International Journal of Biological Macromolecules 98 (2017) 139–149

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International Journal of Biological Macromolecules

journal homepage: www.elsevier.com/locate/ijbiomac

An experimental and quantum chemical study of removal of utmostly

quantified heavy metals in wastewater using coconut husk: A novel
approach to mechanism
Reena Malik, Shefali Dahiya, Suman lata ∗
Department of Chemistry, Deenbandhu Chhotu Ram University of Science and Technology, Murthal, Haryana, India

a r t i c l e i n f o a b s t r a c t

Article history: The present study explores the uptake capacity of low cost agricultural waste i.e.Unmodified Coconut
Received 22 December 2016 (Cocos nucifera L.) Husk for the removal of heavy metal (Pb2+ , Cu2+ , Ni2+ and Zn2+ ) ions from industrial
Received in revised form 6 January 2017 wastewater. The effect of various operational parameters such as adsorbent dose, high initial metal con-
Accepted 23 January 2017
centration (100 mg/L–500 mg/L), pH, temperature and agitation time on the removal of these ions has
Available online 24 January 2017
been investigated using batch experiments. The results showed that maximum uptake through adsorp-
tion occurred at 443.0 mg/g (88.6%) for Cu, for Ni with 404.5 mg/g (80.9%), 362.2 mg/g (72.4%) for Pb2+
Keywords:
and 338.0 mg/g (67.6%) for Zn2+ ion simultaneously. The adsorption capacity was found to be sensi-
Adsorption
Isotherms
tive to the amount of adsorbent, heavy metal ion concentration, pH, temperature and contact time. The
Quantum study experimental statistics have been correlated and interpreted by a new proposed mechanism based upon
Heavy metal quantum chemical study of the adsorbent. The theoretical study using quantum has provided the rich
Mechanism electron donation sites of Coconut Husk and hence proposed mechanism of removal. The various adsorp-
tion isotherms (Langmuir, Freundlich, Temkin, Dubinin-Radushkevich and Flory-Huggins), SEM study
and physico-chemical properties of the ions suit well to the observed data.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction
Scientists and engineers are searching for various ways to
minimize the quantity of contaminants and improve the quality
of industrial wastewater. Industries are looking to comply with
water quality criteria and are adopting best practice environmen-
tal management before discharge. The worldwide Governments
are encouraging individuals and companies to use water wisely
through education programs, legislation and pricing [1,2]. As a
result of increasing technological development and industrializa-
tion, industrial and municipal water pollution by the harmful
substances (heavy metals, dyes etc.), their indiscriminate and heavy
discharge into the water bodies is prospering day by day. Moreover,
the metallurgical and chemical industries as well as metal process-
ing units need to treat the waste water having utmostly quantified
heavy metals before discharging it to the environment [1–4].
The application of plant products such as coconut husk, shells
and fibre for the removal of heavy metals has many advantages
over other methods such as their availablity in large quantities,
renewable nature, eco-friendly and low-costs [5–8]. In previous
∗ Corresponding author.
E-mail address: sumanjakhar.chem@dcrustm.org (S. lata).
studies and till date, the removal of heavy metals has been investi-
gated at their low concentrations [9,10]. It was found that coconut
shell can be used as a low cost adsorbent for the removal of heavy
metals in aqueous solution containing low concentrations of the
metals within range 5–50 mg/L considering to cover the concen-
tration range of actual gold mine wastewater [11]. Moreover, for
coconut shell, 100 and 200 mg/L Cu(II) solutions were used as well,
because it has the capacity to remove Cu(II) at these concentrations
[11]. It was studied that 50 mg/L Fe(III), 50 mg/L Cu(II) and 10 mg/L
of Pb(II) were removed best in pH 5, where the removal capacities
were almost 90% [12]. Coconut shell has also been studied by taking
initial metal ion concentration 20–100 mg/L and it was found that
with increase in metal ion concentration, % removal increases from
18.02 to 65.21 mg/L [13]. Similar type of study on coconut husk was
also done by Agbozu and Emoruwa [14]. The% removal of metals
increases with initial metal ion concentration (0.3k0.9 mg/L) and
observed trend was Cr > Cu > Cd > Fe > Pb [14]. Hence, at low metal
ion concentration, lot of work has been performed using coconut
products during last decade but such type of work needs further
attention at high metal concentration.
The removal of heavy metal ions at their higher concentra-
tion have been performed by only few researchers [15–19] on
the material other than coconut products. Researchers [15] have
investigated the removal of Cd2+ , Zn2+ , Cu2+ by using maize cope

