Accepted Manuscript

Title: One pot synthesis of chitosan grafted quaternized resin

for the removal of nitrate and phosphate from aqueous solution

Authors: H. Thagira Banu, Sankaran Meenakshi

PII: S0141-8130(16)32711-8
DOI: http://dx.doi.org/doi:10.1016/j.ijbiomac.2017.03.043
Reference: BIOMAC 7209

To appear in: International Journal of Biological Macromolecules

Received date: 30-11-2016

Revised date: 24-2-2017
Accepted date: 8-3-2017

Please cite this article as: H.Thagira Banu, Sankaran Meenakshi, One pot
synthesis of chitosan grafted quaternized resin for the removal of nitrate and
phosphate from aqueous solution, International Journal of Biological Macromolecules
http://dx.doi.org/10.1016/j.ijbiomac.2017.03.043

This is a PDF file of an unedited manuscript that has been accepted for publication.
As a service to our customers we are providing this early version of the manuscript.
The manuscript will undergo copyediting, typesetting, and review of the resulting proof
before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that
apply to the journal pertain.
One pot synthesis of chitosan grafted quaternized resin for the removal of nitrate and

phosphate from aqueous solution

H. Thagira Banu and Sankaran Meenakshi*

Department of Chemistry, The Gandhigram Rural Institute - Deemed University

Gandhigram – 624 302, Dindigul, Tamil Nadu, India

*Corresponding author. Tel.: +91-451-2452371; Fax: +91-451-2454466.

E-mail address: sankaranmeenakshi2014@gmail.com

Highlights
 Maximum adsorption capacity of chitosan quaternized resin was obtained. It
is a promising adsorbent to remove both nitrate and phosphate.
 Adsorption was carried out with solution pH for both the ions.
 Mechanism involved in this process is ion exchange as well as hydrogen
bonding.
 Chitosan quaternized resin was regenerated using 0.1 M NaCl upto 7th
regeneration cycle with small drop in adsorption capacity.

Abstract

The present study deals with the synthesis of chitosan quaternized resin for efficient

removal of nitrate and phosphate from aqueous solution. The resin was characterized with FTIR,

SEM with EDX and XRD. Batch method was carried out to optimize various parameters such as

contact time, initial concentration of nitrate and phosphate, dosage, pH, co-anions and

temperature on the adsorption capacity of the adsorbent. The adsorption process illustrated that

the Freundlich isotherm and the pseudo-second order are the best fitted models for the sorption

of both anions. The respective negative values of ∆H° and ∆G° revealed that the adsorption of

both the anions were exothermic and spontaneous. The removal efficiency of nitrate and

phosphate on chitosan quaternized resin were 78% and 90% respectively with 0.1g of adsorbent

and the initial concentration as 100 mg/L. Nitrate and phosphate anions adsorbed effectively on

chitosan quaternized resin by replacing Cl− ions from quaternary site through electrostatic

attraction as well as ion-exchange mechanism. Hydrogen bonding also played important role in
adsorption process. Even after 7th regeneration cycle the adsorbent retained its adsorption

capacity as 23.7 mg/g and 30.4 mg/g for both nitrate and phosphate respectively.

Keywords: Nitrate; Phosphate; Quaternized Resin; Adsorption; Isotherm.

1. Introduction

Nitrate and phosphate are the two major nutrients for plant growth. However water

pollution by nitrate and phosphate anions creates serious environmental problems. The main

sources of such anions are due to excessive usage of fertilizers in agricultural fields and

untreated disposal of industrial and municipal wastes. High nitrate and phosphate concentration

in water could root eutrophication [1] which disturbs the ecological balance of organisms present

in water. Nitrate is also hazardous to infants which creates methemoglobinemia i.e. blue baby

syndrome where nitrite ions oxidizes the ferrous in hemoglobin to ferric ions and binding of

oxygen in hemoglobin is not possible which directs to the effect known as methemoglobinemia

[2] and also formation of nitrosamine and nitrosamide possesses carcinogenic diseases [3]. As

stated by WHO the accepted level of drinking water of nitrate concentration is 40 mg/L [4] and

for phosphate it is about 0.1 mg/L [5]. When compared with phosphate, it’s a difficult task to

remove nitrate from water because of its high solubility and very weak adsorption ability [6] thus

removal of nitrate is a challenging problem.

To overcome those complications, there are several biological and physicochemical

processes have been investigated to remove such dissolved pollutants in water. Among several

methods, adsorption method shows to be potential due to its simplicity, cost effectiveness, less
sludge production and easy operation [7]. Various adsorbents have been investigated to remove

nitrate and phosphate from water, such as activated carbon [8], agricultural wastes [9], ion

exchange resins [10], zeolites [11], layered double hydroxides [12], cellulose [13] etc.,

The main objective of this study is to produce the sorbent using chitosan which is a bio-

sorbent has the properties of hydrophilicity, non-toxicity, biodegradability, easy availability, less

cost etc., obtained by deacetylation of bio-polymer chitin. The adsorption capacity of chitosan is

due to presence of bi-functional groups like amine and hydroxyl which undergo chemical

modifications such as metal chelation, protonation, acylation, carboxyalkylation, Schiff base

formation etc., Thus modified chitosan is used for several applications in the field of water

treatment, drugs, foods, cosmetics, gene technology, gel implants etc., The present work

discussed the removal of nitrate and phosphate ions from aqueous solution using chitosan

grafted quaternized resin. The synthesized sorbent was characterized by using FTIR, XRD and

SEM with EDX techniques. To study the nature of adsorption process, sorption isotherms

studies, thermodynamic parameters such as ∆Gº, ∆Hº and ∆Sº were determined. Reaction and

diffusion-based kinetic models were also discussed.

2. Materials and methods

2.1. Chemicals

85% deacetylated commercial chitosan was purchased. Potassium dihydrogen phosphate

(99.5 %), potassium nitrate (98 %), ammonium molybdate (98 %), ammonium-m-vanadate

(99 %), sodium hydroxide (98 %), concentrated hydrochloric acid (35.4 %), glacial acetic acid

(98.5 %), formaldehyde (37 %), epichlorohydrin (98 %), N,N-dimethylformamide (99.5 %),

ethylenediamine (90.5 %) and triethylamine (99 %) were supplied by Merck. All the reagents and

chemicals purchased were of analytical grade. The required concentrations of nitrate and
phosphate solutions were obtained from respective 1000 mg/L nitrate and phosphate standard

solution.

