Carbohydrate Polymer Technologies and Applications 7 (2024) 100516

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Carbohydrate Polymer Technologies and Applications

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carbohydrate-polymer-technologies-and-applications

Synthesis and application of fatty acid-modified chitosan for heavy metal

remediation from waste water
Shabbah Begum a, Nor Yuliana Yuhana a, *, Noorashikin Md Saleh a, Zishan Shaikh b
a
Department of Chemical and Process Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor,
Malaysia
b
Solar Energy Research Institute, Universiti Kebangsaan Malaysia, 43600 UKM, Bangi, Selangor, Malaysia

A R T I C L E I N F O A B S T R A C T

Keywords: A novel modified chitosan was synthesized using palmitic acid to selectively remove Cd(II), As(III), and Pb(II)
Chitosan from water samples. Chitosan was dissolved in acetic acid solution and N, N’-dicyclohexylcarbodiimide was used
Palmitic acid crosslinking agent, to further functionalize with palmitic acid to introduce O-donor sites in the chitosan chain.
Modification
These sites entrap metal ions forming covalent bonds leading to removal of heavy metal ions. The product was
Contaminated water
Heavy metal removal
characterized using Fourier transform-infrared spectroscopy (FTIR), scanning electron microscopy (SEM),
elemental analysis, X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy, and proton nuclear magnetic
resonance. The introduction of palmitic acid into the chitosan chain did not only alter its original structure and
crystallinity, as evidenced by XRD and SEM data, but enhanced stability and increased the affinity toward heavy
metal ions. The adsorption processes were extensively examined under optimized conditions, and results
revealed the maximum absorptivity values of 40.98, 21.8, and 47.6 mg/g for Cd(II), As(III), and Pb(II),
respectively, indicating high adsorption capacity. The kinetic study suggested a pseudo-second-order reaction,
and the Langmuir isotherm model demonstrated the best fit. The limits of detection for Cd, As, and Pb were 2.9,
4.3, and 15.1 ppb, while the limits of quantification were 9.07, 13.23, and 45.77 ppb, respectively. The
desorption studies showed the regeneration and reusability of the adsorbent up to four cycles.

1. Introduction et al., 2017).

To combat this issue, scholars have investigated sustainable and
Water is essential for life, but pollution from various sources, such as efficient methods for heavy metal removal. Mitigating heavy metal
domestic actions, agriculture, and industry, poses a significant threat to contamination in water bodies is crucial for safe water consumption and
its quality (H. Wu et al., 2023). Pollution disrupts the natural balance of daily activities. Various methods, such as chemical precipitation,
water and affects the environment, economy, and health. Pollutants membrane technologies, electrochemical reactions, ion exchange, and
include heavy metals, chemicals, and microbial contaminants, which adsorption on carbon-based materials, are used to remove heavy metal
harm the aquatic ecosystems and make water unfit for consumption ions from wastewater (Ishihara et al., 2015; Kim et al., 2023; Kot­
(Remoundou and Koundouri, 2009). Heavy metal pollution has been a taichamy, Begum, Chattanahalli, et al., 2020, 2020). Adsorption,
nuisance at a global level. Heavy metals, such as Pb, Hg, and Cd, orig­ wherein heavy metals are chelated or attached to material surfaces, is a
inate from natural sources but pose risks because of their toxic nature, widely researched approach in water treatment, environmental reme­
accumulation, and biomagnification in the food chain (Jordan et al., diation, and industrial processes (Nyamato, 2023; Panda et al., 2019).
2014; Lin et al., 2022). Heavy metals are toxic even at low concentra­ Common adsorbents include activated carbon, zeolites, clay, metal ox­
tions and affect aquatic ecosystems and human health. Heavy metals are ides, and biopolymers. Adsorption plays a pivotal role in purifying water
non-biodegradable, and they can persist in the environment and enter and treating wastewater to remove organic and inorganic pollutants
humans through contaminated water, aquatic organisms, and industrial (Begum et al., 2021; Himmi et al., 2022). The effectiveness of waste­
exposure. Heavy metal pollution is a global issue in various countries as water treatment depends on pollutant characteristics, thereby under­
a result of industrial activities and poor waste management (Wasana scoring the need for efficient practices to ensure clean and safe water

* Corresponding author
E-mail address: [email protected] (N.Y. Yuhana).

