the initial rapid
and quantitatively predominant step, large number of
sites are available for uptake of Cu(II) metal ions on the
adsorbents which permits to overcome all the external
mass transfer resistances and occupying the active sites on
the biosorbent with higher affinity through bonding with
the functional groups on sorbent14. During the second
slower and quantitatively insignificant step, the diffusion
of Cu(II) into the deeper pores creates repulsive forces
between the Cu(II) on the solid and the aqueous phases and the existence of different sorption mechanisms
might hamper the adsorption process2 leading to slower
adsorption rate. During the final equilibrium phase, the
sorption process ceases due to unavailability of active
sites on biosorbents to be occupied by the metal ions
or the difficulties in adsorbate-adsorbent interactions.
Figure 3. Effect of contact time on Cu(II) sorption, at 5 pH,
36 mg L–1 Cu(II), 200 rpm, 15 g L–1 SSP and 5 g L–1
CFP and BSP and RT
Further research on kinetics of adsorption was carried
out by employing pseudo first order (Eq. 2)29 and pseudo
second order (Eq. 3)30 kinetic equations to examine the
mechanism of Cu(II) adsorption (Fig. 4).
ln(qe – qt) = lnqe – k1t
(2)
t/q = (1/k2qe2) + (t/qe)
(3)
–1
Where qt and qe (mg g ) are the amounts of copper
adsorbed on adsorbent at time t and at equilibrium,
respectively, k1 and k2 are the corresponding pseudo
71
Figure 4. Pseudo second order adsorption model for the sorption
of 36 mg L–1 Cu(II) on 15 g L–1 SSP and 5 g L–1 CFP
and BSP at 5 pH and RT
first and second order adsorption rate constants. In the
present case, kinetic data is in good agreement with
pseudo second order in terms of coefficient of determination (R2) than pseudo first order in all three cases of
adsorbents and the adsorption kinetic parameters were
given in Table 1. Based on kinetic data, the predicted
qe values were close to experimental values for pseudo-second-order model. Suitability of pseudo-second-order
model suggests chemisorption as the rate limiting step.
This chemical adsorption can be explained by the valence forces through sharing electrons between biosorbent
(containing N and O atoms) and the sorbate ions31.
A wide variety of interactions between metal ions and
adsorbents like ion exchange, chelation, adsorption by
physical forces and entrapment in inter and intra-fibrillar
capillaries as well as space of the structural polysaccharide network. As a result, concentration gradient
and diffusion are responsible for effective uptake of
Cu(II) in solution and making biosorption as a complex
process32. Moreover, some non-conventional adsorbents
contain cellulose and the polar hydroxyl groups on the
cellulose that could be involved in chemical reaction
and hence bind heavy metals from solutions33. Hence,
simple Elovich equation (Eq. 4) was also employed for
its applicability on adsorption process (Fig. 5), where,
qt is the amount of Cu(II) sorbed at a time t, a is the
initial copper(II) sorption rate (mg g–1 min–1) and b is the
desorption constant (mg g–1) during any one experiment.
Their values were given in Table 2.
qt = 1/b ln(ab) + 1/b ln(t)
(4)
The interactions between adsorbate and adsorbent
materials follow film diffusion, pore diffusion and intraparticle transport among which pore diffusion and intraparticle diffusion are often rate-limiting in a batch reactor
whereas film diffusion is more likely the rate limiting
step for a continuous flow system34. Hence, Weber’s intra
particle diffusion (Eq. 5) model was analyzed and showed
reasonably good correlation. The estimated model and
the related statistic parameters Kd = rate constant of
the intraparticle transport (mg g–1 min1/2), θ = constant
Table 1. Pseudo first and second order Cu(II) adsorption kinetic parameters using BSP, CFP and SSP as biosorbents
72
Pol. J. Chem. Tech., Vol. 18, No. 2, 2016
Figure 5. Elovich’s and b. Weber’s intraparticle diffusion kinetic adsorption models for the sorption of 36 mg L–1 Cu(II) on 15 g L–1
SSP and 5 g L–1 CFP and BSP at 5 pH and 303 K temperature
Table 2. Weber’s intraparticle, Boyd and Elovich’s kinetic
parameters, of adsorbents, BSP, SSP and CFP
related to the thickness of the boundary layer (mg g–1)
were reported in Table 2.