2.2. Synthesis of chitosan quaternized resin

About 10 g of powdered chitosan taken in a three necked flask followed by adding 20 mL

of epichlorohydrin and 12 mL of N,N-dimethylformamide to react with chitosan. The reactants

were stirred at 70 C for 1h. About 6 mL of ethylenediamine was added slowly and the mixture

was stirred for 10 min at 70 C, followed by adding 18 mL of triethylamine for grafting and

stirred continuously for about 2 h. The amine grafted chitosan was washed with distilled water

till the unreacted chemicals were removed and the chitosan quaternized resin was dried at 60 C

for 12 h.

2.3. Adsorbent characterization

FTIR spectra of chitosan quaternized resin before and after adsorption of both nitrate and

phosphate were sketched by JASCO-460 plus model using KBr pellet method. Surface

morphology were recorded using scanning electron microscopy (SEM) and the elements present

in CsQ were examined by energy dispersive X-Ray spectroscopy (EDX) using Vega3 Tescan

fitted with Bruker Nano GmbH, Germany. The crystalline nature of sorbent was determined by

X-ray powder diffraction method (XRD, X’per PRO model-PANalytical make). Nitrate and

phosphate were analyzed using UV/vis Spectrophotometer (Spectroquant Pharo 300, Merck) and

the pH adjustments were carried out by using Expandable Ion Analyzer (Orion EA940, USA).

2.4. Measurement of pH at zero point of charge (pHzpc)

The pHzpc (pH of zero point charge) was determined by pH drift method in order to

examine the surface charge of the adsorbent [14]. The pH of background electrolyte was adjusted

between 2 and 12 by addition of 0.01 M HCl/NaOH. About 0.15 g of the adsorbent was added to
50 mL of 0.01M NaCl solution. After stabilizing the pH, the final pH was recorded after 24 hrs

of reaction. The graphs of initial pH versus final pH was plotted to find out the points at which

initial pH and final pH were equal.

2.5. Adsorption experiments

Adsorption experiments were carried out with 50 mL of analyte solutions (100 mg/L) and

0.1 g of sorbent was taken in a stopper conical flask at ambient temperature in mechanical shaker

at 120 rpm for a particular time followed by filtration. After adsorption, the concentration of the

supernatant solution of nitrate was analyzed by ultraviolet spectrophotometric method at a

wavelength of 202 nm and phosphate by vanadomolybdophosphoric acid method analyzed at a

wavelength of 400 nm [15] using UV/vis Spectrophotometer. The concentrations of the analyte

solutions were varied between 50- 400 mg/L to study the effect of initial concentration. Contact

times were set as 60 and 45 min for nitrate and phosphate respectively after optimization. Effects

of dosage were examined by varying the dose between 0.025-0.15 g of resin. To observe the pH

effect, adsorption studies were carried out by altering the pH from 2 to 12 using 0.01 M

HCl/NaOH. Sorbent was regenerated using 0.1 M NaCl for both anayltes upto 7th generation.

Isotherms studies were studied using various concentrations at 303, 313 and 323 K. The amount

of analyte adsorbed by sorbent, qe, was calculated by Eq. (1) and the removal percentage by Eq.

(2).

(C i  Ce )
Adsorptioncapacity, q e  V mg/ g (1)
m

C i  Ce
Percentage anion removal  ( )100 (2)
Ci

Where V-volume of adsorbate solution (L)

Ci -initial concentration of the adsorbate solution (mg/L)

 Ce- equilibrium concentration of adsorbate solution (mg/L)

m- mass of the adsorbent (g)

2.6. Statistical tools

Computations were made using Microcal Origin (Version 8.0) software. The significance

of data and goodness of fit were discussed using coefficient of determination (r2) and chi-square

(χ2) analysis.

3. Results and discussion

3.1. Physicochemical characterization of chitosan quaternized resin

3.1.1. FTIR spectra

The FTIR spectra of (A) chitosan, (B) quaternized chitosan, (C) nitrate and (D) phosphate

adsorbed chitosan quaternized resin are shown in Fig. 1. The peaks assigned for raw chitosan are

as follows: broad band at 3432 cm−1 was due to stretching vibrations of -OH and NH2 groups

and the peaks at 2926 and 2856 cm−1 were assigned to asymmetric and symmetric C–H

stretching vibration of -CH2 respectively [16]. Bending vibration of -NH2 group found at 1633

cm−1 and C=O stretching vibration in -CONH is attributed at 1036 cm−1 and -CH bending

vibrations in -CHOH group was indicated at 1317 cm−1 respectively.

After quaternization appearance of new peak at 1461 cm−1 was due asymmetry angular

bending of alkyl group of quaternary nitrogen [17]. Strong band at 493 cm−1 due to special

vibration of C-Cl group which was gained from the grafted chemical reagent of epichlorohydrin

further confirmed the formation of the long carbon segment of the quaternary ammonium salt

[18]. In nitrate adsorbed resin, a new sharp peak at 1382 cm−1 [19] was appeared due to N-O

stretching frequency of nitrate ions and in phosphate adsorbed resin, the broadening of band at

1070 cm−1 which is the characteristic peaks of phosphate ions [20] confirmed the phosphate
adsorption and the C–Cl bond after adsorption of nitrate and phosphate ions were diminished

further proved that these two ions were removed by electrostatic attraction as well as ion

exchange mechanism.

3.1.2. XRD pattern

X-ray diffraction patterns of (A) chitosan quaternized resin, (B) nitrate and (C) phosphate

adsorbed chitosan quaternized resin are represented in Fig .2. Chitosan showed characteristic

peaks of 2θ at 10.1◦, 20.3◦, 26.0◦ and 42.0◦. These peaks correspond to a crystalline nature of

chitosan as reported by K. Ogawa et al [21]. After quaternization the shift in 2θ values at 10.26 ◦,

20.39◦, 29.26◦ and 43.94◦ were observed. Compared with chitosan quaternized resin, the intensity

of nitrate and phosphate adsorbed resin were reduced at 29.26◦. Only significant variations was

found for nitrate adsorbed resin emphasized that the crystallinity of the resin became semi

crystalline whereas for phosphate adsorbed resin, the peak at 10.26◦ was weaken and peak

broadening with reduced intensity at 20.3◦ indicated that after adsorption with phosphate, the

crystalline nature of resin was lost and thus phosphate adsorbed resin as amorphous nature as

reported by Liping Sun et al in quaternization of carboxymethyl chitosan [22].