https://doi.org/10.1016/j.carpta.2024.100516

Available online 22 May 2024

2666-8939/© 2024 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
S. Begum et al. Carbohydrate Polymer Technologies and Applications 7 (2024) 100516

access. of an adsorbent is essential to enhance its absorptivity and decrease

A low cost, effective, biocompatible, and sustainable approach for agglomeration. Therefore, fatty acids, such as palmitic acid, stearic acid,
heavy metal remediation is essential (Rajendran Royan et al., 2018). and linoleic acid, have been used as stabilizing agents. The stabilized
Hence, chitosan, a deacetylated chitin, is an ideal material for heavy and enhanced adsorbent can be used successfully to separate metal ions
metal remediation (Gagné and Simpson, 1993; Zhao et al., 2019). Chi­ (Palanisamy et al., 2013). These adsorbents can entrap heavy metal ions
tosan is obtained through deacetylation using concentrated alkali solu­ through covalent bonds. The presence of oxygen donors forming cova­
tion at high temperature. It consists of pyranose cycles of β-(1, lent bonds with hydrophobic chitosan adsorbent leads to the chelation of
4)-2-amino-2-deoxy-β-D-glucose and N-glucosamine linked by glyco­ heavy metals (Hashem et al., 2020; Usman et al., 2021). The crosslinking
sidic bonds. The deacetylation of chitin introduces acetylated and agent for chitosan modification depends on the intended application and
deacetylated units onto the chitosan chain, and the ratio of glucosamine desired properties of crosslinked material. N,N’-Dicyclohex­
to N-acetylglucosamine determines its degree of acetylation (DA) (Iber ylcarbodiimide (DCC) is commonly used as a coupling agent in organic
et al., 2023; Joao et al., 2016; Muzzarelli et al., 1986). Physical prop­ synthesis and biochemistry. It is frequently employed in the formation of
erties, such as surface area, tensile strength, and solubility and biological amide bonds between carboxylic acids and amines or amino acids during
properties, such as adsorption, biodegradability, and bioavailability, are peptide synthesis. DCC acts as a zero-length crosslinker and facilitates
influenced by synthesis method and conditions. Chitosan is a versatile the reaction between a carboxylic acid group and an amino group
substance that can undergo modifications with a variety of compounds. (López-Pérez et al., 2020; Tian et al., 2020). DCC converts carboxylic
It possesses qualities, such as biocompatibility, degradability, acid into an active acylating agent called an “acylurea.” This interme­
physio-electrochemical properties, and non-toxicity, which render it as diate readily reacts with an amino group to form an amide bond (Ala­
an exceptional bioadsorbent (Ismail et al., 2022). Thiol-functionalized varse et al., 2022; Kłodzińska and Nielsen, 2021). DCC helps preserve
chitin nanofibers exhibit an adsorption capacity of 149.9 mg g − 1 for the stability and improve bond strength. It creates reversible polymer
arsenic (R. Yang et al., 2015). Chitosan/clinoptilolite/magnetite nano­ networks that can be adjusted and adapted according to the physical and
composites demonstrate significant Pb(II) adsorption capabilities, chemical properties of the polymers (Comba et al., 2020; Luo et al.,
reaching up to 136.99 mg g − 1 at pH 6 (Javanbakht et al., 2016). The 2023; Shi et al., 2020). DCC increases the stability of chitosan without
exceptional metal ion adsorption capacity of chitosan is attributed to the compromising its adsorbent capacity (Luo et al., 2023; Upadhyay et al.,
abundance of hydroxyl and amino groups within its molecular structure 2021).
(de Souza and Giudici, 2021). Moreover, chitosan/clay/magnetite bio­ Fatty acids play a significant role in the removal of heavy metals
adsorbent exhibits notable removal capacities for Cu(II), As(V), and Pb from various environments, such as water and soil. Fatty acids con­
(II) at 17.4, 5.9, and 136.99 mg g − 1, respectively (D. Cho et al., 2012). taining biosurfactants, which are used for decontamination and recov­
Chitosan/clay biocomposite beads also demonstrate high adsorption ery of heavy metal ions, can form complexes with heavy metals to
capacities of 73 mg g − 1 for Cr(VI) and 2.38 mg g − 1 for Pb(II) (Biswas facilitate their extraction (Mulligan et al., 2001). The involvement of
et al., 2017). Additionally, surfactant-modified chitosan beads exhibit fatty acids, particularly within biosurfactants, in heavy metal removal
an adsorption capacity of 125 mg g − 1 for Cd(II) at pH 7 (Pal and Pal, encompasses several mechanisms. Certain types of rhamnolipids sur­