http://dx.doi.org/10.1016/j.ijbiomac.2017.01.100
0141-8130/© 2017 Elsevier B.V. All rights reserved.
140 R. Malik et al. / International Journal of Biological Macromolecules 98 (2017) 139–149
and husk and found that they removed the metals as 456, 493.7,
495.9 mg/L respectively. Ahluwalia and Goyal [16] also studied for
the heavy metal removal by using bacillus – bacterial biomass and
was found that it removes 467, 85.3, 418, 381, 39.9 mg/L (Pb2+ ,Cd2+ ,
Zn2+ , Cu2+ Cr6+ , Ni2+ respectively). A new organic heavy metal
chelator dipropyl dithiophosphate [17] can remove the high con-
centration of Pb, Cd, Cu and Hg being 200 mg/L up to over 99.9%.
[18] found that varying the initial concentration of HM ions from
50 mg/L to 5000 mg/L did not affect the removal rates and at higher
concentration, the removal of Cr, Zn, Cu, Ni and Ag further got
accelerated. [19] also studied% removal at high initial heavy metal
ion concentration from the range 25–800 mg/L. [20] discusses fur-
ther that the metal loading capacity of corncob particles has been
slightly influenced by the presence of their competitive ions [20].
Most of the work has been performed at low concentration of
HM ions using coconut husk and shell [12–14], keeping in mind
the actual composition of waste water, however, the similar kind
of study is not available at high concentration of metals. As, high
quantities of the metals may also be found in some of the waste
waters [21–23]. The maximum permissible limit (MPL) of lead in
drinking water is 0.05 mg/L (WHO). The permissible limit (mg/L) for
Pb (II) in wastewater, given by Environmental Protection Agency
(EPA), is 0.05 mg/L [21], but, in industrial wastewaters, Pb ion con-
centrations approach 200–500 mg/L, this concentration is very high
in relation to water quality standards, and Pb concentration of
wastewaters must be reduced to a level of 0.05–0.10 mg/L before
discharging to water ways or sewage systems [21–23]. Hence,
proper treatment of industrial wastewaters which are releasing
lead into the aquatic, land systems and irrigation waters is very
important [23]. [24] reported the maximal amount of Cu upto
590 ppm present in offsite ground water. A survey of raw and
treated waste water from 20 industrial categories indicated that
nickel is commonly found in some waste waters [25]. The max-
imum levels of Ni in treated discharges from various industries
were found upto 310,000 ␮g/L [25]. Ilou and et al. have investigated
the quantification of pollution discharges from tannery wastewa-
ter [26] and found that the waste water discharge contains highly
quantified zinc.
Coconut husk constituents include lignin-29.2%, cellulose-23.9%
as water insoluble matter whereas pectins and hemicellulose
(26.0% as water soluble matter) and around 5% as inorganic mat-
ter [27]. The upcoming multiplied growth of chemical and metal
processing industries for future generations, the low cost and clean
removal of highly quantified heavy metals from wastewater has
been the alarming issue for present environmentalists [4]. As, lot of
work has been performed using coconut products at lower metal
concentration till date, but such type of work needs further atten-
tion at high metal concentration too and by hypothesizing the
enhanced uptake of metals even at higher concentrations of metals,
it was planned to examine the HM removal at their higher levels
from aqueous solution using coconut husk.
The aim of present study is to apply unmodified coconut husk as
an efficient and low cost material in order to remove heavy metals
Pb2+ , Cu2+ , Ni2+ and Zn2+ from industrial wastewater at their higher
concentration. The theoretical approach has been exploited for the
first time to extract the support from quantum study of the major
component of coconut husk and the obtained information has fur-
ther been used to suggest a novel mechanism for removal of these
metals.
2. Materials and methods
2.1. Preparation of biosorbents and batch solutions
Coconut husk was harvested into small pieces and washed with
de-ionised water to remove dirt and color and air- dried for 24 h to
Table 1
Experimental conditions for batch experiments.
Amount of adsorbent (g) 0.2, 0.4, 0.6, 0.8, 1.0, 1.2
Initial Metal Conc. each (mg/L) 100, 200, 300, 400 and 500
pH (Initially) 2.0, 3.0, 4.0, 5.0, 6.0, 7.0 and 8.0
Agitation time (min.) 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120
Adsorption temperature (◦ C) 10, 20, 30, 40, 50, 60, 70 and 80
Particle size (␮m) 100 only
avoid thermal deactivation of the adsorbent surface and then dried
it in oven at 70◦ C for 7 h. The dried material was ground using a
laboratory mill and sieved through 100 ␮m size fraction and a por-
tion of adsorbent was stored in clean polyethylene containers prior
to analysis. All the chemicals used in the experiments were of ana-
lytical grade and they were used without further purification. All
the solutions were made in de-ionized water. Different solutions of
heavy metals (Cu(II), Pb(II), Ni(II) and Zn(II)) (Qualigens fine chem-
icals, Mumbai, minimum assay 99%) were prepared from solution
containing 500 mg/L as stock solution as well as one of the test
solution and further dilutions were made as 400 mg/L, 300 mg/L,
200 mg/L and 100 mg/L. The pH of the aqueous solution was 5.0,
which did not change much with dilution. For experiments at dif-
ferent pH, the acidity of heavy metal (Cu(II), Pb(II), Ni(II) and Zn(II))
solutions were adjusted by addition of 0.1 M HNO3 and 0.1 M NaOH
solution drops. All the batch experiments were authenticated after
observing the data in triplicate.
2.2. Adsorption experiments
The adsorption was carried out in conical flasks by agitating a
pre-weighed amount of the powder with 100 mL of the aqueous
heavy metal solution in a constant temperature, water bath shaker
(NSW, Mumbai) for a pre-determined time interval at a constant
speed (220 rpm). After adsorption, the mixture was filtered and
remaining heavy metal in solution was determined with atomic
absorption spectrometry (Labindia Analytical AA-7000, India). The
amount of heavy metal adsorbed per unit mass of the adsorbent
was computed by using the Eq. (1).
C0 − Ct
q= (1)
M
where C0 and Ct are heavy metal concentrations in mg/L before and
after adsorption for time t in min., and M is the dose of adsorbent
in g taken for 1 L of heavy metal solution. The extent of adsorption
in percentage is found from the Eq. (2).
C0 − Ct
Adsorption% = × 100 (2)
C0
To investigate the effect of various operational parameters like
pH, temperature etc., on removal rates of metals, the following
experimental conditions were opted for different batch experi-
ments (Table 1).
2.3. FTIR study
The FTIR spectrum of fine powder of CH was recorded by
Perkin-Elmer FT-IR/RZX and ranges from 4000 cm−1 –400 cm−1 .
The spectrum shows the presence of phenolic OH (correspond-
ing to 3430–3456 cm−1 ) and C H stretching at 2924 cm−1 . The
peak at 1626–1633 cm−1 represents the finger print region of C O
stretching as well as C C vibrational stretching of aromatic ring.
The absorption at 1121 cm−1 corresponding to –COC– functional
group, along with presence of C O C polysaccharide (may be due
the presence of lignocelluloses) [28]. After adsorption, 1270 cm−1
shifted to 1121 cm−1 proving the attraction between CH and HM
ions and C O bonds become weak. The presence of these functional
 R. Malik et al. / International Journal of Biological Macromolecules 98 (2017) 139–149 141