qt = Kd t1/2 + θ
(5)
Information about boundary layer effect can be obtained from a plot of qt versus t0.5 (Fig. 5). Higher value
of θ shows that the solute adsorbed by the boundary
effect is higher35. A linear graph results when intraparticle diffusion is involved in the adsorption process. The
process of intraparticle diffusion would be the controlling
step if this line passed through the origin. On the other
hand, if the line does not pass through the origin then
there is some degree of boundary layer control which
further shows that intraparticle diffusion is not the only
rate-controlling factor, but can be controlled by the
other mechanisms. In the present study, Weber’s intra
particle diffusion linear data not passing through the
origin clearly indicates that the existence of pore diffusion process along with intra-particle transport during
adsorption. Further, the kinetics data subjected to Boyd
kinetics model analysis, Bt = –0.4977 – ln(1 – F) where
F represents the fraction of solute adsorbed at any time,
t (min) revealed the deviation of the metal ions uptake
from aqueous system on the adsorbent suggesting that
the adsorption mechanism was governed by external mass
transport where particle diffusion is the rate limiting
step. Though Boyd plot was reasonably linear in case of
SSP as adsorbent (R2 = 0.927), but has intercept, hence,
internal diffusion may not be the sole rate controlling
step in the adsorption process36.
Effect of adsorbent dose
The study of varying pattern of adsorption with amount of adsorbent gives the adsorption efficiency of each
adsorbent. It was clear from the experimental results
(Fig. 6) that the adsorbent dose can greatly affect the
adsorption of Cu(II) and adsorption increased with
increase in adsorbent concentration in reaction mixture
due to the availability of more number of active sites
on the surface of adsorbent37. However, in the case of
CFP, percent removal of copper (II) decreased with the
increase in adsorbent dosage beyond 10 g L–1. This may
be due to overlapping of adsorption sites as a result
of overcrowding of adsorbent particles in the form of
aggregates leading to a reduction in total surface area
of adsorbent and increase in diffusion length38.
Figure 6. Effect of biosorbent quantity on Cu(II) uptake by
BSP, SSP and CFP at 5 pH, 36 mg L–1 initial Cu(II)
concentration, 250 rpm and 303 K
Effect of pH
Solution pH is critical during adsorption as it governs
the adsorption affinity of the adsorbent by affecting
surface charge and metal speciation in solution which
in turn depends on degree of ionization and the type of
adsorbate species. Hence, it was thought of important to
study the effect of pH on the removal of Cu(II). Patrulea
et al.5 reported that the protonation of the primary amine
groups with positive charge in the acidic media effects
the adsorption process by electrostatic repulsion of the
cationic Cu(II) ions present in the medium. According
to previously reported findings, precipitation of Cu(II)
ions as copper hydroxides, such as Cu(OH)+, Cu(OH)2,
Cu(OH)3−, Cu(OH)42− occurs at pH values higher than
5 and beyond this point the adsorption efficiency results
could be hampered because of the higher concentration
of OH− ions in the medium39. In general, a decreasing
Pol. J. Chem. Tech., Vol. 18, No. 2, 2016
trend in adsorption can be observed after pH 7 due to
the formation of the copper hydroxyl precipitates and
soluble hydroxy complexes11, 40. Therefore, the effect of
pH on adsorption using BSP, SSP and CFP was studied
in the initial pH range of 2 to 5 in solution. It is reported
in the literature that the uptake of Cu(II) increases with
increase in pH in acidic medium and is predominantly
removed in the pH vicinity of 526, 41. Similar pattern of
increasing adsorption percentage with increase in pH was
observed from 2 to 5 (Fig. 7). In particular, the sorption
of Cu(II) increased slowly in the pH range 2 to 4, stabilized at pH 4 to 5 in all three cases of adsorbents. As
explained previously, the lower adsorption rate at lower
pH values is due to the higher concentration of H+ ions
present in the reaction mixture inducing repulsive forces,
between Cu(II) ions for the adsorption sites of biosorbents where the adsorbent surface acquired a positive
charges and hence the repulsive forces41. In addition,
an increase in removal with an increase in pH can be
attributed to the release of H+ ions from the sorbent
sites which help in increase of electrostatic attraction
force between the active surface and Cu(II) ions where
the negative charged carboxylic/phenolic surface provides
affinity site for the uptake of divalent copper ions.