3.1.3. Surface morphology and elemental analysis

The SEM images of (A) chitosan quaternized resin, (B) nitrate and (C) phosphate

adsorbed resin are shown in Fig.3.The average particle size of chitosan quaternized resin was

found to be 1.6 µm. Heterogeneous surface with pits and pores of resin was covered with pebble

like structures after adsorption with nitrate ions whereas the adsorption of phosphate ions onto

the resin was roofed with tetrahedral like structure indicated that nitrate and phosphate ions were

adsorbed onto the resin. Further study on EDX also explained adsorption of nitrate and
phosphate on adsorbent with replacement of chloride ion indicated by decrease in weight

percentage from 7.91 % to 6.04 % in case of nitrate adsorption and 2.13 % in case of phosphate

adsorption when compared to chitosan quaternized resin. Presence of phosphorous (2.03 %) and

increase in nitrogen element weight percentage (16.16 %) revealed that nitrate and phosphate

were adsorbed onto the resin was shown in Fig.4.

3.2. Studies on various parameters

Variation in adsorption capacity with contact time of the analytes towards chitosan

quaternized resin was examined at ambient temperature and it is represented in Fig.5 using 100

mg/L of nitrate and phosphate initial concentration by varying time between 10-80 min for

nitrate, 5-60 min for phosphate. Adsorption capacity increased with increased in contact time and

attained saturation at 60 min and 45 min for nitrate and phosphate respectively and the maximum

adsorption capacity were 34.5 and 49.4 mg/g respectively. Studies on various initial

concentrations ranging from 50 to 400 mg/L were carried out with fixed contact time for both the

analytes with a constant dosage of 0.1 g and the result is illustrated in Fig.6. Adsorption capacity

increased with increased in concentration. This might be due to increase in the driving force

obtained by the concentration gradient of analytes between the bulk solution and solid phases

[23]. Studies on dosages were carried out by varying 0.025 -0.150 g as reported in Fig.7. As the

dose of adsorbent increased the availability of sorption surface sites also increased which made

more ions to attract towards the sorbent [24] and there by its corresponding removal percentage

was found to be increased. When compared with nitrate the removal capacity of phosphate was

gradually increased due to its polyprotic nature. Further experiments were carried out with

optimum dosage of 0.1 g.

3.2.1. Effect of solution pH

 Adsorbent-adsorbate interfaces on adsorption of anions were influenced by pH of the

solution. The effect of pH studies of both analytes were carried out by adjusting the ranges from

2 to 11 using 0.1 M HCl/NaOH solution. From the Fig.8 it was evident that sorption capacity

increased from pH 2-4 and reached a plateau with pH 4-8 for nitrate and 4-10 for phosphate and

then drastically decreased. Similar results were found for most of the bio-polymeric quaternary

sorbents where the maximum removal was observed when the adsorbent surfaces acquire

charges in the pH range of 5.0−8.0 [25]. At higher basic pH range, there might be competition

between the OH- and NO3 - ions thus the adsorption capacity was observed to be decreased in

NO3- ion adsorption. But in the case of phosphate adsorption, the adsorption capacity was based

on both the surface charge of the sorbent and also the polyprotic nature of phosphate ions. Since

phosphate as in the form of H3PO4, H2PO4−, HPO42− and PO43− respectively, at different pH

ranges of <2, 2–7, 7–12.5 and >12.5 as reported by L.A. Rodrigues et al [26]. Thus in phosphate

adsorption, the adsorption capacity increased even at higher pH was due to polyprotic nature

and the zero point charge of chitosan quaternized resin was 6.9 respectively, where below those

range the surface of the adsorbent showed the positive nature. From ZPC value, it was proved

existence of H2PO4− was higher than HPO42− ions. Similarly higher ZPC were reported by Xing

et al and Deng et al for amine grafted sorbents [27, 28].

3.2.3. Competition effects of anions

Nitrate and phosphate removal efficiency with other ions were studied with 200 mg/L of

initial concentration and 0.1g of chitosan quaternized resin. The adsorption abilities of resin for

both the analytes in the presence and absence of Cl−, HCO3− and SO42− ions are represented in

Fig.9. It was investigated that the sorption capacities of both the analytes were altered by Cl− and

much higher by SO42− which in turn the effect was less significant in the case of HCO 3−. This
was due to anionic charges, SO42− ion has more anionic charge than other ions, thus multivalent

anion with greater charge density was adsorbed more promptly than monovalent anions [29].

Effects on binary solutions emphasized that phosphate sorption capacities was found to be

greater than nitrate ions due to polyprotic nature of phosphate ions [26] and anions with higher

ionic potential have greater affinity towards the adsorbent [30].

3.2.4. Desorption and regeneration studies

The regeneration of adsorbent was carried out by leaching the adsorbate from adsorbent

by treating 0.1M NaCl solution with contact time of 30 min for both the analytes and it is

represented in Fig.10. The sorption capacities for respective nitrate and phosphate regenerated

sorbents were found to be retained to about 23.7 mg/g and 30.4 mg/g even after seven

adsorption and desorption cycle. In the 7th regeneration studies about 70% adsorption efficiency

was retained and thus chitosan quaternized resin acted as good sorbent for removing both the

analytes.

3.3. Isotherm studies

The equilibrium relationship between the ion concentration in the adsorbent / adsorbate

inter phases are illustrated by adsorption isotherm studies. The most commonly used isotherms

viz., Langmuir [31], Freundlich [32] and D–R isotherms [33] were used. The linear form of

Freundlich isotherm equations are represented as follows:

1
log qe  log k F  log Ce (3)
n

The values of kF and n were calculated using the slope and intercept values for both the anions

by plotting the linear plot of log q e vs log Ce. The values of 1/n ranging between 0 to1 and the

value of n lying between 1 to10 proved the favorable condition for adsorption. With increased in
temperature the adsorption capacity (kF) decreased indicated that the adsorption was exothermic

for both nitrate and phosphate ions.