Fig. 1. FTIR of Coconut Husk before and after adsorption.

Fig. 2. (a) SEM images of Coconut Husk before and (b) after adsorption.

groups of coconut husk before and after adsorption are evidenced

by the structure given in Fig. 1. Moreover, the different intensity
of the peaks before and after adsorption may be the function of
quantitative estimation.

2.4. Quantum chemical analysis

The quantum chemical studies were performed for the present

biosorbent using AM1 (Austin Model1), a semi empirical method
based on the neglect of differential diatomic overlap approxima-
tion. The quantum parameters were calculated using HyperChem
Professional 8.0 package (Hypercube Inc., USA). The following
quantum chemical descriptors were taken into consideration:
energy of the highest occupied molecular orbital (EHOMO ), energy
of the lowest unoccupied molecular orbital (ELUMO ), energy gap:
Egap = ELUMO − EHOMO , dipole moment (␮), electron affinity (A),
ionization potential (I), the absolute electronegativity (␹), absolute
hardness (␩), electrophilicity (␻), and nucleophilicity(n). The tech-
nique was studied to correlate the various quantum parameters
with the observed experimental data and hence, a novel mecha-
nism of adsorption has been suggested.
2.5. SEM analysis before and after adsorption
Surface morphology of CH before and after adsorption was
imaged under Model Zeiss Ultra 55 at 3 kV for SEM technique at
×2000 magnification. There are significant changes to the surface
of the biosorbent, as well as the formation of discrete aggregates on
the surface following metal ion adsorption. The SEM images of CH
before and after metal uptake are shown in Fig. 2a and b, respec-
tively showing that the CH particles were of various dimensions
containing steps and kinks on the external surface. CH displayed
Fig. 3. % Removal of Cu2+ , Ni2+ , Zn2+ and Pb2+ each at 500 mg/L, contact time (40 min)
and pH(6.0) for different CH doses at 30 ± 1 ◦ C.
a dense and porous surface texture. Interaction of CH with heavy
metals has resulted in the formation of flake-like shiny deposits on
its surface (Fig. 2b).
3. Results and discussion
3.1. Effect of biosorbent (CH) dose
The adsorption experiments were carried out in a batch process
under the experimental conditions (Table 1) and the equilibrium
concentration for each metal was computed using AAS spectropho-
tometer. Fig. 3 shows that at lower doses of adsorbent, % removal is
low but it goes on increasing with increase in CH dose and reaches
at highest(optimization range) around 1.0 g dose of CH due to equi-
libration. It may happen due to almost all of the vacant active sites
are occupied by the HM ions [29]. The increase in% removal occurs,
since the accelerated number of freely available active sites with
142 R. Malik et al. / International Journal of Biological Macromolecules 98 (2017) 139–149
Fig. 4. Variation of initial metal ion concentration with CH (1.0 g) with contact time
(40 min) and pH (6.0) at 30 ± 1 ◦ C.
Fig. 5. Effect of contact time on adsorption of heavy metals on coconut husk at
30 ± 1 ◦ C (Pb(II),Co(II),Ni(II),Zn(II): 300 mg/L each, adsorbent: 1.0 g, pH-6.0).
the higher doses of CH. In the very beginning, comparable rates of
removal for two ions Cu and Ni ions and similarly for Pb and Zn
were noticed and contained in Fig. 3 with much demarkations at
higher doses of CH.
3.2. Effect of initial metal ion concentration
Batch adsorption was carried out using initial metal ion concen-
trations of 100, 200, 300, 400 and 500 mg/L aqueous solution of Cu,
Pb, Ni and Zn ions all at one time. Variation of initial metal ion con-
centration of the heavy metals on coconut husk (1.0 g) with contact
time (40 min) and pH(6.0) at 30 ± 1 ◦ C are shown in Fig. 4. With
increasing initial HM ion concentration, % removal rises and this
type of behavior is also observed in [30], but after certain level of
initial HM ions, increase of% removal lowers down. As discussed by
[31], high initial metal concentration accelerates the driving force
and reduces the mass transfer resistance [29].
3.3. Effect of contact time
The biosorption of the metal ions on CH was studied at
10–120 min range of time with each interval of 10 min (Fig. 5).
In biosorption experiments, (Pb(II),Co(II),Ni(II),Zn(II)) ions, each at
300 mg/L, with fixed adsorbent dose of 1.0 g and pH = 6.0 in 100 mL
solution into 250 mL flask at 30 ± 1 ◦ C were observed. At the end
of each contact time, the content of each flask were filtered. The
concentration of metal ions in the filtrates was determined using
AAS and the amount of metal ion adsorbed was calculated. In
the beginning, the rate of removal is very high for each of the
metal (specifically with faster removal rates of Ni) providing max-
imum removal upto around 30 min contact time, still to obtain the
equilibrium, around 40 min of the contact time is required [32].
Interestingly, the% removal curves for Cu and Pb intersect that of
Fig. 6. Effect of temperature on adsorption of heavy metals on coconut husk for
40 min (Pb(II), Co(II), Ni(II), Zn(II): 200 mg/L each, adsorbent: 1.0 g, pH-6.0).
