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Batch adsorption and desorption studies on the removal of lead (II) from
aqueous solution using nanochitosan/sodium alginate/microcrystalline
cellulose beads

Article  in  International journal of biological macromolecules · May 2017

DOI: 10.1016/j.ijbiomac.2017.04.120

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Accepted Manuscript

Title: Batch adsorption and desorption studies on the removal

of lead (II) from aqueous solution using nanochitosan/sodium
alginate/microcrystalline cellulose beads

Authors: K. Vijayalakshmi, B. Mahalakshmi Devi, Srinivasan

Latha, Thandapani Gomathi, P.N. Sudha, Jayachandran
Venkatesan, Sukumaran Anil

PII: S0141-8130(16)32016-5
DOI: http://dx.doi.org/doi:10.1016/j.ijbiomac.2017.04.120
Reference: BIOMAC 7484

To appear in: International Journal of Biological Macromolecules

Received date: 15-10-2016

Revised date: 27-2-2017
Accepted date: 30-4-2017

Please cite this article as: K.Vijayalakshmi, B.Mahalakshmi Devi, Srinivasan Latha,
Thandapani Gomathi, P.N.Sudha, Jayachandran Venkatesan, Sukumaran Anil, Batch
adsorption and desorption studies on the removal of lead (II) from aqueous solution using
nanochitosan/sodium alginate/microcrystalline cellulose beads, International Journal of
Biological Macromoleculeshttp://dx.doi.org/10.1016/j.ijbiomac.2017.04.120

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Batch adsorption and desorption studies on the removal of lead (II) from aqueous
solution using nanochitosan/sodium alginate/ microcrystalline cellulose beads
1K. Vijayalakshmi, 2B. Mahalakshmi Devi, 3Srinivasan Latha, 1Thandapani

Gomathi, 1*P.N. Sudha, 4Jayachandran Venkatesan and 5Sukumaran Anil

1, 1*PG & Research department of chemistry, DKM College for Women, Vellore, Tamil
Nadu, India
2Department of Chemistry, Bharathiar University, Coimbatore 641 046, Tamilnadu,
India
3Department of Chemistry, SRM University, Chennai, Tamil Nadu, India
4Marine Bioprocess Research Center and Department of Marine-bio Convergence
Science, Pukyong National University, Busan, Republic of Korea
5Division of Periodontics, Department of PDS, College of Dentistry, Prince Sattam Bin
Abdulaziz University, Riyadh, Saudi Arabia
(*Corresponding Author: Tel: (+91) 9842910157; e-mail-id: drparsu8@gmail.com)
Abstract

The feasibility of adsorption and desorption behavior of nanochitosan(NCS) /sodium

alginate(SA)/microcrystalline cellulose (MC) bead prepared in 2:8:1 ratio for Pb(II) removal has

been investigated through batch studies. The proof of adsorption of Pb(II) ions onto

NCS/SA/MC beads was identified from FT-IR and EDX-SEM Studies. Studies of the effect of

pH, adsorbent dose, metal ion concentration and temperature reveals that the optimum conditions

for adsorption was found to be pH:6; adsorbent dose:4g ; initial metal concentration: 62.5 mg/L

and temperature:50°C. Various equilibrium adsorption isotherm models namely Langmuir,

Freundlich, Temkin and D-R applied for the analysis of isotherm data indicate that the

Freundlich adsorption isotherm model was found to be followed. On the basis of kinetic studies,

specific rate constants involved in the processes were calculated and the observed result shows

that the pseudo second order kinetics was found to be a better fit. The desorption studies reveals

1
that the recovery of Pb(II) from NCS/SA/MC bead was found to be effective by using 0.1 M HCl

solution. From the results it was evident that the NCS/SA/MC bead showed better Pb(II) uptake

performance and regeneration for further use and hence it was found to be an efficient biosorbent

for treating industrial effluent.

Keywords: Nanochitosan, sodium alginate, cellulose, adsorption.

1. Introduction

The quality of life on earth is inextricably linked to the overall quality of the environment

comprising mainly of water, temperature, light and other living and non-living things [1]. Water

our gift of nature which is a finite and precious resource essential for all the human beings and

living organisms. But recently almost 70 per cent of water gets contaminated by biological,

toxic, organic and inorganic pollutants[2].Water pollution is a serious problem since the

indiscriminate release of hazardous pollutants by industries especially pose a major threat to all

kinds of organisms inhabiting aquatic as well as terrestrial ecosystems [3]. Due to their

bioaccumulative and toxic nature, the heavy metals, in particular are a group of pollutants

(mostly from industrial, agricultural and domestic activities) is of major concern in the aquatic

environment [4].

According to the Environmental Protection Agency (EPA), the presence of heavy metals

even in lower concentration in water can have a potential toxicity and hence it should be treated

before discharge into the environment. Some of the most important toxic pollutants enter to the

water bodies through industrial wastewater treatment plants were lead, nickel, cadmium and so

on [5]. Among all the heavy metal ions special attention has been given to lead (II) since the lead

ion accumulates mainly in kidney, bones, brain leading to many serious health disorders like

nervous disorders, kidney failure, anemia and even death and hence it is essential to remove
2
Pb(II) from wastewater before disposal. Technologies were developed by many researchers for

the heavy metal removal including the ion exchange, reverse osmosis, chemical precipitation,

membrane filtration, adsorption etc., When compared to the other technologies, the adsorption

method is widely accepted in environmental treatment applications since it is more economical

and efficient for removing dyes, organic pollutants and heavy metals from polluted waters [6][7].

Various low cost sorbents such as sawdust, lignin, orange peel, chitin, zeolite, activated

carbon, dead biomass, clay, fly ash, algae etc., have been implemented for the adsorption but due

to high cost of certain adsorbents, there is a need for development of low-cost adsorbents.