2019a, 2019b). Zeolite imidazolate framework (ZIF)-modified bacterial factant removed of 36 %–56 % Cd, 51 % Ni, and 70 % Cu (A. J. Das et al.,
cellulose/chitosan composites show adsorption capacities of 200.6 mg g 2017). Palmitic acid contains carboxyl groups that can act as ligands to
− 1
for Cu(II) and 152.1 mg g − 1 for Cr(VI) (Bandura et al., 2020). The form complexes with heavy metal ions through chelation. Chelation
conventional methods of chitosan production involve the use of toxic entails the binding of metal ions to organic molecules, thereby influ­
chemicals, high cost, and complex procedures leading to time and en­ encing their mobility and reactivity. While palmitic acid itself is not a
ergy consumption while generating secondary pollution. The main biosurfactant, it does possess surface-active properties. In certain cases,
advantage of chitosan stems from the presence of modifiable positions these surface-active agents can alter the behavior of contaminants in
within its chemical structure. Through modification techniques like (i) water and potentially aid in their removal (Mishra et al., 2021a; Šiška,
grafting (the incorporation of functional groups) or (ii) cross-linking 2005). Palmitic acid can form complexes with various metal ions. The
reactions (the interconnection of macromolecular chains), chitosan formation of these complexes may affect the solubility and mobility of
can yield derivatives characterized by improved properties, including metals in water, which could be relevant in certain remediation strate­
higher adsorption capacity and enhanced resistance in challenging gies. Such biosurfactants offer a multifaceted approach to heavy metal
environmental conditions. Removal of organic dyes or other metal ion removal, with implications for environmental cleanup efforts (Mishra
pollutants from the water also depends on the type of functional group et al., 2021b). Biosurfactants are recognized as promising contenders for
added to the chitosan adsorbent. While crosslinking is frequently bioremediation because of their ionic nature, minimal toxicity, potent
employed to fortify the chemical stability of chitosan, it may entail a emulsifying capabilities, versatility, surface activity, and environment
compromise in the availability of active functional groups, particularly friendliness (Akbari et al., 2018; A. J. Das et al., 2017). Furthermore,
amino and hydroxyl groups. To obtain adsorbents with enhanced biosurfactants can offer specific advantages in heavy metal remediation
adsorption capacity and selectivity, diverse functional groups, encom­ owing to their small size, low toxicity, high biodegradability, and
passing amino groups, sulfur groups, carboxyl groups, alkyl groups, and effectiveness across a wide range of pH and temperature conditions
other distinctive structures, are investigated through chemical modifi­ (Akintunde et al., 2015; Ravindran et al., 2020).
cations in the chitosan. In this study, the primary objective is to develop a new approach to
Acylation of chitosan with different substitution groups enhances its modified chitosan with fatty acids, specifically palmitic acid, and using
efficacy in removing metal ions (Cazón and Vázquez, 2020). However, N,N′-dicyclohexylcarbodiimide (DCC) acting as a crosslinking agent in
pristine chitosan does not offer high selective and removal efficiency for the presence of acetic acid. This modification process aims to enhance
heavy metals because of deficiency of active binding sites. Hence, adsorption capacity of chitosan and selectivity, thereby making it more
chemical and physical modification of chitosan is crucial for enhanced effective in removing heavy metal ions from water, even at trace levels.
adsorption and selective removal of heavy metals. Introduction of The effects of dosage, initial concentration, temperature, and contact
functional groups onto the chitosan chain through chemical reactions time of the adsorbent were systematically studied. Additionally, the
with amino and methyl or hydroxy group are essential (Ellina et al., study evaluates the sensitivity of the modified chitosan adsorbent by
2021; Rahman et al., 2021). For example, functionalization of chitosan determining the limit of detection (LOD) and limit of quantification
using clay–magnetite (Cho 2012), carboxylmethyl (Borsagli 2019), (LOQ). These metrics are crucial as they provide insights into the lowest
lactic acid (Zia et al., 2020), and sulfactant (Pal and Pal, 2019a) in­ concentration of heavy metal ions that can be reliably detected and
creases the adsorption capacity of heavy metals. However, the stability quantified using the modified adsorbent. This assessment ensures the