Fig. 7. Effect of pH on adsorption of Heavy metals on coconut husk at 30 ± 1 ◦ C
(heavy metal ion (each at 500 mg/L), adsorbent: 1.0 g, agitation time: 40 min).
Ni curve proving rapid removal of Cu and Pb than Ni after around
30 min exposure time.
3.4. Effect of temperature
The adsorption of the metal ions on CH was studied at various
temperatures from 10 to 80 ◦ C each interval of 10 ◦ C. With tem-
perature increase, a general trend is observed for all the HM ions
which shows enhancement of% removal, but to different extent for
individual metal ion. After optimization (around 80 ◦ C) for three
metals except Pb, the decrease in% removal was noticed as shown
in Fig. 6, which may be due to the initiation of desorption pro-
cess, whereas for Pb still increasing% removal is obtained which
may be understood in terms of its higher ionic radius as well as
larger atomic weight (Table 6). It may also be noticed that the nar-
row pores get widened at elevated temperatures due to increased
activation which accords the more uptake of larger Pb ions [33].
3.5. Effect of pH
The pH of the solution significantly affects the amount of metal
ion adsorbed onto biosorbents as it influences the properties of
the biosorbents, as well as the speciation of metal ions in aque-
ous solution [34,35]. For experiments at different pH, the acidity
of heavy metal solutions were adjusted by adding 0.1 M HNO3 and
0.1 M NaOH solution drops. The effect of solution pH on metal ion
removal is shown in Fig. 7, which reflects that with gradual increase
in batch pH, increase in the% removal of each of HM ion and shows
optimization at different pH levels. The maximum removal of Cu
and Pb occurs at pH 5.0, Ni at pH 6.0 and Zn at pH 7.0 whereas
after each maxima, sharp fall in metal removal is obtained due to
initiation of precipitation as soluble metal hydroxides and/or des-
orption phenomenon. It is pertinent to mention that fast removal
rate is observed for Pb and Ni in the beginning, which became
 R. Malik et al. / International Journal of Biological Macromolecules 98 (2017) 139–149
Fig. 8. a-Langmuir, b-Freundlich, c- Temkin, d- Dubinin–Radushkevich, e- Flory Huggins plots for adsorption of heavy metals on CH.
slower gradually towards higher values of pH. Many adsorption
studies report that pH in the range 5.0–7.0 as the optimum pH
for Cu(II),Pb(II),Ni(II) and Zn(II) adsorption by various biosorbents
[34–36]. At low pH (2.0–3.0), more H+ ions will be available to com-
pete with HM ions for the adsorption sites of the adsorbent. In
addition, at low pH, most of the functional groups are protonated
too [35]. This will reduce the number of binding sites available for
the adsorption of metal ions.
3.6. Thermodynamics and adsorption isotherms
The thermodynamic criteria for the biosorption sequence for the
four ions were evaluated using Gibbs free energy (G), enthalpy of
adsorption (H), and entropy of adsorption (S) by carrying out
the adsorption experiments at different temperatures and using
the subsequent Eq. (3).
G = H − TS
q
H S
log =− + (4)
ce 2.303RT 2.303R
Where (q/Ce ) is called the adsorption affinity and is the ratio of q, the
amount adsorbed per unit mass at equilibrium to Ce , the equilib-
rium concentration of the adsorbate. The values of H and S were
determined from the slope and the intercept of the Van’t Hoff plots
of log (q/Ce ) versus 1/T (Eq. (4)) whereas, G values were calculated
using Eq. (3) and the data, placed in Table 3 explaining the fact that
the adsorption process becomes more spontaneous towards higher
temperatures [37,38].
143
3.6.1. Adsorption isotherms
Adsorption equilibrium is established when the concentration
of adsorbate in the bulk solution is in dynamic balance with that
of the interface [30]. Moreover, the equilibrium adsorption studies
determine the capacity of the adsorbent, which can be described
by an adsorption isotherm, characterized by certain constants
whose values inform the surface properties, heterogeneity, adsorp-
tion intensity and affinity of the particular adsorbent. Equilibrium
relationships between adsorbent and adsorbate are described by
adsorption isotherms. Five isotherm models have been proposed
for the adsorption of solutes/adsorbates in a liquid solution onto
solid surface of CH.
3.6.1.1. Langmuir adsorption isotherm. The equilibrium data were
analysed in accordance with the Langmuir adsorption isotherm (Eq.
(5)).
(3) Ce 1 ce
= K + (5)
q qmax d qmax
Where Kd is the Langmuir constant related to energy of adsorption
(L/mg). A plot of (Ce /q) vs. Ce should give a straight line if the Lang-
muir equation is obeyed by the adsorption equilibrium (Fig. 8a). The
slope and intercept of this line are used to calculate the values of q
max and Kd respectively. These expressions have been shown to be
valid in higher concentration ranges [39]. The regression coefficient
(R2 > 0.95) values along with all the thermodynamic parameters are
given in Table 2a.
144 R. Malik et al. / International Journal of Biological Macromolecules 98 (2017) 139–149

Table 2
(a) Isotherm parameters. (b). Isotherm Parameters.