Figure 7. Effect of pH on Cu(II) uptake using 10 g L–1 BSP, SSP
and CFP at 303 K, 36 mg L–1 initial Cu(II) concentration, 250 rpm agitation speed
Effect of temperature
The adsorption percentage increased with an increase
in temperature in case of SSP and CFP, whereas, in case
of BSP, the adsorption percentage did not significantly
change with increasing temperature (Fig. 8). The enhanced metal sorption capacity of CFP and SSP with
an increase in temperature may be attributed to the
rise in the kinetic energy / mobility of metal ions from
the bulk solution towards the adsorbent surface leading
to an increase in collision frequency between sorbent
and sorbate as well as extent of penetration within biosorbent structure overcoming the rate of intraparticle
diffusion42, 43. Additionally, at high temperature, there
73
Figure 8. Effect of temperature on Cu(II) uptake by 20 g L–1 BSP,
SSP and CFP at 5 pH, 36 mg L–1 initial Cu(II) concentration and 250 rpm agitation speed
may be an enlargement of pore size of biosorbents and
increase in number of active sorption sites due to bond
rupture of functional groups on adsorbent44. However,
in case of BSP as adsorbent, a slight decrease in the adsorption percentage with an increase in temperature was
observed (Fig. 8). This observation can be explained based
on (i) increased escaping tendency of already adsorbed
molecules from adsorbent into the bulk solution due to
increase in total energy of sorbate molecules at higher
temperature45 and (ii) dissolution of sorbing solution
because adsorbent functional groups are soluble at high
temperatures46. Though, this seems to be corroborates
with the well-known fact that sorption capacity is expected
to decrease with an increase in solution temperature
when sorption process is exothermic, the present case
involves both physical and chemical adsorptions and
such simultaneous occurrence of both adsorptions was
reported earlier by Ho et al. McKay47 and Panday et
al.48. Thermodynamic parameters calculated as a function
of temperature were presented in Table 3. The positive
value of ΔS reflects the affinity of the adsorbent for the
adsorbate and suggests some structural changes in both
of them. In addition, positive value of ΔS may show
the increasing randomness at the solid/liquid interface
during the adsorption. ΔS value is zero when the entire
process is reversible. The negative ΔS value indicated
the decrease in the randomness of the system and the
adsorption process is not irreversible49.
Effect of initial Cu(II) concentration
Initial metal concentration of the solution is the driving
force to overcome all the mass transfer resistances of
the metal between aqueous and solid phase and hence
a higher initial concentration of metal ions may increase
the adsorption capacity1. Incompletion of adsorption
sites during adsorption reaction and the aggregation
of adsorbent particles at higher concentration are the
important factors which contribute to the adsorbate con-
Table 3. Thermodynamic parameters for the adsorption of Cu(II) onto 10 g L–1 of BSP, SSP and CFP at 5 pH, 35 mg L–1 initial
Cu(II) concentration and 250 rpm agitation speed
74
Pol. J. Chem. Tech., Vol. 18, No. 2, 2016
centration effect. Figure 9 shows the effect of metal ion
concentration on its removal from the aqueous solution
for adsorbent materials. On changing the initial concentration of Cu(II) from 35 to 200 mg L–1, the amount
adsorbed increased from 1.75 to 6.10 mg g–1 in case
of BSP, 1.42 to 5.92 mg g–1 in case of SSP and 1.24 to
3.73 mg g–1 in case of CFP as adsorbent. A continuous
decline of percentage removal with increase in metal
ion concentration was observed. This appears to be due
to increase in number of metal ions competing for the
available binding sites in the biomass and also due to
the lack of binding sites for the attachment of Cu(II)
ions at higher concentration levels11.