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S. Begum et al. Carbohydrate Polymer Technologies and Applications 7 (2024) 100516

Fig. 1. Step by step modification of chitosan using palmitic acid.

effectiveness and reliability of the modified chitosan in practical appli­ 2.3. Sample preparation for characterization
cations for water treatment, especially in scenarios where detecting and
removing heavy metal ions at very low concentrations is essential. This Samples were prepared for FT-IR analysis using K-Br pellet method.
research contributes to the advancement of water purification technol­ ChiPA was pulverized into a fine powder and then compressed into KBr
ogies by introducing a modified chitosan material with enhanced pellets. FT-IR spectra were recorded using a Perkin Elmer FTIR spec­
adsorption capabilities, paving the way for more efficient and selective trometer. XRD patterns of the dry ChiPA samples were obtained using a
removal of heavy metal contaminants from water sources. Bruker D8 Advance XRD machine. FESEM images of the dry powder
samples were captured using a ZEISS Merlin FESEM. Bruker Advance III
2. Experimental HD 400 MHz FT-NMR was utilized to obtain 1H NMR spectra of the
adsorbent. The samples were dissolved in DMSO by using a sonicator to
2.1. Reagents and materials ensure a homogeneous solution. Perkin Elmer ICP-MS was employed to
analyze the samples for heavy metals before and after adsorption. The
Double-distilled deionized water was used throughout the experi­ ChiPA adsorbent and heavy metal ion solutions were prepared with
ment. All chemicals were of analytical reagent grade to ensure accuracy distilled water at pH 7 at room temperature (~26 ◦ C).
in the experiments. Chitosan shell flakes (extra pure) was obtained from
Nacalai Tesque, Japan. Palmitic acid (C16H32O2), acetic acid 2.4. Sorption studies
(CH3COOH), sodium arsenate (NaAsO2), and nitric acid (HNO3, ≥69 %)
were procured from R&M chemicals (Essex, UK). Essential reagents such All the samples were investigated for its optimum adsorbent dosage,
as methanol (CH3OH, ≥99 %), ethanol (C2H6O, ≥99 %) and acetone heavy metal ion concentration, temperature, and contact time. The
(C3H6O, ≥99 %) were acquired from System, Malaysia. Cadmium experiment was conducted in batch mode. The adsorbent dosage varied
chloride (CdCl2) and lead chloride (PbCl2) were provided by Chemiz. N, from 1 mg/L to 20 mg/L, and the concentration of heavy metals ranged
N’-dicyclohexylcarbodiimide (C13H22N2, ≥99 %) was supplied by from 1 ppm to 20 ppm. The contact time and temperature ranges varied
Sigma-Aldrich, Germany. Analytical grade ammonia (NH3, 25 %) was from 5 min to 20 min and 5 ◦ C to 60 ◦ C, respectively. These parameters
obtained from Chem-Lab, Belgium. As(III), Cd(II), and Pb(II) were were used to optimize the adsorption parameters of the study. Real
concocted at a concentration of 100 ppm to prepare stock solutions of water samples were analyzed for AAS at optimum dosage, concentra­
heavy metals. tion, contact time, and temperature. Following adsorption, the resulting
mixtures were subjected to centrifugation at 4000 × g for 10 minutes.
2.2. Chemical modification of chitosan The solution was filtered using Whatman filter paper to capture any
remaining residue. The concentration of metal ions was determined
Chitosan was dissolved in 1 % acetic acid solution in 100 mL of through atomic absorption spectroscopy (AAS). To gain a comprehen­
deionized water. In a separate beaker, a mixture of DCC and palmitic sive understanding of the adsorption procedure, we examined the effect
acid was prepared in the ratio of 10:1 in 100 mL of ethanol solution. The of dosage, concentration, temperature, and contact time.
solution was continuously stirred for 24 h at room temperature (~ 26 Equation (1) was used to determine the adsorption capacity (mg g −
◦
C) to form a clear solution. Chitosan was modified with palmitic acid. 1
) of metal ions in the solution at equilibrium. (Hefni et al., 2020)
The solution was then slowly added to chitosan/acetic acid solution
while stirring continuously with a magnetic stirrer. The mixture was left V
qe = (Co − Ce ) (1)
for reaction under continuous stirring at room temperature for 24 h. M
After 24 h, a solution of ammonia and ethanol was prepared in a ratio of
where qe (mg g − 1) denotes the quantity of adsorbed metal ions per unit
7/3 (v/v) to obtain chitosan/palmitic acid (ChiPA) mixture. Under a
mass of biopolymer at equilibrium, while C0 (mg L − 1), Ce (mg L − 1), M
fume hood, the mixture was precipitated and slowly poured into the
(g), and V (L) represent the initial concentration, equilibrium concen­
ammonia solution while stirring continuously. The precipitated solution
tration of the heavy metal ion solution, the mass of the adsorbent, and
was filtered under Millipore vacuum filtration with ethanol to remove
the volume of the metal ion solution, respectively. The following
any by-product and then washed with deionized water three to four
equations were used to determine the limit of detection (LOD) and limit
times. The filtered product was left to dry at 60 ◦ C for 2 days in a hot air
of quantification (LOQ) through the data obtained from regression
oven (Fray et al., 2012; Sharma and Singh, 2017; Thotakura et al.,
analysis (Pattar and Nandibewoor, 2015; P. C. Yang et al., 2023; Yildiz
2017). The final product was pulverized, and a white powder was ob­
et al., 2013).
tained. The resultant modified chitosan (ChiPA) was characterized using
Fourier transform-infrared spectroscopy (FTIR), field-emission scanning LOD = 3.3 × (SD of intercept / slope) (2)
electron microscopy (FESEM), and X-ray diffraction (XRD) to confirm
the modification of chitosan with palmitic acid. The schematic repre­ LOQ = 10 × (SD of intercept / slope) (3)
sentation is shown in Fig. 1.
where SD is the standard deviation.
Isotherm studies were conducted using heavy metal ion concentra­
tion ranging from 1 mg L − 1 to 20 mg L − 1 for 24 h at room temperature
and pH 7.