CH 1.0 (g) Langmuir constants Freundlich constants

R2 qmax (mg/g) Kd (L/mg) R2 1/n Kf (L/mg)

Cu 0.9759 117.6 0.0097 0.9540 0.42 0.53

Pb 0.9584 188.6 0.0216 0.8906 0.90 0.65
Ni 0.9751 169.5 0.0158 0.9480 0.57 0.57
Zn 0.9518 108.7 0.0082 0.9519 0.98 0.67

CH (1.0/g) Temkin constants D-R constants Flory Huggins constants

2 2
R AT (L/mg) bT (J/mol R E (kJ/mol) R2 x

Cu 0.9452 1.64 8040.67 0.7305 5.00 0.9587 1.0646

Pb 0.9854 1.36 4943.37 0.9037 2.50 0.9695 0.0481
Ni 0.9780 1.05 6371.12 0.7190 3.16 0.9139 0.1707
Zn 0.9877 1.44 4616.34 0.7991 4.08 0.9318 0.0457

Table 3 Supplementary to the Langmuir adsorption, the Dubinin-

Thermodynamic parameters for adsorption of heavy metal ions.
Radushkevich (D-R) isotherm was also studied, using the Eq. (7).
Heavy Metals S Jmol−1 H kJmol−1 G (kJ/mol) at temperature
ln = ln max − ˇε2 (8)
30 ◦ C 60 ◦ C 80 ◦ C  1

Where ε can be correlated as; ε = RTln 1 + C
where R, T and C rep-
Cu 17.61 0.27 −5.06 −5.59 −5.94
Pb 19.91 0.25 −5.77 −6.37 −6.77 resent the gas constant (8.314 J mol−1 K−1 ),absolute temperature
Ni 14.55 0.16 −4.24 −4.68 −4.97 (K) and adsorbate equilibrium concentration (mg/L), respectively,
Zn 6.12 0.15 −1.69 −1.88 −2.00  and ˇ were obtained from intercept and slope of the D-R isotherm
between ln  and ε2 (Fig. 8d), the E, was then calculated using Eq.
(9) and defined as the mean free energy change.
3.6.1.2. Freundlich adsorption isotherm. This isotherm model
describes heterogeneous adsorption systems with uniform energy 1
E= √ (9)
as expressed by the following Eq. (6). 2ˇ
1/n Where ˇ is denoted as the isotherm constant. From Table 2b, it can
q = Kf Ce (6)
be seen that the E values lie in the range of 0–8 kJ/mol indicating
where Kf and 1/n are known as Freundlich coefficients which can physical adsorption [43,45] for all the four metal ions, but for Cu,
be determined from the plots(Fig. 8b) of log q versus log Ce on the its value is highest [46].
basis of the linear form of Eq. (7).
1 3.6.1.5. Temkin adsorption isotherm. The Temkin isotherm [47]
log q = logKf + logCe (7)
n contains a factor that explicitly takes into the account of
The slopes (1/n) of the plots (0.90 for Pb2+ and 0.42 for Cu2+ adsorbent–adsorbate or adsorbate- adsorbate interactions. By
and 0.57 for Ni ions) are found to be in the range of 0–1, proving ignoring the extremely low and large value of concentrations, the
their better adsorption intensity or surface heterogenity suggesting model assumes that heat of adsorption (function of temperature)
slight chemisorption process, whereas 1/n is 0.98 for Zn (very close of all molecules in the layer would decrease linearly rather than
to 1) may show co-operative adsorption for Zn [39–41]. logarithmic with coverage [47].
This model describes that the heat of adsorption decreases
3.6.1.3. Flory-Huggins isotherm. The heavy metals are present in linearly with increasing surface coverage and the adsorption is
hydrated form in the aqueous solution [42] and before their adsorp- characterized by a uniform distribution of binding energies. The
tion, each metal ion should be free from this hydrated sheath either Temkin isotherm has a convenient linear form, which is expressed
partially or fully by removing those water molecules present in the by Eq. (10).
primary hydration sphere [43] which is supported by Flory-Huggins q = BlnAT + BlnCe (10)
isotherm. As the number of removed water molecules is maximum
RT
in case of Cu, (Table 2b) which advocates the better binding and B= (11)
bT
hence, maximum removal of Cu whereas for Pb, Ni and Zn, there is
partial substitution of lesser number of water molecules showing where, AT is Temkin isotherm equilibrium binding constant corre-
lowered extent of adsorption of other three metals following the sponding to the maximum binding energy (L/mg), B is a constant
observed order of removal through experimental observations. related to the heat of biosorption (J/mol), R is the universal gas
constant (8.314 Jmol−1 K−1 ), T at 30 ± 1 ◦ C, bT is Temkin isotherm
3.6.1.4. Dubinin–Radushkevich (D-R) isotherm. constant, which indicates the adsorption potential of the adsorbent
Dubinin–Radushkevich isotherm, is an empirical model, gen- and the bT values again, are, in support of highest adsorption of Cu
erally applied to express the adsorption mechanism with a followed by the other three metals in the same order of removal
Gaussian energy distribution onto a heterogeneous surface [44]. (Table 2b). Both AT and B can be determined from a plot q vs. ln Ce
The model has often successfully accorded with high solute (Fig. 8c) and the constants were determined from the intercept and
activities and the intermediate range of concentrations data. The slope, respectively.
approach was usually applied to distinguish the physical and
chemical adsorption of metal ions [44], with its mean free energy, 3.7. Kinetic studies
E per molecule of adsorbate (for removing a molecule from its
location in the adsorption space to the infinity) can be computed According to [48–50], adsorption may occur through different
by the relationship [39]. types of adsorbate transfer processes and the kinetics are mainly
 R. Malik et al. / International Journal of Biological Macromolecules 98 (2017) 139–149 145