The linear form of Langmuir equation is represented as:

Ce 1 C
 o  eo (4)
qe Q b Q

From the slope and intercept values of the plot Ce/qe vs Ce , Langmuir constants Qo and b were

calculated. In order to find the feasibility of the isotherm, the important characteristics of the

Langmuir isotherm is expressed in terms of equilibrium parameter or dimensionless constant

separation factor, RL [34] was calculated using Eq. (5) and was explained by Webber and

Chakkravorti.

1
𝑅𝐿 = (1+𝑏𝐶 ) (5)
𝑜

The values RL between 0 and 1 implied that at all the temperature studies which were carried out

indicated the favorable condition for adsorption.

Linear form of D–R isotherm equation is given as:

ln qe  ln X m  k DR  2 (6)

Slope and intercept values obtained from the plot of ln q e vs ε2, the values of kDR and Xm were

calculated. Polanyi potential () can be calculated using Eq. (7)

1
 = 𝑅𝑇𝑙𝑛 (1 + 𝐶 ) (7)
𝑒

The value of mean free energy E (kJ mol−1) of the sorption process can be obtained from the

value of k as shown in Eq. (8)

E= − (2k) −0.5 (8)

The value of E represents the type of adsorption mechanism in the adsorption process and if the

value of E lying below 8 kJ/mol indicates physisorption and above 8 kJ/mol is due to
chemisorption respectively. In order to identify the most suitable isotherms for adsorption of

nitrate and phosphate on chitosan quaternized resin, the chi-square analysis was carried out. The

mathematical expression of chi-square analysis is shown in Eq. (9)

(q e  q e,m ) 2
χ2   (9)
q e,m

The parameters of adsorption isotherms for nitrate and phosphate equilibrium studies carried out

at different temperatures are given in the Table 1. The data revealed that the value of 1/n

between 0.829 to 0.654 for nitrate and for phosphate the value between 0.851 to 0.717. RL value

between 0.151 to 0.099 for nitrate and between 0.096 to 0.219 for phosphate illustrated the

favorable condition for adsorption. The value of n ranging between 1.205 to 1.529 for nitrate and

1.173 to 1.392 for phosphate revealed that adsorption is favorable. When compared to other

isotherms, the higher r and lower Sd and 𝜒2 values indicated the applicability of the Freundlich

isotherms as the best fit. Both the anions showed the similar order as Freundlich > Langmuir >

D–R. Hence, it was concluded that adsorption of chitosan quaternized resin on nitrate and

phosphate was non-ideal adsorption on the heterogeneous surface of the adsorbent. Thus, the

adsorption mechanism undergoes multilayer adsorption mechanism and this might be due to

presence of 1о, 2о and 3о amines present in the adsorbent as reported by Aniruthan et al [30]. E

values obtained from D–R isotherm for nitrate and phosphate were 0.737and 0.912 kJ/ mol

respectively, which confirmed that the physical adsorption was possible where the values of E

was below 8 kJ/ mol [35, 36].

3.4. Thermodynamic treatment of the adsorption process

Thermodynamic parameters were calculated using Khan and Singh method [37] at three

different temperatures at 303, 313 and 323K are represented in the Table 2. Parameters such as
standard free energy change (∆Gº), standard enthalpy change (∆Hº) and standard entropy change

(∆S°) were determined using the Van’t Hoff equations (Eq. 10 and 11).

(10)
Go   RT ln Ko

S o H o
ln K o   (11)
R RT

The values of ∆H° and ∆S° can be obtained from the slope and intercept of a plot of ln K o

against 1/T. From the calculated values it was stated that the negative ∆G° values of nitrate and

phosphate at different temperatures discussed the spontaneous nature of adsorption. ∆G° values

confirmed the effective interaction between adsorbate and adsorbent and from the values ∆G°

(-20< ∆G°<0 kJ/mol) it was proved that the adsorption was spontaneous and physical adsorption

process [38] and the positive value of ∆S° suggested the enhanced randomness at the adsorbent–

adsorbate interface during the adsorption of both the anions on chitosan quaternized resin.

Further the negative value of ∆H° confirmed the nature of adsorption to be exothermic for both

the ions.

3.5. Kinetics

3.5.1. Reaction-based models

To study the adsorption mechanism of both nitrate and phosphate ions removal, the

pseudo-first-order and the pseudo-second-order kinetic models have been carried out at different

experimental conditions. The values of q and qt in Lagergren pseudo-first-order [39] rate

expression is represented as

Kad
log(qe − qt) = log qe − t (12)
2.303
A linear plot of log (qe− qt) against t provides a straight line indicate the applicability of the

pseudo-first-order model. Kad and qe can be determined from the slope and intercept values. The

linear pseudo-second-order [40] form is shown as follows

t 1 t
= + (13)
qt h qe

where qt = qe2kt/(1 + qekt) is the quantity of both the adsorbate on the surface of the adsorbent at

any time, t (mg/g), k is known as rate constant of pseudo-second-order model (g/mg min), q e

stand for the amount of anions adsorbed at equilibrium (mg/g) and the initial sorption rate, h =

kqe2. In order to obtain the value of h (1/intercept), q e (1/slope) and k (slope2/intercept), the

pseudo-second-order equation can be calculated experimentally by plotting t/qt against t. The

values of kinetic parameters and their corresponding correlation coefficients and standard

deviation values are shown in Table 3. It was observed that among two reactions based models,

pseudo-second-order equation was to be best fit for both the anions where it was confirmed from

higher r and lower Sd values. Furthermore, the calculated adsorption capacities of the pseudo-

second-order model agreed with the experimentally calculated values and its corresponding

graphs at 303 K are shown in Fig. 11.