Chitosan is polysaccharide absorbent composed of poly(1-4)-2-amino-2-deoxy-D-glucopyranose

units consisting of amino group in its structure which causes increasing adsorption capacity and

removal ability [8]. Recently, the nanomaterials (NMs) have been suggested as efficient, cost-

effective, environmental friendly alternative to existing treatment materials especially for the

environmental remediation [9][10]. Due to some disadvantages such as weak mechanical

properties and low porosity of chitosan, its fullest adsorption capacities are not met and hence

chemical modifications by cross linking agent such as sodium tripolyphospate can be carried out

in chitosan leading to the formation of nanochitosan resulting in the prevention of chitosan

dissolution in strong acids, improvement of mechanical strength and increase of adsorption

capacities.

Seyed Masoud Seyedi and his coworkers reported about the increased adsorption

behaviour of nanochitosan using Cd(II) aqueous solution than chitosan [11]. In addition,

Govindarajan and his coworkers also revealed about the good adsorption potential of

nanochitosan/ carboxymethyl cellulose blend in removing the cadmium ions [12] and hence from

literature survey in this work the nanochitosan, a non toxic material is preferably formed from

3
chitosan by ionotropic gelation method and utilized in sorbent preparation. Alginate, a water-

soluble linear polysaccharide composed of alternating blocks of 1-4linked α-L-guluronic and β-

D-mannuronic acid fragments extracted mainly from brown seaweeds. The carbonyl and

hydroxyl groups present on its alginate chain are excellent functional groups for anchoring heavy

metals [13] and also due to its biodegradable, biocompatible, economical, environmental friendly

nature alginates could play an important role in wastewater treatment.

The utilization of lignocellulosic fibers for the metal ion removal was reported by many

researchers. The metal ion binding by lignocellulosic biosorbents is believed to take place

through chemical functional groups such as carboxyl, amino, or phenolics. Banana fibers are

associated with some challenges including high moisture uptake, low thermal stability and low

bonding with polymers [14]. The raw lignocellulosic biosorbents were modified by various

physical and chemical pretreatment methods to increase their adsorption capacities and hence in

this study initially the cellulose was extracted from banana fiber in microcrystalline form by

steam explosion method and utilized in sorbent preparation.

The adsorption properties of the adsorbent depend on a number of factors including

shape, distribution and method of its preparation. Many researchers reported that the

biopolymers in the form of beads can effectively remove heavy metals from industrial

wastewater [15]. Hence based on the survey of literature, this work aims to evaluate the

efficiency of blended form of nanochitosan with sodium alginate and microcrystalline cellulose

extracted from the banana fiber in the form of bead for the removal of lead ions from aqueous

solutions. The effects of various parameters such as adsorbent dose, contact time, pH,

temperature and initial metal concentration on lead ion adsorption were investigated and the

kinetics of adsorption was also studied.

4
2. Materials

The chemicals such as the sodium hydroxide (commercial grade), sodium alginate,

sodium hypochlorite and oxalic acid were purchased from Central Drug House Pvt. Ltd, Nice

chemicals, Kerala, India. The crosslinking agent calcium chloride, sodium tripolyphosphate and

the solvent glacial acetic acid were procured from Finar chemicals, Ahmedabad and Thomas

Bakers chemicals Pvt. Ltd., Mumbai. The banana fiber was collected from local farms and all the

chemicals utilized in this present study were of analytical grade

3. Materials and methods

3.1. Extraction of microcrystalline cellulose from banana fiber by steam explosion

process: As per the procedure reported by Bibin Mathew cherian and his coworkers [16], the

microcrystalline cellulose was extracted from the banana fiber by utitlizing the alkaline treatment

followed by bleaching, acidic and mechanical treatment in steam explosion process. The detailed

extraction procedure has been already reported in Vijayalakshmi et al., 2016 [17].

3.2. Preparation of nanochitosan: By utilizing the ionotropic gelation method,

nanochitosan was prepared from chitosan as per the procedure reported by Sivakami and her

coworkers [18]. A homogeneous viscous chitosan gel was prepared by stirring 1g of chitosan

dissolved in 200ml of 2% acetic acid for a period of 20 minutes. To the above prepared

homogeneous chitosan solution, an ionic ccrosslinking agent, sodium tripolyphosphate (0.8 g of

sodium tripolyphosphate dissolved in 107 ml of deionized water) was then added in drop wise

with rapid stirring (30 min). After this process is over, the obtained milky emulsion like

appearance of nanochitosan was allowed to stand overnight to settle as suspension, the

supernatant solution was decanted and finally the thick suspension of nanochitosan settled at the

bottom of the beaker was preserved in the refrigerator.

5
 3.3. Preparation of NCS/SA/MC (2:8:1) bead: The NCS/SA/MC bead was prepared by

pouring the homogeneous blended mixture of nanochitosan (2g), sodium alginate (8g) and

microcrystalline cellulose (1g) dispersed in minimum amount of water prepared at 500 rpm

stirring rate (30 minutes) into 0.2M calcium chloride solution with the help of syringe. The beads

so formed were then allowed to stand in 0.2 M calcium chloride solution for few hours and after

this process is over, the beads were rinsed with double distilled water to remove any excess

CaCl2 followed by drying for 24 hours.

3.4. Adsorbate Preparation: Factors such as pH, contact time, adsorbent dose and

temperature which affect the adsorption process has been studied by utilizing standard solution

(200mg/L) of lead (II) prepared by dissolving 0.3197g of lead nitrate in 1000 ml deionised water.

In order to study the effect of initial metal concentration on adsorption process, the stock solution

of lead nitrate (1000 ppm) was prepared separately and suitably diluted accordingly to various

initial concentrations.

4. Characterization

4.1. Dynamic light scattering (DLS) studies

The particle size of the chitosan was analyzed using the Nanotrac 150 particle size

analyzer (measurement range from 0.8–6500 nm (10-9 m)).