Fig. 9. a-Pseudo-First-order kinetics (plot of time vs. log (q − qt ), b-Pseudo-Second-order kinetics (plot of time vs. t/q), c-Intraparticle model (plot of t1/2 vs. q) for heavy metal
biosorption on CH).

Fig. 10. HOMO and LUMO of Coconut husk (Major component).

controlled by various factors as (i) adsorbate diffusion from the
solution to the boundary film surrounding the adsorbent (bulk
diffusion), (ii) diffusion from the film to the surface of the adsor-
bent (film diffusion or external diffusion), (iii) diffusion from the
surface to the intraparticular sites (intraparticular diffusion or
pore diffusion) and (iv) adsorption of metals by complexation,or
physico-chemical adsorption or ion exchange, all occurring in the
sequential stages/steps. In the present case, as the proper agitation
was provided in order to avoid adsorbent and metal gradients, so
minimizing bulk diffusion and hence, the rate may not be limited by
mass transfer from the bulk liquid to the CH external surface. Hence,
diffusion from the film to the surface of the adsorbent (external dif-
fusion or film diffusion) and intraparticle diffusion may take place
in addition to the solute adsorption by partial complexation and/or
physico-chemical adsorption might govern the overall biosorption
process.
For the present investigation, the adsorption kinetics of metals
were estimated by pseudo-first-order, pseudo-second-order and
intraparticle models. The straight-line fits of the pseudo-second-
order (t/qt versus t, Eq. (12)) with (Fig. 9b), intraparticle model,
qt versus t1/2 (Fig. 9c) and Eq. (13), pseudo-first-order [log(q - qt )
versus t, Eq. (14) (Fig. 9a)] and various parameters of the models
are shown in Table 4,
According to Intraparticle theory [48]:
qt = kpi t 1/2 (13)
where kpi (mg/g min1/2 ), the rate parameter of stage i, is obtained
from the slope of the straight line of qt versus t1/2 (Fig. 9c). Ci , the
intercept of stage i, gives an idea about the thickness of boundary
layer, i.e., the larger the intercept, the greater the boundary layer
effect [48,50].
t
log (q − qt ) = logq − kpi (14)
2.303
where q and qt signify the amount adsorbed at equilibrium and at
any time t, kpi is the rate constant. The graph of log (q − qt ) versus t
(Fig. 9a) exhibits straight lines at different concentrations.
Many authors [48–50] report that plots of adsorption capacity
against the square root of time are linear while the initial curved
portions of the graphs may be attributed to boundary layer diffu-
sion which is also clear from Fig. 9c [50]. This linear portion is due to
intraparticle diffusion effects [51] as also clear from Fig. 9c. If intra-
particle diffusion occurs, then qt versus t1/2 will be linear and if the
plot passes through the origin, then the rate limiting process is only
due to the intraparticle diffusion,otherwise, some other mechanism
like instantaneous adsorption or external surface adsorption (first