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S. Begum et al. Carbohydrate Polymer Technologies and Applications 7 (2024) 100516

Fig. 2. (a) FTIR spectra showing the characteristic peaks of chitosan, palmitic acid and modified ChiPA adsorbent; and (b) XRD spectra showing the 2θ shift in ChiPA
adsorbent after modification of chitosan with palmitic acid.

amino groups of chitosan. The stretching vibrations of the -C-OH group

appear at 1030 and 1150 cm− 1, while the -C-O–C group is represented
at 1240 cm− 1. Furthermore, the intensity of the -NH2 peak at 1600 cm− 1
decreases possibly due to the protonation of the -NH2 group of chitosan,
− 1
with characteristic peaks of NH+ 3 appearing at 1523 and 1540 cm
(Sharma and Singh, 2017; Thotakura et al., 2017). In the XRD dif­
fractogram in Fig. 2(b) of chitosan, a major crystalline peak is evident at
around 20◦ , indicating a relatively regular crystal lattice structure.
Additional peaks at 8◦ , 11◦ , 16◦ , 18◦ , and 22◦ can be attributed to pal­
mitic acid, while the characteristic peak of chitosan shifts to approxi­
mately 20.2◦ . The presence of multiple peaks, variations in peak
intensity and width, and changes in diffraction angles for the ChiPA
adsorbent strongly suggest the successful modification of chitosan
(Zhang et al., 2017). Table S1 summarizes FTIR peak assignment for
chitosan, palmitic acid and ChiPA.

3.1.2. 1H NMR
The substitution of palmitic acid on the chitosan backbone was
verified through 1H NMR and FTIR. The 1H NMR spectra of chitosan are
illustrated in Fig. 3. The resonance signals of the three N-acetyl protons
Fig. 3. 1H NMR spectra of chitosan before and after modification using pal­ from N-acetylglucosamine (-CO–CH3) and the two protons H2 from the
mitic acid. glucosamine residue were observed at 1.9 and 3.0 ppm, respectively.
The proton signals for the ring protons (H-3, -4, -5, -6, -6′) of chitosan
2.5. Specification of real water samples were detected in the range of 3.4–3.8 ppm. The appearance of a new
proton peak between 1.1 and 0.8 ppm can be attributed to the resonance
Water samples laced with heavy metals (As, Pb, and Cd) were care­ of the -CH2 and -CH3 groups from the fatty acyl residues. Additionally,
fully prepared in various concentrations, ranging from 1 ppm to 20 ppm, the proton associated with the fatty acyl residue forming the amide bond
at 25 ◦ C and pH 7. Water samples collected from nearby lakes were also (-CO-)-CH2 resonates within the range of 2.4–2.7 ppm. The peaks around
kept at room temperature and pH 7 to prevent any physiological and 3.13 ppm indicate the presence of the alkoxy group (R-CO–NH), while
chemical changes. All the experiment were conducted at room temper­ those between 1.0 and 1.7 ppm confirm the existence of protons from
ature, unless stated otherwise. Real water samples were obtained from the methyl group (-CH3). Furthermore, a peak at 4.3 ppm, representing
Bestari Jaya river and Kolej Pendeta Zaba lake, UKM, Selangor. the amide group (R-CO–N–H), provides strong evidence for the for­
mation of the amide bond (Sharma and Singh, 2017; Thotakura et al.,
3. Results and discussion 2017; Zhang et al., 2017). The degree of substitution (DS) could be
determined by elemental analysis with reference to previous published
3.1. Characterization literature (Baran and Menteş, 2016; Inukai et al., 1998; Shibano et al.,
2014). DS was calculated according to the following equation:
3.1.1. FTIR and XRD
No. of C introduced into chitosan
The FTIR spectra in Fig. 2(a) reveal specific absorption peaks. The DS = (4)
peak at 1660 cm− 1 can be attributed to the stretching of the carbonyl No. of C of fatty acid group
group in secondary amide, and the peak at 1585 cm− 1 corresponds to the
α(C/N)m − (C/N)0
bending vibration of the -N-H group in the amide. The absorption peak DS = (5)
η
between 2850 and 2950 cm− 1 arises from the -CH2 group within the N-
acyl moiety, and its intensity is directly related to the length of the fatty
where α and η are the number of N and C atoms added following
acid chain. The presence of an amide bond is clearly confirmed by the
modification, and (C/N)m and (C/N)0 are the C/N of modified chitosan
peaks at 3330, 1660, and 1090 cm− 1, which correspond to the -N-H, -C =
and unmodified chitosan, respectively. The DS is 1.4, which indicates
O, and -C-N groups, respectively. The peak at 1250 cm− 1 is attributed to
the successful modification of chitosan with palmitic acid. The use of
the -C-O group of chitosan. The characteristic broad band of chitosan
acetic acid as a solvent leads to slow disassociation of ions (Rinaudo
between 3200 and 3500 cm− 1 is diminished due to a reduction in the
et al., 1999).