4.2. Fourier Transform Infra Red Spectroscopy Studies (FTIR)

The FT-IR spectrum of the prepared NCS/SA/MC bead were recorded using the Perkin

Elmer 200 FTIR spectrophotometer in the wave number range from 4000 cm-1 to 450 cm-1

during 64 scans, with 2 cm-1 resolution.

6
 4.3. Energy dispersive scanning electron microscopic (EDX-SEM) studies

The surface morphology of the prepared samples were examined with the Scanning

Electron Microscope (Zeiss EVO 40) coupled with energy dispersive X-ray (EDX) spectrometer

and the photographs were taken at different magnifications.

4.4. Batch adsorption experiments

The extent of adsorption onto NCS/SA/MC bead (2:8:1) was investigated with lead

nitrate (200mg/L) using the batch studies by changing the pH, adsorbent dose, contact time,

initial metal ion concentration and temperature. Initially the pH of lead (II) solution was adjusted

to the required value (pH=4, 5, 6) by adding 2N NaOH solution for increasing the pH and 1:1

HCl for decreasing the pH. After the adjustment of pH, about 1g of above prepared NCS/SA/MC

bead (2:8:1) was added to 100ml of lead nitrate (200mg/L) solution taken in a conical flask. This

solution mixture was allowed to agitate well at 30ºC for one hour using orbital shaker at fixed

speed of 160 rpm. After the attainment of equilibrium, the adsorbent was separated by filtration

using Whattmann filter paper and the filterate collected was analysed using the atomic

absorption spectroscopic (AAS) studies. A similar procedure was carried out by varying the

adsorbent dose, contact time, metal ion concentration and temperature. The percentage of

adsorption of Pb(II) ion was determined by following equation

Initial metal ion conc − Final metal ion conc

Adsorption (%) = × 100
Initial metal ion conc

4.5. Batch desorption experiments

Batch desorption studies was done using 1g of M(II) loaded adsorbent with 100 ml of

0.1M HCl as desorbing agent. This solution mixture was shaken well for a period of 30 minutes

7
and the collected effluent concentration was then analyzed using AAS studies. The percentage of

desorption [19] was calculated using the following equation

released metal concentration

Desorption (%) = × 100
initially sorbed metal concentration
5. Results and discussion

5.1. Particle size measurement

The particle size measurement of nanochitosan prepared from chitosan by ionotropic

gelation method was carried out by dynamic light scattering (DLS) studies in order to prove its

formation and the obtained DLS studies were represented in Fig.1.

<Insert Fig.1>

The dynamic light scattering (DLS) results presented in Fig.1 indicate that that the

particle size of the nanochitosan was found to be 100.02 nm and from this obtained result it was

concluded that the nanochitosan had been formed from chitosan by ionotropic gelation method.

5.2. Scanning electron microscopic (SEM) studies

Fig.2 represents the SEM micrograph details of nanochitosan prepared from chitosan by

ionotropic gelation method.

<Insert Fig.2>

The scanning electron micrograph of nanochitosan presented in Fig.2 demonstrates the

good dispersion of the nanoparticles which are entangled one on the other with a larger exposed

surface making the material very suitable for adsorption. Several authors reported that the

nanochitosan prepared from chitosan was found to be having the spherical shape [20], whereas

the obtained image reveals that the formation of nanoparticles is not spherical shaped but they

are in the rod shaped structure which is a peculiar structure.

8
 Different characterization techniques were utilized to confirm the sites of attachment of

metal ion onto NCS/SA/MC bead. The proof of Pb(II) ion attachment onto the adsorbent was

clearly evidenced from the results of FT-IR and EDX-SEM results taken before and after Pb (II)

adsorption processes and the observed results are represented below.

5.3. FT-IR studies

The FTIR spectral details of NCS/SA/MC (2:8:1) bead taken before and after Pb(II)

adsorption was shown in Table 1, Fig.3(a) and 3(b). The FTIR spectrum of NCS/SA/MC

(2:8:1) bead before and after metal ion (Pb(II)) adsorption were obtained to identify the possible

sites of attachment in the bead for the bonding of metal ions.

<Insert Fig. 3(a) and 3(b)> <Insert Table 1>

The FT-IR spectral details of NCS/SA/MC bead (2:8:1) before metal ion (Pb(II)) adsorption

(Fig.3(a)) shows a broad peak at 3424.96 cm-1 corresponding to the presence of intermolecular

hydrogen bonded OH stretching and NH stretching vibration [21]. The combination bands

arising at various wave numbers such as 2376.82 cm-1, 2311.20 cm-1 and 2252.58 cm-1 was due

to the combination of asymmetrical NH3+bending vibration and the torsional oscillation of the

NH3+ group [22]. A strong peak observed at 1630.49 cm-1 and 1512.57 cm-1 was indicative of the

presence of carbonyl stretching and NH bending respectively. Certain peaks obtained at 1458.77

cm-1, 1364.29 cm-1, 1338.23 cm-1, 1124.55 cm-1 and 669.55 cm-1 indicate the presence of CH

deformation, OH in plane bending in alcohols, C-N stretching, P-O-H bending and NH wagging

respectively.

Almost similar type of peaks with slight differences in wavenumbers were observed in the

case of NCS/SA/MC bead (2:8:1) after metal ion (Pb(II)) adsorption (Fig.3(b)). On comparing

the FTIR spectrum of NCS/SA/MC bead taken after metal ion adsorption (Pb(II)) with

9
NCS/SA/MC bead before metal ion adsorption, the shift in the –OH band from 3424.96 cm-1 to

3375.43 cm-1 after Pb(II) adsorption were observed. The peak obtained at 1338.23 cm-1 which

can be assigned to –C-N stretching vibration in amines was also shifted to lower wave number

after metal ion adsorption. This above observed reduction in peak position suggested that certain

interaction had taken place effectively between Pb(II) ions and nitrogen atoms.