1 1 1
  region in Fig. 9c) along with intraparticle diffusion also involved.
= + t (12) In the present investigation, the metals adsorption follow pseudo
qt k2 q2 q first order as well as pseudo second order kinetics in addition to
146 R. Malik et al. / International Journal of Biological Macromolecules 98 (2017) 139–149
Table 4
Kinetic parameters for metal adsorption.
CH (1.0/g) Intraparticle diffusion parameters
Ci kpi R2
Cu 97.49 19.57 0.7306
Pb 61.87 22.39 0.7180
Ni 87.81 17.98 0.6955
Zn 69.68 13.37 0.6636
Fig. 11. Proposed mechanism of action for removal of heavy metals by catechin.
slight intraparticle diffusion. So,external diffusion or film diffu-
sion and intraparticle diffusion may take place, consequently, the
metal adsorption by partial complexation and/or physico-chemical
adsorption(electrostatic forces) might govern the overall biosorp-
tion process.
3.8. Quantum study of the major constituent of the biosorbent
Catechin as the main constituent of coconut fibre or husk [52]
possessing the structure placed in Fig. 11 and the HOMO and LUMO
orbitals placed in Fig. 10. HOMO and LUMO orbitals of catechin
are obtained using Hyperchem 8.0 alongwith some other quan-
tum parameters (Table 5). Although, several extracts and fractions,
obtained from the C. nucifera fiber/husk are rich in polyphenols,
compounds such as catechins, epicatechins, tannins, and flavonoids
etc. but for performing the quantum study, the main constituent i.e.
catechin [52] has been considered for the present case.
3.9. A novel approach for mechanism of adsorption based on
quantum study
According to the Lewis theory [53], Lewis acids and bases can
further be divided into hard or soft or border line type. Hard
Lewis bases are characterized by small ionic radii, strongly sol-
vated, highly electronegative, weakly polarizable and with high
energy HOMOs. Soft Lewis bases are characterized by large ionic
radii, intermediate electronegativity, highly polarizable and with
low energy HOMOs. Moreover, it is not necessary for Lewis acid or
base to possess all the properties to be classified as hard or soft or
borderline. A new approach to explain the mechanism of adsorp-
tion has been proposed in the present study based on the HOMO
and LUMO structures of the major constituent of coconut husk [52]
i.e. catechin (Fig. 11) which possesses both parts i.e. OH and COC-
groups acting as hard Lewis bases and ␲-electron cloud present on
aromatic ring may act as soft base (HSAB principle). Hard Lewis
acids are characterized by small ionic radii, high positive charge,
strongly solvated, empty orbitals in the valence shell and with high
energy LUMOs while Soft Lewis acids are characterized by large
ionic radii, low positive charge, completely filled atomic orbitals
and with low energy LUMOs. Hence, on these grounds, Cu2+ , Ni2+
and Pb2+ may be treated as borderline acids and Zn2+ ions due to
completely filled atomic orbitals may be taken as soft acid [53].
Mul1iken has developed a theory of covalent bonding meant for
simplifying the complicated behaviour of soft bases and soft acids.
Bonding will be strong if the electron affinity of the acid is large and
the ionization potential of the base is low. Thus, closer approach
Pseudo-second order constants Pseudo-first order constants
R2 ki(2) R2 ki(1)
0.9884 0.0370 0.9797 2.30
0.9594 0.0591 0.9808 2.24
0.9934 0.1920 0.9856 1.85
0.9809 0.0556 0.9943 1.46
may happen and better overlap of the wave functions used in cova-
lent bonding between adsorbent (Lewis base) and metals (Lewis
acid). Mulliken’s treatment is also intended specifically for charge
transfer complexes [54]. Electron affinity of four HM ions (Table 6)
follows the same order of adsorption as observed due to experi-
mental study. Also, chemical hardness, essentially, measures the
resistance to change in the electron distribution in a collection of
nuclei and electrons [55].
The theoretical approach which has been introduced by the
researchers [56–58] and similar approach has also been exploited
for the first time to extract the support from quantum study of the
major component of coconut husk and it may be believed that the
effective binding through partial complexation may occur from 1,2
disubstituted side in comparison to 1,3 disubstituted side as shown
in Fig. 11. This fact may be proved with the help of HOMO and LUMO
of the active as well as major constituent of CH given in Fig. 10. From
this Figure the high electron density may be observed precisely at
the HOMO of the flat aromatic ring whereas the LUMO is towards
1,3 disubstituted side of the molecule of adsorbent contributing
less electron density and hence less probability of donation from
this part of the biosorbent. All the three ions except Zn may show
tendency towards partial complex formation with the hard basic
part of the coconut husk as shown in Fig. 11 while for Zn being soft
acid, electrostatic forces of attraction from aromatic ring of CH may
occur. Here, it is pertinent to mention that the three aromatic rings
of the adsorbent do not lie in a single plane, rather the molecule as
a whole exists in twisted form providing better binding for multi
metals with minimized repulsive effects. It may also be noticed that
the heavy metal may bind more effectively through the two oxygen
atoms through one as in Fig. 11 or four oxygen atoms of two similar
constituents of CH as well as with the other rich constituents of CH
[27,52,12] possessing good donor groups like OH, COC- etc.
The low value of hydration energy (−30.33 Kcal/mol) of CH com-
ponent also indicates its lessened tendency to remain in aqueous
phase sparing itself for metal ions adsorption. The quantum chem-
ical parameters placed in Table 5, namely EHOMO (highest occupied
molecular orbital energy), ELUMO (lowest unoccupied molecular
orbital energy), the energy difference (E) between EHOMO and
ELUMO , dipole moment (), electron affinity (A), ionization poten-
tial (I), the absolute electronegativity (), absolute hardness () and
softness ( ).
where, I = −EHOMO and A = −ELUMO
 = (I + A)/2
 = (I − A)/2
= 1/
of CH also shown in Table 5. Hence, the quantum study can be
explored to understand the mechanism by identifying the donation
sites of the biosorbents. Moreover, the suggested mechanism is also
fully supported by the FTIR study and its observations. Also, the high
dipole moment, a measure of high electron density which is 3.067
D for catechin given by quantum study (Table 5), hence, availabil-
ity of electrons with tendency to donate to the HM ions, as well
 R. Malik et al. / International Journal of Biological Macromolecules 98 (2017) 139–149 147

Table 5
Quantum chemical parameters of Coconut husk main constituent [52].

Descriptors Value of Descriptor Descriptors Value of Descriptor

Total energy −389392.9117 kJ/mol Electron Affinity −0.1587

Dipole Moment 3.067 Debye Ionisation Potential 8.8157
E HOMO −8.815762 eV Polarizability 28.65 Å3
E LUMO +0.1587403 eV Surface area 365.4 Å2
Electronegativity 4.328 eV Volume 777.88 Å3
Softness 0.2228 Hydration Energy −30.33 Kcal/mol
Hardness 4.4872 Mass 290.27 amu

Table 6
Physico-chemical properties of Cu, Pb, Ni and Zn divalent ions.