Figure 9. Effect of initial Cu(II) concentration in solution on
adsorption of Cu(II) using 20 g L–1 BSP, SSP and CFP
at 5 pH, 250 rpm and 303 K
Adsorption isotherms
Adsorption isotherms are significant in describing the
mechanism of adsorption for analyzing the interaction of
metal ion on the surface of adsorbent. Figures 10a and
10b described the Langmuir and Freundlich adsorption
isotherms respectively for Cu(II) removal using BSP,
SSP and CFP. The values of characteristic parameters
Langmuir, Freundlich, D-R and Temkin models were
given in Table 4. The Temkin isotherm equation explicitly
takes into the account of adsorbent-adsorbate interactions by ignoring the extremely low and large value of
concentrations. It assumes that the heat of adsorption of
all the molecules in layer decreases linearly rather than
logarithmic with coverage due to adsorbent-adsorbate
interactions50. The best fitting order of these models is
concluded to be
Freundlich > Temkin > Langmuir > D-R : for BSP
and SSP
Langmuir > Temkin > D-R > Freundlich : for CFP
Langmuir isotherm model fitted the results quite well
for removal of copper ions by CFP (Table 4) suggesting
that (a) the surface of the sorbent is homogenous, (b)
all sites are energetically equivalent and each binding
site accepts only one Cu(II) molecule, (c) the sorbed
molecules are organized as a monolayer and (d) no
interaction between sorbed molecules. Similar observations were reported in the Cu(II) removal by saw
dust1, fish bones27 and chitosan5. Table 4 showed that
the best correlation of the experimental results was
obtained with the Freundlich isotherm model with BSP
and SSP and it also confirmed favorable from 1/n values
<1. This suggests that Cu(II) ions were adsorbed onto
these adsorbent surfaces in different ways. Dubinin–
Radushkevich (D-R) isotherm can be generally applied
to express the adsorption mechanism with a Gaussian
energy distribution onto a heterogeneous surface51. The
approach was usually applied to distinguish the physical
and chemical adsorption of metal ions with its mean free
energy. Compared to other adsorbents, D-R isotherm
fitted well to CFP. Table 5 described the favorable shape
factor values which were between 0 to 1 determined
from the Langmuir isotherms for all three cases of adsorbents (BSP, SSP and CFP) at different initial Cu(II)
concentrations47.
Table 4. Copper (II) biosorption isotherm parameters i.e. Langmuir, Freundlich, D.R. and Temkin models by 20 g–1 of adsorbents,
BSP, SSP and CFP at 5 pH, 303 K and 250 rpm agitation speed
Figure 10. Linear adsorption isotherm plots for a. Langmuir’s model and b. Freudlich’s model on Cu(II) uptake by BSP, SSP and CFP at 5 pH,
250 rpm agitation speed and 303 K temperature
Pol. J. Chem. Tech., Vol. 18, No. 2, 2016
Table 5. The shape factor Langmuir parameter, RL values for
Cu(II) uptake by adsorbents, BSP, SSP and CFP
A comparison of the copper ions uptake capacities of
BSP, CFP and SSP with other biomaterial based sorbents
is presented in Table 6. However, a direct comparison
may not be possible due to a variety of parameters and
conditions employed in each referenced work. In spite
of lower removal capacity of these adsorbents, considering the fact that these three adsorbents are abundantly
available, the efficient Cu(II) removal from industrial
wastewater could be achieved by utilizing these waste
materials as adsorbents in large quantities.
Table 6. Comparison of maximum adsorption capacities of
various adsorbents for Cu(II) ions
CONCLUSIONS
The maximum adsorption efficiencies of the three
adsorbents for Cu(II) removal from aqueous solutions
were 6.5, 7.9 and 4.5 mg L–1 using BSP, SSP and CFP
respectively and can be correlated with their microporous structures, where, rough surface with some cavities
for all three adsorbents indicating high possibility of
adsorption. It is evident from the kinetic data that the
chemosorption is the possible adsorption mechanism
involved in Cu(II) removal using BSP and CFP as adsorbents, whereas, a combination of both physisorption
and chemical attachment involved when SSP was used
as an adsorbent. Adsorption isotherm studies describe
that both mono and multilayer adsorptions occur in the
present studies with preference to monolayer adsorption
in case of CFP and multilayer adsorption in case of
BSP and SSP. Presented results affirmed suitability of
low-cost, adsorbents (BSP, SSP and CFP) for copper
removal from aqueous environment.