Generally the metal ions chelate with the COO- and OH groups of alginate macromolecular

chains through partially ionic and partially coordinate bonds, respectively [23][24]. After the

adsorption of metal ions, the stretching vibrations due to the carboxylate ion group (1630.49

cm-1) [25][26] and bending vibration due to P-O-H group (1124.55 cm-1) was also shifted to

lower wavenumber [27][28] and this obtained result suggest that the oxygen atom present in the

OH, COO- ion and P-OH group were found to be active sites for metal ion attachment.

The metal carbon, metal nitrogen and metal oxygen stretching frequencies in the spectra of

adsorbed species (metal-adsorbate) were observed in the region of around 200-450 cm-1 [29]. In

this work, the proof of metal ion attachment onto the bead was clearly evidenced from the

appearance of peaks at 443.23 cm-1 due to M-N/ M-O stretching vibrations in case of metal

loaded NCS/SA/MC bead. Hence from the above observations it was concluded that during the

metal ion adsorption process the functional groups such as NH2 (which were not involved in

cross linking process), OH groups of nanochitosan, COO-, OH groups of sodium alginate and

OH groups of microcrystalline cellulose were involved in the coordinate bond formation with the

metal. The reduction in the peak positions confirms that these functional groups would have

taken part in chelation of metal ions.

10
 5.4. EDX –SEM studies

The EDX-SEM analysis was performed to observe the surface morphology of the

biosorbents before and after metal ion adsorption [30]. The EDX-SEM details of NCS/SA/MC

bead taken before and after Pb(II) adsorption was represented in Fig.4(a) and 4(b).

<Insert Fig.4(a) and 4(b)>

SEM analysis revealed that there were significant changes on the surface of biosorbents

after interaction with metal ions. Generally the specific surface area of the adsorbent increased

with the increasing roughness of the surface which increases the number of the sites for metal ion

adsorption [31]. From the SEM photographs presented in the Fig.4(a), it is evident that

NCS/SA/MC bead (2:8:1) before metal ion adsorption exhibited good rough suface morphology

and this observed result indicate that the NCS/SA/MC bead having rough surface morphology is

suitable for the metal ion adsorption process. Also it can be observed that after Pb (II) adsorption

onto NCS/SA/MC bead (Fig.4(b)), the surface morphology drastically changed whereby the

surface was more in irregular form showing agglomerate-like surface [32]. The presence of white

particles of Pb (II) ions on bead surface confirms that adsorption of Pb(II) ions had taken place.

After biosorption process with Pb (II) ions, it can be observed through the EDX analysis

that some of the sodium and calcium ions which were initially present in NCS/SA/MC bead were

removed during the biosorption and from this observation it is possible to say that the Pb (II)

ions replaced some of the sodium and calcium ions initially present in NCS/SA/MC bead which

created stronger cross-linking [33].In addition, the EDX-SEM micrograph of NCS/SA/MC bead

taken after sorption process shows a characteristic peak due to lead (II) and this showed the

diffusion or accumulation of metal ions onto the surface of NCS/SA/MC bead.

11
 In case of EDX-SEM results of Pb(II) loaded samples, certain new peaks were appeared

due to the adsorption of lead (II) onto the NCS/SA/MC bead (Fig.4b) and also in addition the

accumulation of white particles due to Pb(II) were seen over the surface after sorption process.

These observed results concluded that the adsorption of Pb(II) ions onto surface of NCS/SA/MC

bead takes place effectively and also suggest that the prepared NCS/SA/MC (2:8:1) bead has the

potential of acting as a very good adsorbent for practical applicability for the removal of Pb(II)

from aqueous solution.

Based on the results obtained by various researchers [34[[35] the following binding

mechanism was proposed for the adsorption of metal ions onto NCS/SA/MC bead (Fig.5).

<Insert Fig.5>

5.5. Adsorption studies

5.5.1. Effect of Solution pH

The adsorption of metal ions is mainly affected by the pH of the metal solution since the

pH affects both the adsorbent and adsorbate chemistry in solution [36]. The pH of the solution

influences properties of biosorbents, the availability of metal ions in solution and as well as the

number of binding sites on the adsorbent[37]. The extent of removal of lead (II) were analysed

by varying the pH of the solution from 4-8, by keeping the other variables as constant. The effect

of pH on the adsorption of Pb(II) ions onto the NCS/SA/MC bead was represented in Fig.6.

<Insert Fig.6>

From the results presented in the Fig.6, it was observed that the percentage removal of

lead ions increases as the pH increases from 4 to 6 but thereafter it declines. The reason behind

the fact is that at low pH, the protonation of active sites (OH, NH2) takes place, the protonated

H+ ion competes with Pb(II) ions for the available active sites of the adsorbent for adsorption

12
process and hence the percentage removal is low (at pH:4). But as pH increases, the

concentration of H+ decreases, they do not involve in metal ion on adsorption sites and hence it

shows an increased percentage removal (from pH:4-6) [38][39]. Beyond these pH values, a

decrease in uptake of the lead ions was observed. This was accounted for the precipitation of

metal hydroxide species [40].

5.5.2. Effect of adsorbent dose

To study the influence of adsorbent dose, adsorption of lead was studied at room

temperature at pH 6. The adsorbent dose was varied from 1g-6g g in 100 ml of 200mg/L of lead

nitrate solution. The effect of adsorbent dose was shown in Fig. 7.

<Insert Fig.7>

The obtained results clearly indicated that the removal efficiency increases up to the

optimum dosage beyond which the removal efficiency is constant. The initial increase of

percentage removal of Pb(II) with increased adsorbent dose was mainly due to the greater

availability of more binding sites for complexation of metal ion [41]. But beyond 4 g, there was

no appreciable improvement in the removal of metal ions and this can be attributed to two

reasons. Firstly at constant Pb(II) ions concentration and volume, the increase in the adsorbent

dosage will lead to unsaturation of the adsorption sites and secondly due to the particulate

interaction such as aggregation of adsorbents. In addition, the surface metal ions concentration

(on adsorbent) and the solution metal ion concentration also come to equilibrium with one

another at higher adsorbent dose and hence % removal remains constant [42].