3.5.2. Diffusion-based models

The solute transfer is usually described either by intra particle diffusion or particle

diffusion [41] in solid-liquid sorption process. Equation used to study the particle diffusion

sorption process is as follows

ln (1 − Ct /Ce ) = −kpt (14)

Where kp represents the particle rate constant (1/min) and the value of particle rate constant is

calculated from the slope of ln (1 − C t/Ce) against t. The intra-particle diffusion model discussed
with the theory proposed by Weber and Morris [42]. Equation for intra-particle diffusion is as

follows,

qt = ki t1/2 (15)

where ki is the intra-particle diffusion coefficient (mg/g min0.5). Intra-particle diffusion

coefficient is obtained from the slope of the plot of qt against t1/2. Calculated values carried out

at 303K are shown in the Table 3 represented the higher r and lower Sd values for both anions

confirmed the particle diffusion model was better fitted than intra particle diffusion model and its

graphs at 303 K are shown in Fig. 12.

3.7. Mechanism of chitosan quaternized resin

The adsorption mechanism accounted that the nitrate and phosphate were removed mainly due to

electrostatic attraction between positively charged quaternized sites and negative anions followed

by ion exchange by replacing chloride ions from the matrix as reported earlier [43] and primary

amine groups of chitosan undergoes hydrogen bonding with hydrogen present in H2PO4− and

HPO42− ions. In case of nitrate adsorption there was a possibility of hydrogen bonding of nitrate

with hydroxyl groups present in side chains (NO 3 −··· HO–) as reported by Mohan et al [44]. The

results revealed that the adsorption capacity of phosphate was greater than nitrate might be due

to higher ionic potential of phosphate than nitrate as reported earlier [30]. Moreover, though the

conventional anion exchange resins which have hydrophobic character were not much effective

in removing phosphate ions from water, but binary ions studied gave evidences that phosphate

was more active than nitrate ions, this might be due to presence of primary amine groups of

chitosan, where epichlorohydrin used in preparation attacks the –OH group than –NH2 thus the

primary amino groups, which showed hydrophilic character effectively remove phosphate than

nitrate as reported by Awual et al [45]. The effective removal of nitrate and phosphate with
chitosan quaternized resin was compared with other sorbents are represented in Table 4 and the

schematic representation of chitosan quaternized resin before and after adsorption is shown in

Fig.11.

4. Conclusions

Adsorption capacity of phosphate (181.29 (mg/g)) was greater than nitrate (84.09 (mg/g))

from 100 mg/L aqueous solution using 0.1 g of adsorbent at 60 min and 45min contact time for

nitrate and phosphate. Nitrate sorption was effective in the pH ranges of 3 to 8 and phosphate of

3-10. In adsorption study of co-ions, sulfate remarkably altered the sorption capacity of both the

anions. Thermodynamic studies showed negative values of ∆H° and ∆G° revealed that the

adsorption of both the anions were exothermic and spontaneous. The positive value of ΔS°

suggested the enhanced randomness at the solid-solution interface. The adsorption isotherms and

the kinetics models data were best fitted with Freundlich adsorption and the pseudo-second-order

for both the anions which showed experimentally the higher correlation co-efficient and lower χ2

and Sd values. Calculated higher r values and lower Sd values for both anions showed particle

diffusion model was better fitted than intra particle diffusion. The adsorption mechanism was

clearly due to ion exchange as well as hydrogen bonding. Regeneration studied revealed that

even after the 7th generation about 70% efficiency was obtained thus proved that chitosan

quaternized resin acted as good and cost effective sorbent for removing both the anions.

Acknowledgement

First author is thankful to UGC-BSR, New Delhi, India, for the financial support to carry out this
research work.
References

[1] S. Hamoudi, K. Belkacemi, Adsorption of nitrate and phosphate ions from aqueous,

solutions using organically-functionalized silica materials: Kinetic modeling,

Fuel. 110 (2013) 107–113.

[2] P. Ganesan, R. Kamaraj, S. Vasudevan, Application of isotherm, kinetic and

thermodynamic models for the adsorption of nitrate ions on graphene from aqueous

solution, J. Taiwan .Inst. Chem. Eng. 44 (2013) 808–814.

[3] A. Sowmya, S. Meenakshi, Removal of nitrate and phosphate anions from aqueous

solution using strong base anion exchange resin, Desalin. Water. Treat. 51 (2013)

7145 −7156.

[4] World Health Organization (WHO), Guidelines for Drinking Water Quality, 4 thed, 2011.

[5] T. S. Anirudhan, P. Senan, Adsorption of phosphate ions from water using a novel

cellulose- based adsorbent, Chem. Ecol, 27 (2011) 147–164.

[6] P.Loganathan, S.Vigneswaran, J.Kandasamy, Enhanced removal of nitrate from water

using surface modification of adsorbents a review. J. Environ. Manag. 131 (2013)

363– 374.

[7] Y. Sangeetha, S. Meenakshi, C. Sairamsundaram, Corrosion mitigation of N -( 2-

hydroxy-3-trimethyl ammonium ) propyl chitosan chloride as inhibitor on mild steel,

Int. J. Biol. Macromol. 72 (2015) 1244–1249.

[8] R. Mahmudov, C. P. Huang, Selective adsorption of oxyanions on activated carbon

exemplified by Filtrasorb 400 (F400), Sep. Purif. Technol. 77 (2011) 294–300.

[9] M. Kalaruban, P. Loganathan, W. G. Shim, J.Kandasamy, H. H. Ngo, S. Vigneswaran,

enhanced removal of nitrate from water using amine-grafted agricultural wastes, Sci.

Total. Environ. 565 (2016) 503–510.

[10] S. N. Milmile, J.V. Pande, S. Karmakar, A. Bansiwal, T. Chakrabarti, R. B. Biniwal,

 Equilibrium isotherm and kinetic modeling of the adsorption of nitrates by anion

exchange Indion NSSR resin, Desalination, 276 (2011) 38- 44.

[11] L. Lin, C. Wan, D. Lee, Z. Lei, X. Liu, Ammonium assists orthophosphate removal from

high- strength wastewaters by natural zeolite, Sep. Purif. Technol, 133 (2014) 351–356.

[12] K. Yang, L. Yan, Y. Yang, S. Yu, R. Shan, H. Yu, Adsorptive removal of phosphate by

Mg – Al and Zn – Al layered double hydroxides : Kinetics , isotherms and mechanisms,

Sep. Purif.Technol, 124 (2014) 36–42.

[13] A.S.K. Kumar, S. Kalidhasan, V. Rajesh, N. Rajesh, Application of cellulose-clay

composite biosorbent toward the effective adsorption and removal of chromium from

industrial wastewater, Ind. Eng. Chem. Res, 51 (2012) 58–69.