ACKNOWLEDGEMENT
The authors are highly thankful to Acharya Nagarjuna
University for providing the support for conducting the
research work. Authors are also wish to thank SAIF, IIT,
Madras for providing SEM-EDX instrumentation facility.
75
LITERATURE CITED
1. Larous, S. & Meniai, A.H. (2012). Removal of copper (II)
from aqueous solution by agricultural by-products-sawdust.
Ener. Proc. 18, 915–923. DOI: 10.1016/j.egypro.2012.05.106.
2. Rozaini, C.A., Jain, K., Oo, C.W., Tan, K.W., Tan, L.S.,
Azraa, A. & Tong, K.S. (2010). Optimization of nickel and
copper ions removal by modified mangrove barks. Int. J. Chem.
Eng. Appl. 1(1), 84–89. DOI: 10.7763/IJCEA.2010.V1.14.
3. WHO, World Health Organization (2004). Guidelines for
Drinking-water Quality, third ed., Recommendations, Geneva.
4. Manzoor, Q., Nadeem, R., Iqbal, M., Saeed, R. & Ansari,
T.M. (2013). Organic acids pretreatment effect on Rosa bourbonia phyto-biomass for removal of Pb (II) and Cu (II) from
aqueous media. Biores. Technol. 132, 446–452. DOI: 10.1016/j.
biortech.2013.01.156.
5. Patrulea, V., Negrulescu, A., Mincea, M., Pitulice, L., Spiridon, O. & Ostafe, V. (2013). Optimization of the removal
of copper(ii) ions from aqueous solution on chitosan and
cross-linked chitosan beads. BioResources. 8. DOI: 10.15376/
biores.8.1.1147-1165.
6. Acar, F.N. & Eren, Z. (2006). Removal of Cu(II) ions
by activated poplar sawdust (Samsun Clone) from aqueous
solutions. J. Hazard. Mater. 137(2), 909–914. DOI: 10.1016/j.
jhazmat.2006.03.014.
7. Ramya, P.M., Venkata, N.R., Jayasravanthi, M. & Dulla,
B.J. (2015). Chemical oxygen demand reduction from coffee processing waste water-A comparative study on usage of
biosorbents prepared from agricultural wastes, Global NEST
J. 17(2), 291–300.
8. Cestari, A.R., Vieira, E.F., de Oliveira, I.A. & Bruns, R.E.
(2007). The removal of Cu(II) and Co(II) from aqueous solutions using cross-linked chitosan--evaluation by the factorial
design methodology, J. Hazard. Mater. 143(1–2), 8–16. DOI:
10.1016/j.jhazmat.2006.08.063.
9. Lima, I.S., Lazarin, A.M. & Airoldi, C. (2005). Favorable
chitosan/cellulose film combinations for copper removal from
aqueous solutions. Int. J. Biol. Macromol. 36(1), 79–83. DOI:
10.1016/j.ijbiomac.2005.04.001.
10. Jamnongkan, T., Kantarot, K., Niemtang, K., Pansila, P.P.
& Wattanakornsiri, A. (2014). Kinetics and mechanism of
adsorptive removal of copper from aqueous solution with poly
(vinyl alcohol) hydrogel. Trans. Nonfer. Met. Soc. China 24(10),
3386–3393. DOI: 10.1016/S1003-6326(14)63481-6.
11. Weng, C.H., Lin, Y.T., Hong, D.Y., Sharma, Y.C., Chen,
S.C. & Tripathi, K. (2014). Effective removal of copper ions
from aqueous solution using base treated black tea waste.
Ecol. Eng. 67, 127–133. DOI: 10.1016/j.ecoleng.2014.03.053.
12. Vieira, M.G.A., de Almeida Neto, A.F., da Silva, M.G.C.,
Carneiro, C.N. & Melo Filho, A.A. (2014). Adsorption of lead
and copper ions from aqueous effluents on rice husk ash in
a dynamic system. Braz. J. Chem. Eng. 31(2), 519–529. DOI:
10.1590/0104-6632.20140312s00002103.