13
 5.5.3. Effect of contact time

Optimization of contact time is one of the important studies performed during batch

adsorption process. In order to optimize it, the effect of contact time on removal of lead (II) by

NCS/SA/MC bead was studied by varying the time of contact from 60 min to 360 min. The

observed results were presented in Fig.8.

<Insert Fig.8>

It can be seen form Fig. 8 that there was a rapid uptake within the first 60 min and

adsorption equilibrium was attained within 240 min. The percentage removal of Pb(II) increases

from 86.88% to 94.48%. This rapid initial increase in the removal percentage was mainly

attributed to more number of vacant available adsorption sites and also due to the larger surface

area[43]. But beyond a certain amount of contact time, the adsorption sites get exhausted and

thus lead to decrease in removal of lead ions [44]

5.5.4. Effect of initial metal ion concentration

The effect of initial metal ion concentration on the removal of Pb(II) ions by NCS/SAMC

bead was executed by varying the metal ion concentration from 62.5 mg/L to 1000 mg/L and the

observed results was represented in Fig.9.

<Insert Fig.9>

From Fig.9, it is clear that the percentage removal of each ions increases with decreasing

the initial metal ion concentration. At lower metal ion concentration, due to the availability of

more number of vacant active sites, the metal ions would interact with the binding sites

effectively and thus facilitated almost higher amount of adsorption[45] whereas at higher

concentrations, the active sites of biosorbents are less available when compared to metal ions,

hence more number of metal ions are left unadsorbed in the solution due to the saturation of the

14
binding sites and hence metal ion removal is reduced [46].The percentage removal of Pb (II) has

been found to be higher at lower metal ion concentration, a maximum lead removal of 94.48 %

has been obtained for NCS/SA/MC bead and this obtained result reveals that NCS/SA/MC bead

act as very good adsorbents even at low metal ion concentration.

5.5.5. Effect of temperature

The effect of temperature on the adsorption of Pb (II) from aqueous solution by

NCS/SA/MC bead prepared in (2:8:1) ratio was shown in Fig.10. The adsorption studies were

conducted by varying the temperatures between 30ºC - 70ºC while keeping the other parameters

pH, adsorbent dose and metal ion concentration as constant.

<Insert Fig.10>

The observed results presented in Fig.10 indicate that the percentage of Pb(II) ion uptake

increases with increase in temperature (from 30ºC-50ºC) but thereafter it shows a decrease. The

initial increase with increase in temperature could be attributed to the increased mobility of metal

ions which lead to accelerate the opportunity of their mutual collisions. This will result in the

increased metal ion removal percentage and adsorption efficiency [47]. But when the

temperature is exceeded above 50ºC the decrease in adsorption was observed and this might be

due to the weakening of the binding forces existing between metal cations and active sites

present on the biomass surface [48] and the loss of active sites [49]. In other words we can say

that at higher temperature the desorption rate on the surface accelerate which leads to the

increased tendency of the metal ion to escape from the biomass surface to the solution phase and

hence the decrease in adsorption was obtained [50].

15
 5.6. Adsorption isotherm models

Adsorption isotherm models were mainly used to describe the distribution of adsorbate

molecules between the liquid and the solid phase on the adsorbent surface at equilibrium. In the

present work, the four adsorption isotherms namely Langmuir, Freundlich, Temkin and Dubinin

Radushkevich models were used to correlate the experimental equilibrium adsorption data [51].

5.6.1. Langmuir isotherm model

The Langmuir equation relates the coverage of molecules on a solid surface to

concentration of a medium above the solid surface at a fixed temperature [52]. The linearised

form of Langmuir equation is expressed as follows (Eq. 1):

Ceq/Cads = bCeq/KL + 1/KL ------(1)

where Cads is the amount of metal ion adsorbed (mg/g) ; Ceq is equilibrium concentration

of metal ion in solution (mg/dm3) ; KL is the Langmuir constant (dm3/g) ; b is Langmuir constant

(dm3/mg).The maximum amount of metal ion to adsorb onto 1g of adsorbent (Cmax) was

calculated using the equation given below (Eq.2).

Cmax = KL/b ------(2)

The Langmuir constants KL, b and C max which were determined from the slope and

intercept of the linear plot of Ceq/Cads Vs. Ceq. The separation factor (RL), a dimensionless

constant was mainly used to describe the essential characteristics of Langmuir isotherm [53]

which was defined by Eq.3

R = 1 / 1+bCf ------(3)

where b is the Langmuir constant and Cf is the final concentration of metal ion. The Langmuir

adsorption isotherm plot for Pb(II) ions onto NCS/SA/MC bead was represented in Fig.11. The

16
langmuir adsorption isotherm plot of Ceq/Cads Vs. Ceq produces a straight line confirming the

applicability of the Langmuir adsorption isotherm.

<Insert Fig.11>

The Langmuir constants KL , b and C max which were determined from the slope and

intercept of the linear plot of Ceq/Cads Vs. Ceq was represented in Table 2. From the calculated

higher Cmax values presented in Table 2 it was identified that the prepared NCS/SA/MC bead has

more potential to remove Pb(II) from aqueous solution. The separation factor, RL indicates the

shape of the Langmuir isotherm. The calculated values of the separation factor (R L) were shown

in Table 3.

<Insert Table 2> <Insert Table 3>

Based on higher RL values, it was evident that the Langmuir isotherm is irreversible when

RL= 0, favourable when 0<RL<1 and linear when RL=1 while RL>1 indicates unfavourable. In

the present study, since the calculated values of RL (Table 3) was found to be greater than 0 and

less than 1 (0<RL<1) and hence it was concluded that the adsorption of Pb(II) onto NCS/SA/MC

bead was considered to be highly favorable and the adsorption process would be spontaneous.