[14] M.V. Lopez-Ramon, F. Stoeckli, C. Moreno-Castilla, F. Carrasco-Marin,

Characterization of acidic and basic surface sites on carbons by various techniques,

Carbon, 37 (1999) 1215-1221.

[15] APHA, Standard methods for the examination of water and waste water, 21st ed.,

APHA, Washington, DC, 2005.

[16] M.H. Farzana, S. Meenakshi, Synergistic effect of chitosan and titanium dioxide on

the removal of toxic dyes by the photodegradation technique, Ind. Eng. Chem.Res.

53 (2014) 55-63.

[17] T. Anirudhan, B. Noeline, D. Manohar, Phosphate removal from wastewaters using weak

anion exchanger prepared from a lignocellulosic residue, Environ. Sci. Technol. 40

(2006) 2740–2748.

[18] X. Wang, Y. Zhang, J. Li, G. Zhang, X. Li, Enhance Cr ( VI ) removal by quaternary

amine-anchoring activated carbons, J. Taiwan Inst. Chem. Eng, 000 (2015) 1–7.

[19] A. Sowmya, S. Meenakshi, A novel quaternized chitosan – melamine – glutaraldehyde

resin for the removal of nitrate and phosphate anions, Int. J. Biol. Macromol, 64 (2014)
 224–232.

[20] L. Ding, C. Wu, H. Deng, X. Zhang, Adsorptive characteristics of phosphate from

aqueous solutions by MIEX resin, J. Colloid. Interf. Sci, 376 (2012) 224–32.

[21] K. Ogawa, T. Yui, M. Miya, Dependence on the preparation procedure of the

polymorphism and crystallinity of chitosan membranes, Biosci. Biotech. Biochem, 56

(1992) 858–62.

[22] L. Sun, Y. Du, L. Fan, X. Chen, Y. Yang, Preparation, charactertzation and antimicrobial

activity of quaternized carboxymethyl chitosan and application as pulp-cap, Polymer, 47

(2006) 1796-1804.

[23] Q. Liu, P. Hu, J. Wang, L. Zhang, R. Huang, Phosphate adsorption from aqueous

solutions by Zirconium ( IV ) loaded cross-linked chitosan particles, J. Taiwan Inst.

Chem. Eng, 000 (2015) 1–9.

[24] R.A.K. Rao, F. Rehman, Adsorption studies on fruits of gular (Ficusglomerata) removal

of Cr(VI) from synthetic wastewater, J. Hazard. Mater, 181 (2010) 405-412.

[25] K. Chauhan, J. Kaur, P. Singh, P. Sharma, P. Sharma, G.S. Chauhan, An efficient and

regenerable quaternary starch for removal of nitrate from aqueous solutions, Ind.

Eng. Chem. Res. 55 (2016) 2507–2519.

[26] L.A. Rodrigues, M.L.C.P. Silva, Thermodynamic and kinetic investigations of

Phosphate adsorption onto hydrous niobium oxide prepared by homogeneous solution

method, Desalination 263 (2010) 29–35

[27] X. Xing, B. Gao, Q. Zhong, Q. Yue, Q. Li, Sorption of nitrate onto amine-crosslinked

wheat straw: characteristics, column sorption and desorption properties. J. Hazard.

Mater.186 (2011) 206–211.

[28] S. Deng, L. Niu, Y. Bei, B. Wang, J. Huang, G. Yu, Adsorption of per fluorinated

compounds on aminated rice husk prepared by atom transfer radical polymerization.

 Chemosphere, 91(2013) 124–130.

[29] S. Samatya, N. Kabay, U.Yuksel, M. Arda, M. Yuksel, Removal of nitrate from

aqueous solution by nitrate selective ion exchange resins. React. Funct. Polym. 66

(2006) 1206–1214.

[30] T.S. Anirudhan, T.A. Rauf, S.R. Rejeena, Removal and recovery of phosphate ions from

Aqueous solutions by amine functionalized epichlorohydrin-grafted cellulose,

Desalination. 285 (2012) 277–284.

[31] I. Langmuir, The constitution and fundamental properties of solids and liquids, J. Am.

Chem. Soc. 38 (1916) 2221–2295.

[32] H.M.F. Freundlich, Over the adsorption in solution, J. Phys. Chem. 57 (1906) 385–471.

[33] M.M. Dubinin, L.V. Radushkevich, The equation of the characteristic curve of the

Activated charcoal, Proc. Acad. Sci. USSR Phys. Chem. Sect. 55 (1947) 331–337.

[34] T.W.Webber, R.K. Chakkravorti, Pore and solid diffusion models for fixed-bed

adsorbers, AlChE J. 20 (1974) 228–238.

[35] T.E. Kosea, B. Kivanc, Adsorption of phosphate from aqueous solutions using calcined

waste eggshell, Chem. Eng. J. 178 (2011) 34-39.

[36] S. Chatterjee, D. S.Lee, M. W. Lee, S. H. Woo, Nitrate removal from aqueous

solutions by cross- linked chitosan beads conditioned with sodium bisulfate. J. Hazard.

Mater. 166 (2009) 508–513.

[37] A.A. Khan, R.P. Singh, Adsorption thermodynamics of carbofuran on Sn (IV)

arsenosilicate in H+, Na+ and Ca2+ forms, Colloids Surf. 24 (1987) 33–42.

[38] P. Sun, C. Hui, R. Azim Khan, J. Du, Q. Zhang, Y. Zhao, Efficient removal of crystal

violet using Fe3O4-coated biochar: the role of the Fe3O4 nanoparticles and modeling

study their adsorption behavior., Sci. Rep. 5 (2015) 126-138.

[39] S. Lagergren, About the theory of so-called adsorption of soluble substance, Handlingar,
 24 (1898) 1–39.

[40] Y.S. Ho, J.C.Y. Ng, G. McKay, Kinetics of pollutant sorption by biosorbents: Review.

Sep. Purif. Method. 29 (2000) 189–232.

[41] M. Chanda, K. F. Driscoll, G. L. Rempel, Sorption of phenolics onto cross-linked

poly(4- vinyl pyridine), React. Polym. 1 (1983) 281–293.