13. Hossain, M.A., Ngo, H.H., Guo, W.S. & Setiadi, T.
(2012). Adsorption and desorption of copper (II) ions onto
garden grass. Biores. Technol. 121, 386–395. DOI: 10.1016/j.
biortech.2012.06.119.
14. Liang, S., Guo, X., Feng, N. & Tian, Q. (2010). Isotherms,
kinetics and thermodynamic studies of adsorption of Cu2+
from aqueous solutions by Mg2+/K+ type orange peel adsorbents. J. Hazard. Mater. 174(1), 756–762. DOI: 10.1016/j.
jhazmat.2009.09.116.
15. Bilal, M., Shah, J.A., Ashfaq, T., Gardazi, S.M.H., Tahir,
A.A., Pervez, A. & Mahmood, Q. (2013). Waste biomass
adsorbents for copper removal from industrial wastewater-A review. J. Hazard. Mater. 263, 322–333. DOI: 10.1016/j.
jhazmat.2013.07.071.
16. Chen, J.P. & Yang, L. (2005). Chemical modification of
Sargassum sp. for prevention of organic leaching and enhan-
76
Pol. J. Chem. Tech., Vol. 18, No. 2, 2016
cement of uptake during metal biosorption. Ind. Eng. Chem.
Res. 44(26), 9931–9942. DOI: 10.1021/ie050678t.
17. Li, Y., Xia, B., Zhao, Q., Liu, F., Zhang, P., Du, Q. & Xia,
Y. (2011). Removal of copper ions from aqueous solution by
calcium alginate immobilized kaolin. J. Env. Sci. 23(3), 404–411.
DOI: 10.1016/S1001-0742(10)60442-1.
18. Xue, Y., Gao, B., Yao, Y., Inyang, M., Zhang, M., Zimmerman, A.R. & Ro, K.S. (2012). Hydrogen peroxide modification enhances the ability of biochar (hydrochar) produced
from hydrothermal carbonization of peanut hull to remove
aqueous heavy metals: batch and column tests. Chem. Eng. J.
200, 673–680. DOI: 10.1016/j.cej.2012.06.116.
19. Annual book of ASTM standards part – 23, (1972). Am.
Soc. Test. Mater. Philadelphia.
20. Gong, J.L., Wang, X.Y., Zeng, G.M., Chen, L., Deng, J.H.,
Zhang, X.R. & Niu, Q.Y. (2012). Copper (II) removal by
pectin–iron oxide magnetic nanocomposite adsorbent. Chem.
Eng. J. 185, 100–107. DOI: 10.1016/j.cej.2012.01.050.
21. Li, K., Fu, S., Zhan, H., Zhan, Y. & Lucia, L. (2010).
Analysis of the chemical composition and morphological
structure of banana pseudo-stem. Bioresources 5(2), 576–585.
DOI: 10.15376/biores.5.2.576-585
22. Firdous, R. & Gilani, A.H. (2001). Changes in chemical
composition of sorghum as influenced by growth stages and
cultivar. Asian Australas. J. Anim. Sci. 14(7), 935–940. DOI:
http://dx.doi.org/10.5713/ajas.2001.935.
23. Ogunwande, I.A., Flamini, G., Adefuye, A.E., Lawal, N.O.,
Moradeyo, S. & Avoseh, N.O. (2011). Chemical compositions
of Casuarina equisetifolia L., Eucalyptus toreliana L. and Ficus
elastica Roxb. ex Hornem cultivated in Nigeria. S. Afr. J. Bot.
77(3), 645–649. DOI: 10.1016/j.sajb.2011.02.001.
24. Lerivrey, J., Dubois, B., Decock, P., Micera, G., Urbanska, J. & Kozłowski, H. (1986). Formation of D-glucosamine
complexes with Cu (II), Ni (II) and Co (II) ions. Inorg. Chim.
Acta 125(4), 187–190. DOI: 10.1016/S0020-1693(00)81209-8.
25. Mahaninia, M.H., Rahimian, P. & Kaghazchi, T. (2015).
Modified activated carbons with amino groups and their copper adsorption properties in aqueous solution. Chin. J. Chem.
Eng. 23(1), 50–56. DOI: 10.1016/j.cjche.2014.11.004.