5.6.2. Freundlich isotherm model

The Freundlich adsorption isotherm equation relates the concentration of a solute on the

surface of an adsorbent to the concentration of the solute in the liquid with which it is in contact

[54]. The linearised form of Freundlich equation was shown below (Eq.4):

log qe = log KF + 1/n log Ce ------(4)

where qe is the amount of Pb(II) ion adsorbed per unit weight of adsorbent at equilibrium

(mg/g); Ce is the equilibrium conc of adsorbate in solution after adsorption (mg/L);

KF is the freundlich constant related to adsorption capacity (mg/g) and 1/n is the Freundlich

17
exponent heterogeneity coefficient (dimensionless). A plot of log qe versus log Ce enables the

constant KF and exponent 1/n to be determined. The Freundlich adsorption isotherm plot of lead

(II) onto NCS/SA/MC bead and the calculated freundlich constants (Kf and n) from the slope and

intercept of plot of of loq qe against log Ce was represented in Fig.12 and Table 4.

<Insert Fig.12> <Insert Table 4>

The value of n of this model falling in the range of 1– 10 indicates favorable biosorption.

From the Table 4, it is evident that the value of n of this model falling in the range of 1-10 and

the hence the calculated results indicate that the adsorption of metal ions onto both NCS/SA/MC

bead biosorbents was found to be highly favourable suggesting multilayer phenomenon.

5.6.3. Temkin Model

The Temkin isotherm is usually used for heterogeneous surface energy systems [55].

Temkin and Pyzhev considered the effects of some indirect sorbent/adsorbate interactions on

adsorption isotherms. This isotherm assumes that the adsorption process to be characterized by a

uniform distribution of binding energies up to some maximum energy and that the heat of

adsorption of all the molecules in the layer would decrease linearly due to these interactions[56].

The Temkin isotherm has been used in the following form (Eq.5)

qe = BT ln AT +BT ln Ce ------(5)

where, BT = RT/bT; R is Universal gas constant (8.314 J/K/mol); T is the absolute

temperature (K); bT is the Temkin constant related to heat of sorption (kJ/mol); qe is the amount

of metal ion adsorbed per unit wt of adsorbent at equilibrium (mg/g); AT is the Temkin isotherm

equilibrium binding constant (L/g) representing adsorbent- adsorbate interactions and Ce is the

equilibrium concentration of adsorbate in solution after adsorption (mg/L). The Temkin isotherm

constants of the adsorbent were calculated from the slope and intercept of the linear plot of qe Vs

18
lnCe (Fig.13). The calculated values of Temkin constants and the R2 from the slope and intercept

of the linear plot of qe vs lnCe were represented in Table 5.

<Insert Fig.13> <Insert Table 5>

The values of R2 lying between 0 and 1 confirm the favorable conditions for adsorption.

The Temkin adsorption parameters presented in Table 5 show that the variation in adsorption

energy, bT, was positive characteristic of an endothermic interaction between sorbate and

sorbent. According to Atkins [57], the enthalpy of physisorption gives typical values in the

region of less than 20kJ /mol whereas the enthalpy of chemisorption is in the range of around

200kJ/mol. Based on the values reported by Atkins, from the above calculated bT values

presented in Table 5 (around 200 kJ/mol) it was concluded that the chemisorption process takes

place more effectively to a great extent in case of NCS/SA/MC bead when compared to

physisorption process.

5.6.4. Dubinin–Radushkevich (D-R) Model

The Dubinin-Radushkevich (D-R) model was applied to the equilibrium data to assess the nature

of the adsorption process, i.e. whether it is physical or chemical adsorption [58]. This isotherm

assumes that the characteristics of the sorption curve are related to the porosity of the

biosorbents. The linearised form of the D-R isotherm equation was represented in Eq.6

ln(qe) = ln(qm) − β² ------(6)

where qe is the amount of metal ion adsorbed per unit weight of adsorbent (mg/g); qm is

the theoretical isotherm saturation (maximum sorption) capacity (mg/g); β is the Dubinin–

Radushkevich isotherm constant (mol2/kJ2) which is the activity coefficient related to sorption

energy and ε is Polanyi potential related to the equilibrium concentration. The Polanyi potential

[59] can be calculated using the following equation (Eq.7)

19
 1
𝜀 = RT ln(1 + ) ------(7)
Ce

where R is the universal gas constant (8.314 J/K/mol), T is the temperature (K) and Ce is

the equilibrium concentration of adsorbate in solution after adsorption (mg/L). The saturation

limit qm may represent the total specific microspore volume of the sorbent. The sorption potential

is independent of the temperature but varies according to the nature of sorbent and sorbate.

The β gives the mean free energy (E) of sorption per molecule of the sorbate when it is

transferred to the surface of the solid from infinity in the solution. The mean adsorption energy,

E (kJ/mol) is calculated with the help of following equation (Eq.8)

1
𝐸 = √2𝛽 ------(8)

Fig.14 represents the D-R adsorption isotherm plot for removal of lead (II) ion by

adsorption onto NCS/SA/CMC bead respectively. The D-R isotherm parameters (qm, β and E)

calculated from the slope and intercept of the plot of lnqe versus ε2 was summarized in Table 6 .

<Insert Fig.14> <Insert Table 6>

The mean adsorption energy E (kJ/mol) value gives information about the physical or

chemical nature of the adsorption mechanism. It tells whether sorption occurs through

physiosorption, ion exchange or chemisorption process. The mean adsorption energy value

below 8kJ/mol shows a physiosorption process; that between 8kJ/mol and 16kJ/mol indicates ion

exchange mechanism, while that above 16kJ/mol indicates a chemisorption process [60]. From

Table 6, it is evident that since the calculated values of mean adsorption energy were found to be

greater than16 kJ/mol, it suggests that the adsorption process involved in the present study is the

chemisorption process.