[42] W.J. Weber, J.C. Morris, Equilibria and capacities for adsorption on carbon, J. Sanitary

Eng. Div. 90 (1964) 79–91

[43] A. S. K. Kumar, S. Jiang, W. Tseng, Aqueous solution using ionic liquid functionalized

multiwalled carbon nanotubes as a super sorbent, J. Mater. Chem. A Mater. Energy

Sustain. 3 (2015) 7044 –7057.

[44] N. Mohan , K. P .Vijayalakshmi , N. Koga , C.H .Suresh, Comparison of aromatic

NH ···π, OH ···π, and CH ···π interactions of alanine using MP2, CCSD, and DFT

methods. J Comput Chem. 31 (2010) 2874–82.

[45] R. Awual, A. Jyo, S. A. El-Safty, M. Tamada, N. Seka, A weak-fibrous anion

exchanger effective for rapid phosphate removal from water. J. Hazard. Mater. 188

(2011) 164 -171.

[46] X. Xu, B.Y. Gao, Q.Y. Yue, Q.Q. Zhong, Preparation of agricultural by-product based

anion exchanger and its utilization for nitrate and phosphate removal,

Bioresour.Technol. 101 (2010) 8558–8564.

[47] U.S. Orlando, A.U. Baes, W. Nishijima, M. Okada, Preparation of agricultural residue

anion exchangers and its nitrate maximum adsorption capacity, Chemosphere. 48 (2002)

1041–1046.

[48] M. Kalaruban, P. Loganathan, W.G. Shim, J. Kandasamy, G. Naidu, T.V. Nguyen, S.

Vigneswaran, Removing nitrate from water using iron-modified Dowex 21K XLT ion

exchange resin: Batch and fluidised-bed adsorption studies, Sep. Purif. Technol. 158
 (2016) 62–70.

[49] R. Saad, K. Belkacemi, S. Hamoudi, Adsorption of phosphate and nitrate anions on

Ammonium functionalized MCM-48: Effects of experimental conditions, J. Colloid

Interface Sci. 31 (2007) 375–381.

[50] X. Xua, B. Gaoa, Y. Zhaoa, S. Chena, X. Tana, Q. Yuea, J. Linb, Y.Wanga, Nitrate

removal from aqueous solution by Arundo donax L. reed based anion exchange resin J.

Hazard. Mater. 203– 204 (2012) 86– 92.

[51] M. Chabani, A. Amrane, A. Bensmaili, Kinetics of nitrate adsorption on Amberlite IRA

400 resin, Desalination 206 (2007) 560–567.

[52] T. Nur, W.G. Shim, P. Loganathan, S. Vigneswaran, J. Kandasamy, Nitrate removal

Using Purolite A520E ion exchange resin: batch and fixed-bed column adsorption

modelling, Int. J. Environ. Sci. Technol. 12 (2015) 1311–1320.

[53] H. Song, Y. Zhou, A. Li, S. Mueller, Selective removal of nitrate from water by a

macroporous strong basic anion exchange resin, Desalination. 296 (2012) 53–60.
Figure captions

Fig.1. FTIR spectra of (A) Chitosan , (B) Chitosan quaternized resin,

(C) Nitrate adsorbed chitosan quaternized resin, (D) Phosphate
adsorbed chitosan quaternized resin

Fig.2. XRD spectra of (A) Chitosan quaternized resin,

(B) Nitrate and (C) Phosphate adsorbed chitosan quaternized resin

Fig.3 SEM images of (A) Chitosan quaternized resin,

(B) Nitrate and (C) Phosphate adsorbed chitosan quaternized resin

Fig.4. EDX spectra of (A) Chitosan quaternized resin,

(B) Nitrate and (C) Phosphate adsorbed chitosan quaternized resin

Fig.5. Effect of contact time of chitosan quaternized resin on (A) nitrate and
(B) phosphate (Conditions: Initial concentration of analytes:
100 mg/L; Dose: 0.1 g and Volume: 50 ml)

Fig.6. Experimental studies on initial concentration of chitosan quaternized

resin on nitrate and phosphate removal (Conditions: Initial
concentration of analytes: 100 mg/L; Dose: 0.1 g and Volume: 50 ml)

Fig.7. Dosage effects on the removal of nitrate and phosphate on chitosan

quaternized resin (Conditions: Initial concentration of analytes: 100
mg/L; Volume: 50 ml)

Fig.8. pH studies of chitosan quaternized resin on the removal of nitrate

and phosphate (Conditions: Initial concentration of analytes: 100
mg/L; Dose: 0.1 g and Volume: 50 ml)

Fig.9. Studies of co-ions on chitosan quaternized resin

(Conditions: Initial concentration of analytes: 200 mg/L; Dose: 0.1 g
and Volume: 50 ml)
Fig.10. Regeneration of chitosan quaternized resin using 0.1M NaCl solution
with contact time of 30 min

Fig.11. Pseudo-second order plot of (A) nitrate adsorption (B) phosphate

adsorption on chitosan quaternized resin at 303 K

Fig.12.Intra particle diffusion plot of (A) nitrate adsorption (B) phosphate

adsorption on chitosan quaternized resin at 303 K

Fig.13. Schematic representation of chitosan quaternized resin before and

after adsorption
Fig. 1
 250

200
Intensity (a.u)

150 A

100
B

50 C

0
20 40 60 80

2 Theta (Deg)

Fig. 2
Fig. 3
Fig. 4
 50 Phosphate

Adsorption capacity (mg/g)

45

40

35

30

25

20
0 5 10 15 20 25 30 35 40 45 50 55 60 65
Time (min)

Fig. 5A
 35 Nitrate

Adsorption capacity (mg/g) 30

25

20

15

0 10 20 30 40 50 60 70 80 90
Time (min)

Fig. 5B
 100
Phosphate
90 Nitrate
Adsorption capacity (mg/g)
80

70

60

50

40

30

20

0 50 100 150 200 250 300 350 400 450

Intial concentration (mg/L)

Fig. 6
 100 Phosphate
Nitrate
90

Removal of anions (%)

80

70

60

50

40

30

20
0.025 0.050 0.075 0.100 0.125 0.150 0.175
Adsorbent dose (g)

Fig. 7
 35 Phosphate

Adsorption capacity (mg/g)