Physico-chemical property Cu Pb Ni Zn Ref

Effective Ionic radius (A0 ) 0.73 1.33 0.69 0.74 [67]

Hydrated ionic radius (A0 ) 4.19 4.01 4.04 4.30 [51,63]
Pauling electronagativity (eV) 2.0 1.87 1.91 1.65 [66]
Hydration energy (kJ mol−1 ) −2100 −1480 −2105 −2046 [63]
Chemical hardness (eV) 3.25 3.53 3.25 4.94 [53]
Softness (Reciprocal of hardness) 0.3076 0.2832 0.3076 0.2024 [63]
Electron affinity (eV) 1.237 0.364 1.157 0.0 [58]
Diffusion coefficients of hydrated cations (infinite dilution)(D (10−10 m2 s−1 at 25 ◦ C) 7.4 7.05 9.45 7.03 [63]
Atomic mass 63.55 207.2 58.69 65.38 [68]

as the EHOMO and ELUMO values confirm the ability of the biosor-
bent towards partial complexation and/or electrostatic forces of
attraction inclined to physical adsorption.
3.10. Properties of HM ions affecting their selective and
competitive behavior
3.11. Regeneration of the adsorbent
Desorption experiments showed that 85% of heavy metals could
be recovered simply by washing heavy metal-loaded CH with
deionised water (pH 7.0) and the remaining quantity of metal ions
with dilute nitric acid (pH 4.0). The washed CH after being thor-
oughly dried first in air followed by drying in hot air oven at 80 ◦ C
for 3 h could be reused as an adsorbent with nearly equal activity.

The physico-chemical properties of the metal ions have been
proved to be an important factor in deciding the binding of metal
ions on biosorbents [30]. Due to the chemical interactions between
metal ion species in multi component mixtures, the component
that has higher affinity will readily be adsorbed onto the available
adsorption sites. Electron affinity of four HM ions (Table 6) follows
the same order of adsorption as their% removal. Furthermore, Cu
ions have one unpaired electron leading to better attraction with
the electric field originating from the adsorbent, while the elec-
trons in zinc ions are paired [59]. The authors of the study [51]
also commented that the work done by [60–63] concludes higher
uptake of Pb2+ ions attributed to its lower hydrated ionic radius of
4.01 Å as compared to 4.19 Å for Cu2+ and argued that the smaller
hydrated ionic radius of Pb2+ allows it to approach more closely to
the adsorbing surface for favorable adsorption and the similar logic
also given by [64]. But authors of [51] explained that their findings
are opposite to [60–64] and [51] gives the same order of preference
as obtained in the present study. According to [51], the nonhy-
drated ionic radius of Cu ions (0.73 Å) is much lower than 1.19 Å
for Pb2+ and chelation becomes more favorable with the smaller
Cu2+ with higher charge density and the added entropic advan-
tage due to releasing a larger number of water molecules from its
hydration shell. In addition to the justification given by them, the
present study agrees well with their [51] results, as the number of
removed water molecules is maximum in case of Cu, higher val-
ues of bT , (Table 2a and b), higher electronegativity and electron
affinity of Cu, lower chemical hardness than Pb and consequently
more softness which means more reactivity [56–58] as presented
in Table 6. All these findings justify the maximum adsorption of
Cu whereas for Pb, Ni and Zn, most of these properties placed in
Table 6 suit their observed order of uptake by CH. Moreover, the
higher uptake of Cu than Pb is also observed by [51,65] supporting
the present observations.
3.12. Future recommendations and scope
A more oriented theoretical work based on quantum study and
molecular simulation towards heavy metal removal area needs
to be exercised. A deep and precise insight into the mechanism
adopted by various adsorbents keeping other experimental condi-
tions similar for the competitive adsorption and selectivity of Pb
and Cu along with Ni and Zn etc. is highly required.
4. Conclusion
From the above study, it can be concluded that the adsor-
bent Unmodified Coconut Husk (CH) can be used efficiently to
treat wastewater contaminated with heavy metals. Removal of
heavy metals through emphasis on adsorption/biosorption phe-
nomenon was applied. The removal of HM ions (Pb, Cu, Ni and
Zn) has been studied at the high initial metal concentration
(100 mg/L–500 mg/L) by using coconut husk at different oper-
ating conditions through batch experiments. The experimental
statistics showed that maximum uptake capacity was 443.0 mg/g
(88.6%) for Cu, for Ni 404.5 mg/g (80.9%), 362.2 mg/g (72.4%) for
Pb2+ and 338.0 mg/g (67.6%) for Zn2+ ions. The order of metal
removal suits well the order of adsorption and has been found to
be Cu2+ > Ni2+ > Pb2+ > Zn2+ for most of the operating conditions like
initial metal ion concentration, adsorbent dose, pH, temperature
and contact time. The order of preference for uptake by CH is justi-
fied on the basis of electronegativity value, hardness/softness value,
ionic radii, hydration energy and electron affinity etc. of the metal
ions. The parameters obtained for CH (catechin as main constituent)
using Hyperchem software also confirm its donation behavior as
well as its compatibility for binding with four divalent HM ions
simultaneously, which are in want of electron density. A novel
approach for mechanism of adsorption has been presented. The
148 R. Malik et al. / International Journal of Biological Macromolecules 98 (2017) 139–149
adsorption isotherms specially Flory Huggins, Freundlich, Lang-
muir, D-R and Temkin support the mechanism and favor the order
of removal. The characterization techniques FTIR and SEM also con-
firm validity of the present findings.
Acknowledgement
Authors are thankful to university grant commission [Ref No-
17-06/2012(1)EU-V] for financial support to access this research
work.
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