20
 The comparison of R2 values of all the isotherms presented in Table 2,4,5 and 6 reveals

that the R2 values of the Freundlich isotherm was found to be higher than the R2 values for the

other isotherms. From the observed results, it was concluded that the experimental value is better

fitted with the Freundlich adsorption isotherm model and hence it was evident that the adsorption

of lead ions onto NCS/SA/MC bead follows multilayer adsorption.

5.7. Adsorption kinetics

In order to understand the interactions between the targeted Pb (II) and the NCS/SA/MC

bead as adsorbents, the adsorption rates, rate constants, dynamics of adsorption and reaction

mechanisms [61] the Lagregen pseudo first order and Lagregen pseudo second order models [62]

are fitted to study the kinetics by analyzing adsorptive uptake of heavy metals from the aqueous

solution at different time intervals.

5.7.1. Pseudo-first-order and Pseudo-second-order kinetic models

A linearised form of Lagregen pseudo-first-order model was expressed in the form

(Eq.9):

log (qe-qt) = log qe - k1t / 2.303 ------(9)

where qe and qt are the amounts of metal adsorbed (mg/g) at equilibrium and at time t

(min) and k1 (min-1) is the adsorption rate constant of pseudo-first-order adsorption respectively.

From the linear plot of log (qe− qt) versus t, values of k1and qe were obtained from the slope and

intercept respectively.

The pseudo-second-order rate equation can be represented as follows (Eq.10)

t 1 t
---- = ------- + -----
qt k2qe2 qe ------(10)

21
 where qe and qt are the amounts of metal adsorbed (mg/g) at equilibrium and at time t

(min), and k2 (g mg-1 min-1) are the adsorption rate constant of pseudo second order adsorption

rate, respectively. The values of qe and k2 were obtained from the slope and intercept of linear

plot of t/qt versus t for pseudo second order kinetic model.

The plots of pseudo first order and pseudo second order kinetic models obtained for

removal of lead (II) ions by NCS/SA/MC bead was represented in Fig.15 and Fig.16. Respective

parameters and correlation coefficients derived from pseudo first order plot (log qe-qt vs t) and

pseudo second order plot (t/qt vs t) was summarized in Table 7.

<Insert Fig.15> <Insert Fig.16> <Insert Table 7 >

The results presented in the Fig.15, Fig.16 and Table 7 reveals that the data was found to

fit well to pseudo second order kinetic model. The applicability of pseudo second order kinetic

model to the experimental data obtained for NCS/SA/MC bead was supported by higher

correlation coefficients. The correlation coefficients obtained were close to one (R2 >0.98) for

Pb(II) adsorption onto NCS/SA/MC bead and in addition the theoretical loading capacity (qe)

values derived from plots was also very close to calculated experimental values (qe) obtained

from kinetic experiments. These observations suggest that the adsorption of lead(II) ions onto

NCS/SA/MC bead follows pseudo second order kinetic model.

5.8. Batch desorption Process

The reusability of the NCS/SA/MC bead was investigated by two consecutive adsorption-

desorption processes. The effects of the number of cycles on the Pb (II) ions adsorption and

desorption capacity was shown in Fig.17 and Table 8.

<Insert Table 8> < Insert Fig.17>

22
 In order to establish the reusability of NCS/SA/MC bead, sequential adsorption-

desorption cycles were repeated twice on the same matrix. The percentage removal of Pb(II) was

found to be 97.38% in first adsorption cycle whereas the recycled biopolymer shows a

readsorption capacity (Pb(II)) of around 93.07% at the end of 2nd adsorption-desorption cycle.

The observed loss of sorption performance during the long-term use might be due to the

blockage of some active sites and by changes in the chemistry and the structure of the

biosorbents [63]. The obtained results from the desorption experiments indicate that the

desorption of Pb (II) ion is in the range of 75.10 % in case of bead with a contact time of 30 min

during the first cycle of adsorption- desorption process. During the second cycle of adsorption-

desorption process, desorption of Pb (II) varied 75.10 % to 65.10%. The release of metal ions

from the biopolymer active sites by acid suggests an ion-exchange mechanism [64]. The above

findings suggest that the adsorption and desorption behaviour of NCS/SA/MC bead remained at

a relatively high level after two cycles and hence the NCS/SA/MC bead could be recycled if used

to remove Pb (II) ions from polluted wastewater. Regeneration aspect of NCS/SA/MC bead

affirms its cost effectiveness, as the biopolymer can be recycled for multiple reuses.

6. Conclusion

The NCS/SA/MC bead was employed as adsorbent for the removal of Pb(II) from

aqueous solution by batch process. The FTIR spectra of NCS/SA/MC bead taken before and

after Pb(II) adsorption revealed that the OH, NH2 and COO- functional groups are abundantly

present and these groups are known to bind Pb(II) from aqueous solution. Elemental analysis of

metal loaded NCS/SA/MC bead confirms the involvement of ion exchange mechanism for

removal of Pb(II) ions and in addition the EDX signals due to Pb(II) in case of metal loaded

sample confirms the adsorption of Pb(II)ions. By batch adsorption studies, from the observed

23
results of effect of various parameters, the optimum conditions for adsorption were found to be

given as follows: pH:6; adsorbent dose:4g, contact time: 240 min, initial metal ion

concentration:62.6 mg/L and temperature: 50°C. The equilibrium data obtained for Pb(II) ions

by NCS/SA/MC bead were observed to fit well to Freundlich isotherm suggesting multilayer

adsorption of Pb(II) ions onto surface and the kinetic data was observed to fit well with pseudo

second order kinetic model. Desorption and regeneration studies indicate that NCS/SA/MC bead

(2:8:1) can be used efficiently for two cycles without any significant decrease in loading

capacity. The overall results conclude that NCS/SA/MC bead prepared in 2:8:1 ratio can be used

as a potential adsorbent for the removal of heavy metals from industrial effluent with expected

success.