26. Sarioglu, M., Atay, Ü.A. & Cebeci, Y. (2005). Removal of
copper from aqueous solutions by phosphate rock. Desalination
181(1), 303–311. DOI: 10.1016/j.desal.2005.04.009.
27. Kizilkaya, B., Tekinay, A.A. & Dilgin, Y. (2010). Adsorption
and removal of Cu (II) ions from aqueous solution using pretreated fish bones. Desalination 264(1), 37–47. DOI: 10.1016/j.
desal.2010.06.076.
28. Ge, Y., Cui, X., Kong, Y., Li, Z., He, Y. & Zhou, Q.
(2015). Porous geopolymeric spheres for removal of Cu (II)
from aqueous solution: Synthesis and evaluation. J. Hazard.
Mater. 283, 244–251. DOI: 10.1016/j.jhazmat.2014.09.038.
29. Lagergren, S. (1898). On the theory of so-called adsorption
solutes, The Royal Swedish Academy of Sciences. Handlingar
24(4), 1–39 (in German).
30. Ho, Y.S. & McKay, G. (1999). Pseudo-second order model
for sorption processes. Process Biochem. 34(5), 451–465. DOI:
10.1016/S0032-9592(98)00112-5.
31. Ho, Y.S. & McKay, G. (2000). The kinetics of sorption
of divalent metal ions onto sphagnum moss peat. Water Res.
34(3), 735–742. DOI: 10.1016/S0043-1354(99)00232-8.
32. Ahluwalia, S.S. & Goyal, D. (2007). Microbial and plant
derived biomass for removal of heavy metals from wastewater. Biores. Technol. 98(12), 2243–2257. DOI:10.1016/j.
biortech.2005.12.006.
33. Igwe, J.C. & Abia, A.A. (2005). Competitive adsorption
of Zn (II), Cd (II) and Pb (II) ions from aqueous and nonaqueous solution by maize cob and husk. Afr. J. Biotechnol.
4(10), 1113–1116. DOI: 10.5897/AJB2005.000-3220.
34. Goswami, S. & Ghosh, U.C. (2006). Studies on adsorption
behaviour of Cr (VI) onto synthetic hydrous stannic oxide. Water
SA, 31(4), 597–602. http://dx.doi.org/10.4314/wsa.v31i4.5150
35. Greluk, M. & Hubicki, Z. (2009). Sorption of SPADNS azo
dye on polystyrene anion exchangers: equilibrium and kinetic
studies. J. Hazard. Mater. 172(1), 289–297. DOI: 10.1016/j.
jhazmat.2009.07.007.
36. Kumar, P. S., Ramalingam, S., Kirupha, S.D., Murugesan,
A., Vidhyadevi, T. & Sivanesan, S. (2011). Adsorption behavior
of nickel (II) onto cashew nut shell: Equilibrium, thermodynamics, kinetics, mechanism and process design. Chem. Eng.
J. 167(1), 122–131. DOI: 10.1016/j.cej.2010.12.010.
37. Garg, U.K., Kaur, M.P., Garg, V.K. & Sud, D. (2007).
Removal of hexavalent chromium from aqueous solution by
agricultural waste biomass. J. Hazard. Mater. 140(1), 60–68.
DOI: 10.1016/j.jhazmat.2006.06.056.
38. Chang, Y., Liu, H., Zha, F., Chen, H., Ren, X. & Lei, Z.
(2011). Adsorption of Pb (II) by N-methylimidazole modified
palygorskite. Chem. Eng. J. 167(1), 183–189. DOI: 10.1016/j.
cej.2010.10.081.
39. Özçimen, D. & Ersoy-Meriçboyu, A. (2009). Removal of
copper from aqueous solutions by adsorption onto chestnut shell
and grape seed activated carbons. J. Hazard. Mater. 168(2),
1118–1125. DOI: 10.1016/j.jhazmat.2009.02.148.