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S. Begum et al. Carbohydrate Polymer Technologies and Applications 7 (2024) 100516

Table 1 3.2. Reaction mechanism

Elemental analysis of chitosan and ChiPA.
Sample C% N% C/N The reaction mechanism of palmitic acid modification of chitosan
with DCC involves several chemical process. The carboxylic group (-C =
Chitosan 83.1 3.5 23.742
ChiPA 85.7 2.8 30.6 O–OH) of palmitic acid and the amino group (-NH2) of chitosan are
activated in the presence of organic acid, acetic acid, and ethanol. DCC is
used as a coupling agent in this process. DCC reacts with the carboxylic
3.1.3. FESEM and EDX group of chitosan to form an intermediate known as O-acylisourea,
The elemental analysis of chitosan and ChiPA are listed in Table 1. which undergoes further reaction with the amino group of chitosan. The
The increase in C% is due to the introduction of long chains of palmitic activated carboxyl group of palmitic acid reacts with the amino group of
acid. chitosan, forming an amide bond (-C = O–NH). The reaction results in
The morphology of pristine chitosan flakes in Fig. S1 (a) shows un­ the covalent bonds of palmitic acid to the chitosan backbone and creates
even flakes without porosity, and they have firm, fibrous, and dense a chitosan–palmitic acid conjugate. After the formation of amide bond,
structures. ChiPA in Fig. S1 (b) has a rough surface with uniformly excess DCC can be eliminated from the reaction (Fray et al., 2012). Fig. 4
distributed spherical deposits with particle size less than 100 nm. The depicts the mechanism involved in the chemical reaction in two steps.
aggregated spherical deposition can be attributed to the successful for­ The acylisourea byproduct is soluble in organic solvents and can be
mation of the chitosan adsorbent. Fig. S2 shows the EDX spectra of easily removed. The resultant product is used as an adsorbent for heavy
chitosan and ChiPA adsorbent. metal ions, namely, As(III), Cd(II), and Pb(II). The formation of π− π
covalent bonds lead to the chelation of heavy metal ions. The free
electron pair of oxygen with the amine group is responsible for

Fig. 4. Mechanism of reaction involved in the modification of chitosan showing the formation of o-acylisourea intermediate. (a) Activation of palmitic acid with DCC
and (b) reaction with chitosan to form ChiPA adsorbent.

Fig. 5. (a) Effect of metal ion concentration showing increase in the removal of heavy metal ions with increase metal ion concentration, (b) shows the increase in
metal ion removal with increase in dosage of ChiPA adsorbent, (c) effect of contact time showing metal ion removal reaching equilibrium at 20 min, and (d) effect of
temperature ranging from 5 to 60 ◦ C of ChiPA on As, Pb and Cd.

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S. Begum et al. Carbohydrate Polymer Technologies and Applications 7 (2024) 100516

Fig. 6. Langmuir isotherm model for the adsorption of (a) lead, (b) arsenic, (c) cadmium on the ChiPA adsorbent, and (d) showing metal ion concentration in real
water sample.

adsorption. The hydrophobic properties of palmitic acid and chelating and R2 were obtained through regression analysis is shown in Table S2.
capabilities of chitosan make it suitable for adsorbing heavy metals from Fig. 6(d) presents the metal ion concentration in real water samples. The
aqueous solutions (Hashem et al., 2020; Palanisamy et al., 2013; Usman amount of heavy metals is low in most samples. The high heavy metal
et al., 2021). concentration in the first sample might be due to a nearby source of
sampling. The concentration of heavy metals is under the permissible
limit for all the samples.
3.3. Adsorption studies