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Figure Captions:

Figure-1: DLS studies of nanochitosan

Figure-2: Scanning electron micrograph (SEM) details of nanochitosan
Figure-3(a): FTIR spectra of NCS/SA/MC (2:8:1) bead (a) before Pb(II) adsorption and (b)
after Pb(II) adsorption

Figure-4(a): SEM micrograph and EDX spectra of NCS/SA/MC bead (a) before Pb (II)
adsorption and (b) after Pb (II) adsorption

Figure-5: Proposed mechanism of binding of Pb(II) onto NCS/SA/MC bead

Figure-6: Effect of solution pH
Figure-7: Effect of adsorbent dose
Figure-8: Effect of contact time
Figure-9: Effect of initial metal ion concentration
Figure-10: Effect of temperature
Figure-11: Langmuir adsorption isotherm plot for Pb(II) onto NCS/SA/MC bead
Figure-12: Freundlich adsorption isotherm plot for Pb(II) onto NCs/SA/MC bead
Figure-13: Temkin adsorption isotherm plot for Pb(II) onto NCS/SA/MC bead
Figure-14: Dubinin-Radushkevich(D-R) adsorption isotherm plot for Pb(II) onto
NCS/SA/MC bead
Figure-15: Pseudo first order kinetic plot for Pb(II) onto NCS/SA/MC bead
Figure-16: Pseudo second order kinetic plot for Pb(II) onto NCS/SA/MC bead
Figure-17: Adsorption process and desorption process by NCS/SA/MC bead after two
cycles

33
Figure-1

34
Figure-2

35
Figure-3

36
Figure-4

37
Figure-5

38
 100
% R e m o v a l o f P b ( II)

95

90

85

80

75
2 4 6 8 10
pH

Figure-6

39
 100
% R e m o v a l o f P b ( II )

95

90

85
0 2 4 6 8
A d s o r b e n t d o s e (g )

Figure-7

40
 100
% R e m o v a l o f P b (II)

95

90

85

80
0 100 200 300 400
T im e in m in u t e s

Figure-8

41
 100
% R e m o v a l o f P b ( II)

95

90

85

80

75
0 500 1000 1500
M e t a l io n c o n c e n t r a t io n ( m g /L )

Figure-9

42
 100
% R e m o v a l o f P b ( II)

95

90

85
20 40 60 80

T e m p e ra tu re ( C )

Figure-10

43
 3
C e q / C a d s ( g /d m )
3

0
0 50 100 150 200 250
3
C e q (m g /d m )

Figure-11

44
 2 .5

2 .0

1 .5
lo g q e

1 .0

0 .5

0 .0
0 .5 1 .0 1 .5 2 .0 2 .5
lo g C e

Figure-12

45
 100

80

60
qe

40

20

0
2 3 4 5 6
-2 0 ln C e

Figure-13

46
 5

3
ln q e

0
0 100000 200000 300000 400000 500000
2


Figure-14

47
 1.5

1.0
log(qe -qt)

0.5

0.0
100 200 300 400
-0.5
Time in minutes
-1.0
Figure-15

48
 2.5

2.0
t/qt (min g mg-1)

1.5

1.0

0.5

0.0
0 100 200 300 400
Time in minutes

Figure-16

49
Figure – 17

50
Table-1: Comparison of FT-IR spectral details of NCS/SA/MC bead (2:8:1) before and
after metal ion (Pb(II)) adsorption
Sample OH NH3+ C=O NH def C-N P-O-H Metal
stretch stretch stretch (cm-1) stretch bend ligand
-1
(cm ) -1 -1
(cm ) -1 -1 stretch
(cm ) (cm ) (cm )
(cm-1)
NCS/SA/MC 3424.96 2376.82 1630.49 1512.57 1338.23 1124.55 -
bead
NCS/SA/MC 3375.43 2111.20 1612.49 1512.51 1338.21 1031.92 443.23
bead+ Pb(II)

Table-2: Langmuir constants for Pb(II) removal by NCS/SA/MC bead

Metal ion Langmuir constants

KL (dm3/g) b (dm3/mg) Cmax (mg/g) R2
Pb(II) 1.2967 0.01133 114.47 0.9613

Table-3: Calculated RL values

Metal ion Initial concentration Final concentration RL value

(Ci) (mg/L) (Cf) (mg/L)
Pb(II) 1000 196.26 0.3102
750 110.04 0.4451
500 62.28 0.5863
250 25.79 0.7739
125 10.02 0.8980
62.5 3.45 0.9624

Table-4: Freundlich constants for Pb(II) removal by NCS/SA/MC bead

Freundlich constant
Metal ion
Kf n R2
Pb(II) 2.5586 1.4916 0.9962

Table-5: Temkin constants for Pb(II) removal by NCS/SA/MC bead

Temkin constants
51
 Metal ion AT (L/g) BT bT (KJ/mol) R2
Pb(II) 0.2313 18.81 131.72 0.9171

Table – 6: Dubinin–Radushkevich (D-R) constants for Pb(II) removal by NCS/SA/MC

bead
Metal ion DR constants
β (mol2/J2) qm(mg/g) E (kJ/mol) R2
Pb (II) 5.126 X 10-6 39.331 312.32 0.6288

Table-7: Pseudo first order and pseudo second order kinetic rate constants

Sample Pseudo-first-order kinetic Exp Pseudo-second-order kinetic

model value model
qe k1(min-1) R2 qe qe k2 (g mg- R2
(mg/g) (mg/g) (mg/g) 1 min-1)

NCS/SA/MC
45.81 0.0186 0.9569 188.96 192.16 0.00096 0.9999
bead - Pb(II)

Table – 8: Adsorption-desorption processs- two consecutive cycles

Metal ion Cycles % Adsorption % Desorption

Pb(II) I 97.38 75.10
II 93.07 65.10

52

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