Nitrate

30

25

20

15

10

2 4 6 8 10 12
pH

Fig. 8
 70
Phosphate

Adsorption Capacity (mg/g)

60 Nitrate

50

40

30

20

10

0
Blank Bicarbonate Chloride Sulphate Binary ions

Fig. 9
 7 Nitrate
Phosphate
6

Regeneration cycle
5

0 10 20 30 40 50
Adsorption capacity (mg/g)

Fig. 10
A B

Fig. 11
 70
60 100 mg/L
100 mg/L
150 mg/L 65 150 mg/L
55 200 mg/L
200 mg/L
60
50
55
qt

45

qt
50
40
45
35
40
30
35
3 4 5 6 7 8 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0
t1/2 t1/2
A B

Fig. 12
Fig. 13
Table 1. Isotherm parameters of chitosan quaternized resin at different
temperatures (303 K, 313 K and 323 K)
Isotherms Parameters Nitrate Phosphate
303K 313K 323K 303K 313K 323K

1/n 0.829 0.756 0.654 0.851 0.750 0.717

n 1.205 1.322 1.529 1.173 1.333 1.392
Freundlich kF (mg/g)(L/mg)1/n 15.771 11.470 7.622 22.416 14.124 10.373
r2 0.998 0.995 0.998 0.999 0.999 0.997
Sd 0.007 0.029 0.015 0.008 0.013 0.021
χ2 0.025 0.121 0.083 0.036 0.027 0.047
Q0 (mg/g) 84.092 76.396 75.573 181.296 176.056 154.717
b (L/g) 0.056 0.070 0.090 0.096 0.189 0.219
Langmuir r2 0.979 0.971 0.984 0.977 0.962 0.963
Sd 0.0087 0.003 0.003 0.008 0.002 0.003
RL 0.151 0.124 0.099 0.096 0.189 0.219
χ2 0.116 0.088 0.667 0.145 0.057 0.087
-07 -07 -06 -07 -07
KDR (mol2/J2) 9.18E 1.17E 1.62E 6.00 E 9.41E 1.20E-07
Dubinin– Χm (mg/g) 116.504 118.643 131.392 118.190 120.921 122.146
Radushkevich E (KJ/mol) 0.737 0.652 0.555 0.912 0.728 0.645
r2 0.988 0.948 0.963 0.996 0.996 0.998
Sd 0.206 0.234 0.197 0.203 0.210 0.222
χ2 0.591 1.537 1.477 0.227 0.074 0.071
Table 2. Thermodynamic parameters of chitosan quaternized resin on the
nitrate and phosphate adsorption

Thermodynamic
Temperature Nitrate Phosphate
Parameters
303 K -6.72 -6.47
∆G˚ (kJ mol )
-1 313 K -6.10 -5.57
323 K -5.23 -5.68
∆H˚ (kJ mol-1) -29.36 -18.56
∆S˚ (kJ K-1 mol-1) 0.07 0.04
Table 3. Kinetic parameters for the adsorption of nitrate and phosphate on
chitosan quaternized resin at 303 K

Kinetic Parameters Nitrate (303 K) Phosphate (303 K)

models 100 150 200 100 150 200

mg/L mg/L mg/L mg/L mg/L mg/L

Pseudo kad (1/min) 0.0091 0.0108 0.0093 0.0354 0.0135 0.0115

first
order r 0.9927 0.9895 0.9801 0.9741 0.9764 0.9862

sd 0.0100 0.0029 0.1199 0.0586 0.0082 0.0071

qe(mg/g) 37.078 57.012 69.204 48.851 59.665 74.349

0.0045 0.0081 0.0008 0.0044 0.0040 0.0029
k(g/mg min)
Pseudo
order
second 6.2027 2.6548 3.8370 10.656 14.407 16.144
h(mg/g min)
order
r 0.9962 0.9972 0.9975 0.9965 0.9978 0.9971

sd 0.0495 0.0274 0.0481 0.0280 0.0182 0.0170

Kp (1/min) 0.0086 0.0103 0.0089 0.0325 0.0129 0.0111

Particle
diffusion r 0.9930 0.9994 0.9903 0.9969 0.9966 0.9964

sd 0.0214 0.0071 0.0262 0.1169 0.0175 0.0155

Intra Ki (mg/g 1.7651 3.4147 4.7765 2.6032 3.0402 4.0491

Particle min0.5)
diffusion r 0.9837 0.9991 0.9802 0.9837 0.9912 0.9906
0.6116 0.2788 1.8339 0.8005 0.6827 0.9399
sd
Table 4. Comparative study of chitosan quaternized resin with other resins
 Functional Adsorption
Adsorbent group Sorbate capacity Reference
and ionic (mg/g)
form
Amberlite Quaternary
IRA 400 resin ammonium and Nitrate 65.36 [1]
Cl-
Amine-grafted Secondary amine Nitrate 59 [10]
corn cob and and Cl-
coconut copra
Indion NSSR Quaternary
resin ammonium and Nitrate 119 [13]
Cl-
Wheat Quaternary Nitrate and 52.8 and 45.7 [16]
straw anion ammonium and Phosphate
exchanger (WS- Cl-
AE)
QCMGR resin Quaternary [24]
ammonium and Nitrate and 97.5 and 112.5
Cl- Phosphate
Amine grafted Quaternary Nitrate 74 [47]
lignocellulosic ammonium and
agricultural Cl-
wastes
Dowex 21K XLT Quaternary Nitrate 75.3 [48]
resin ammonium and
Cl-
Ammonium- Quaternary Nitrate and 34.8 and 39.7 [49]
functionalized ammonium and Phosphate
mesoporous Cl-
MCM-48 silica
ALR-AE resin Quaternary [50]
ammonium and Nitrate 38.9
Cl-
Propylammonium Quaternary Nitrate and 45 and 57 [51]
functionalized ammonium and Phosphate
mesoporous silica Cl-
materials

Purolite A 520E Quaternary Nitrate 32.2 [52]

resin ammonium and
Cl-

MD 218 resin Quaternary Nitrate 108.53 [53]

ammonium and
Cl-
CsQ resin Quaternary Nitrate and 84.09 and Present work
ammonium and Phosphate 181.29
Cl-