40. Krishnan, K.A. & Anirudhan, T.S. (2003). Removal of
cadmium (II) from aqueous solutions by steam-activated
sulphurised carbon prepared from sugar-cane bagasse pith:
Kinetics and equilibrium studies. Water SA, 29(2), 147–156.
http://dx.doi.org/10.4314/wsa.v29i2.4849
41. Zheng, W., Li, X. M., Wang, F., Yang, Q., Deng, P. & Zeng,
G.M. (2008). Adsorption removal of cadmium and copper
from aqueous solution by areca-a food waste. J. Hazard. Mater.
157(2), 490–495. DOI: 10.1016/j.jhazmat.2008.01.029.
42. Kumar, U. (2011). Thermodynamics of the Adsorption
of Cd (II) from Aqueous Solution on NCRH. I. Jesd. 2(5),
334–336. DOI: 10.7763/IJESD.2011.V2.147.
43. Agrawal, A., Sahu, K.K. & Pandey, B.D. (2004). Removal
of zinc from aqueous solutions using sea nodule residue. Coll.
Surf. A. 237(1), 133–140. DOI: 10.1016/j.colsurfa.2004.01.034.
44. Tewari, N., Vasudevan, P. & Guha, B.K. (2005). Study on
biosorption of Cr (VI) by Mucor hiemalis. Biochem. Eng. J.
23(2), 185–192. DOI: 10.1016/j.bej.2005.01.011.
45. Sharma, Y.C., Prasad, G. & Rupainwar, D.C. (1991). Removal of Ni (II) from aqueous solutions by sorption. Int. J. Environ. Stud. 37(3), 183–191. DOI: 10.1080/00207239108710629.
46. Dai, J. & Mumper, R.J. (2010). Plant phenolics: extraction, analysis and their antioxidant and anticancer properties.
Molecules 15(10), 7313–7352. DOI: 10.3390/molecules15107313.
47. Ho, Y.S., Porter, J.F. & McKay, G. (2002). Equilibrium
isotherm studies for the sorption of divalent metal ions onto
peat: copper, nickel and lead single component systems. Water
Air Soil Poll. 141(1–4), 1–33. DOI: 10.1023/A:1021304828010.
48. Panday, K.K., Prasad, G. & Singh, V.N. (1984). Removal
of Cr (V1) from aqueous solutions by adsorption on fly ash-wollastonite. J. Chem. Technol. Biotechnol. 34(7), 367–374.
DOI: 10.1002/jctb.5040340703.
49. Varank, G., Demir, A., Yetilmezsoy, K., Top, S., Sekman,
E. & Sinan Bilgili, M. (2012). Removal of 4-nitrophenol from
aqueous solution by natural low-cost adsorbents. Indian J.
Chem. Technol. 19(1), 7–25.
50. Temkin, M.I. & Pyzhev, V. (1940). Kinetics of ammonia
synthesis on promoted iron catalysts. Acta Physio.Chim. URSS,
12(3), 217–222.
51. Dąbrowski, A. (2001). Adsorption-from theory to practice.
Adv. Coll. Interface. Sci. 93(1), 135–224. DOI: 10.1016/S00018686(00)00082-8.
52. Ertugay, N. & Bayhan, Y.K. (2010). The removal of copper
(II) ion by using mushroom biomass (Agaricus bisporus) and
kinetic modeling. Desalination 255, 137–142. DOI: 10.1016/j.
desal.2010.01.002.
53. Weng, C.H. & Wu, Y.C. (2012). Potential low-cost biosorbent for copper removal:pineapple leaf powder. J. Environ.
Pol. J. Chem. Tech., Vol. 18, No. 2, 2016
Eng.-ASCE 138, 286–292. http://dx.doi.org/10.1061/(ASCE)
EE.1943-7870.0000424
54. Weng, C.H., Tsai, C.Z., Chu, S.H. & Sharma, Y.C. (2007).
Adsorption characteristics ofcopper(II) onto spent activated
clay. Sep. Purif. Technol. 54, 187–197. DOI: 10.1016/j.seppur.2006.09.009.
55. Li, Y., Liu, F., Xia, B., Du, Q., Zhang, P., Wang, D., Wang,
Z. & Xia, Y. (2010). Removal ofcopper from aqueous solution
by carbon nanotube/calcium alginate composites. J. Hazard.
Mater. 177, 876–880. DOI: 10.1016/j.jhazmat.2009.12.114.
77