3.3.1. Effect of dosage and concentration 3.4. Isotherm studies

Fig. 5(a) demonstrates that as the concentration of metal ions in the
solution increases, the amount of metal ions absorbed also increases. Adsorption isotherm offers data on the distribution of metal ions in
This phenomenon can be attributed to the increased presence of heavy liquid and solid phases at varying equilibrium concentrations. It also
metal ions in the solution and the presence of numerous active sites on evaluates the efficiency of the interacting molecules between the
the adsorbent material. In Fig. 5(b), increasing the amount of adsorbent adsorbate and the adsorbent. Various isotherm models, including the
used leads to enhanced efficiency in removing heavy metals. This Freundlich and Langmuir models, have been utilized to analyze exper­
improved adsorption with higher doses of adsorbent is likely due to the imental data to enhance the design of adsorption systems for the effi­
larger surface area available for metal ions to interact with (Laus and De cient removal of heavy metal ions from solutions (S. K. Das et al., 2006;
Fávere, 2011). However, as the amount of adsorbent continues to in­ He et al., 2014; McRae et al., 2008).
crease, the adsorption capacity decreases. This decrease may be caused
Ce 1 Ce
by the aggregation of adsorbent sites, resulting in longer diffusion paths = + (6)
qe Kl Qe Q0
and reduced total surface area accessible to the metal ions. The presence
of a substantial number of amino groups, fostering intra and intermo­ The Langmuir model assumes uniform energy of adsorption and the
lecular hydrogen bonds, can be ascribed to the blocking of active sites formation of a single layer of solute molecules on the adsorbent surface
and reducing the effectiveness in removal of heavy metals (Huang et al., at a constant temperature. This monolayer adsorption model is widely
2014; Nowack and Sigg, 1996; Szyguła et al., 2008). used and described by the following equation. A linear model plot was
generated to evaluate the suitability of the Langmuir isotherm model for
3.3.2. Effect of temperature and contact time describing metal biosorption onto the chitosan adsorbent. The values of
In Fig. 5(c), the adsorption time for heavy metals varies depending QMax, KL, and R2 were obtained (Fig. 6 and Table S3). Table S3 dem­
on the size of the metal ions. Beyond the equilibrium time, absorption onstrates that R2 (correlation coefficients) for the Langmuir isotherm
remains nearly constant. This phenomenon can be elucidated by the model exceeds 0.9, indicating that the number of available adsorption
initial availability of unoccupied sites. However, occupation of the sites on the adsorbent is restricted, and metal ions form a monolayer on
remaining sites becomes challenging as the equilibrium is attained the adsorbents surface at saturation (Hefni et al., 2020). As a result, the
because of the repulsive forces between the heavy metal ions in the adsorption process can be described by a linear equation.
adsorbent and in the bulk solution. Notably, an increase in absorption is Table S3 also demonstrates differences in the QMax values for three
observed for lead and arsenic because of the high number of active different types of metals. This disparity can be attributed to variations in
binding sites on the adsorbent’s surface. Fig. 5(d) presents the results of the ionic radii of these metals. As the atomic radius of the metal ions
temperature-related studies with metal ion concentration of 2 ppm at increases, the QMax value decreases. This finding can be reasonably
varying temperatures (5 ◦ C, 25 ◦ C, and 50 ◦ C). As the solution temper­ explained by the fact that smaller metal ions can more effectively
ature increases, the movement of metal ions increases, thereby facili­ approach the active sites of biosorption, leading to stronger binding and
tating the deeper penetration of larger metal molecules. However, reduced system disorder.
temperature plays a role in influencing the rate of adsorption due to
molecular interactions and solubility. Increased temperatures leading to 3.4.1. Thermodynamic studies
enhanced removal of heavy metals can be linked to the chemical re­ Adsorption behavior of As(III), Cd(II), and Pb(II) ions was studied at
actions between the functional groups of the adsorbent and the adsor­ different temperatures (278 – 333 K) to determine ethe effect of tem­
bate. Conversely, a decrease in removal may be attributed to perature on the adsorption process. The thermodynamics parameters
physisorption. (Hefni et al., 2020; Jeon and Kwang, 2005). LOD, LOQ, include free energy (ΔG◦ ), enthalpy (ΔH◦ ), and entropy (ΔS◦ ) of the

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Table 2
Comparative study of the current study* with few selected published modification techniques.
No. Modification Condition Metal Absorptivity Isotherm Kinetics Author
ions

1. Chitosan/Palmitic acid NTP, pH = 7, C0 = 1 – Pb(II) 47.6 mg/g Langmuir PSO *Present study
20 mg/L As(III) 21.8 mg/g
Cd(II) 40.98 mg/g
2. Chitosan-clay/magnetite pH=3–9, Cu(II) 17.4 mg/g Langmuir, Freundlich PSO (D.-W. Cho et al.,
C0 = 16– 356 mg/L As(V) 5.9 mg/g 2012)
Pb(II) 136.99 mg/
g
3. Carboxylmethyl-chitosan pH =8.5, Cd(II) 147.2 mg/g Langmuir PSO (Borsagli and
T = 25 ◦ C Borsagli, 2019)
4. Porous poly (L-lactic acid)-chitosan pH =7, Cu(II) 111.6 mg/g Langmuir PSO (Zia et al., 2020)
nanofibers T = 80 ◦ C,
C0 = 50 – 200mg/L
5. Chitosan-clay biocomposite beads pH = 9, Pb(II) 2.38 mg/g Langmuir, Freundlich, Dubinin- PSO (Biswas et al., 2020)
T = 60 ◦ C; Radushkevich
C0 =25 mg/L
6. Sulfactant modified chitosan beads pH=7, Cd(II) 125 mg/g Langmuir, Freundlich, Sips PSO (Pal and Pal, 2019a)
C0 = 10-100 mg/L,
T = 23 ◦ C
7. Chitosan-CaCO3 nanoparticles Various Cd(II) 83.33 mg/g Langmuir PSO (Hassan et al., 2024)
Cu(II) 47.84 mg/g
Pb(II) 98.03 mg/g
Cr(II) 62.11 mg/g
Ni(II) 63.69 mg/g
8. Fe3O4 nanocomposite pH 6, Ni (II) 30.03 mg/g Langmuir PSO (Sharifi et al., 2023)
C0 = 2 g/L Co(II) 53.19 mg/g
Time = 2 h
9. Carboxymethul chitosan resins C0 = 1.4 g/L Pb(II) 4.78 mg/g Langmuir PSO (Patel et al., 2024)
Time = 420 min Fe(II) 147.06 mg/
Zn(II) g
238.10 mg/
g
10. Magnetic xanthate-modified chitosan/ Time = 240 min Cu(II) 206 mg/g Langmuir, PSO (Dong et al., 2022)
polyacrylic acid hydrogels Cd(II) 178 mg/g Freundlich
Pb(II) 168 mg/g
Co(II) 140 mg/g

adsorption process of As(III), Cd(II), and Pb(II), which were calculated capacities for Pb(II), As(III), and Cd(II), at 47.6 mg/g, 21.8 mg/g, and
using the following equations: 40.98 mg/g, respectively, employing Langmuir isotherm and PSO ki­
netics, indicating its suitability for practical applications. However, the
Kc = Cad /Ce (7)
chitosan-clay/magnetite modification offers only moderate adsorption
where Kc is Langmuir constant, Cad is the concentration of the adsorbed capacities, with a low adsorption capacity for As(V). On the other hand,
metal ions (mg L − 1), and Ce is the equilibrium concentration (mg L − 1) carboxylmethyl-chitosan modification displays a high adsorption ca­
pacity for Cd(II) at 147.2 mg/g, and porous poly(L-lactic acid)-chitosan
ΔG∘ = RTlnKc (8) nanofibers demonstrate significant adsorption capacity for Cu(II) at
111.6 mg/g, albeit limited to single metal ion adsorption at a time.
lnKc = (ΔS∘ / R) − (ΔH∘ /RT) (9) Additionally, chitosan-clay biocomposite beads exhibit relatively lower
adsorption capacities for Pb(II), while sulfactant-modified chitosan
where ΔG◦ is the change in Gibbs free energy (kJ mol− 1), ΔH◦ is the shows adsorption exclusively for Cd(II) removal. Chitosan-CaCO3
change in enthalpy (kJ mol− 1), ΔS◦ is the change in entropy (Jmol− 1 K − nanoparticles and Fe3O4 nanocomposite shows good adsorption for
1
), R is universal gas constant (8.314 J mol− 1 K − 1), and T is the tem­ multiple metal ions where as Carboxymethul chitosan resins and Mag­
perature (K). netic xanthate-modified chitosan/polyacrylic acid hydrogels Despite
The thermodynamic parameters are summarized in Table S4. The notable adsorption capacities exhibited by several chitosan adsorbents
values of ΔH◦ and ΔS◦ can be determined from the slope and intercept for specific metal ions, the ChiPA adsorbent emerges as the most effec­
depicted in the plot of ln Kc vs. 1/T. The negative values of ΔH◦ signify tive choice due to its high adsorption capacities across multiple metal
an exothermic nature of the sorption process. The negative ΔG◦ values ions and the efficient optimization techniques employed.
indicate the feasibility and spontaneity of the sorption process facili­ The new ChiPA adsorbent can selectively remove heavy metals,
tated by the ChiPA adsorbent. The decreasing value of ΔG◦ suggest the namely, As(III), Cd(II), and Pd(II), with a high adsorption rate.
reduction in adsorptivity for As(III) and Pb(II). Whereas, ΔH◦ and ΔS◦
for Cd(II) is positive at higher temperature indication spontaneity of the
reaction. Hence, the optimal temperature of the adsorption of As(III), Cd 3.5. Desorption studies
(II), and Cd(II) was 298K (25 ◦ C) (Petit et al., 2015; Santos et al., 2016).
In this study, nitric acid (HNO3) was used for the desorption of heavy
3.4.2. Comparative study with other published literature metals from the chitosan adsorbent because of its capacity to replace H+
Table 2 shows the comparison of the current study with few selected ions on the surface of the adsorbent. In brief, 0.1 M HNO3 was used for
state of the art published works. Comparing the performance of the three cycles to recover Cd(II), As(III), and Pb(II) from the chitosan
ChiPA adsorbent with other chitosan-based adsorbents reveals that the adsorbent. Desorption by acidic eluents is more effective than using
ChiPA adsorbent from the present study demonstrates high adsorption other eluents. In acidic environments, the high number of H+ ions in the
solution desorbs adsorbed ions. Compared with heavy metal ions, H+

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S. Begum et al. Carbohydrate Polymer Technologies and Applications 7 (2024) 100516

Declaration of competing interest

The authors declare no competing interest.

Data availability

Data will be made available on request.

Acknowledgement

The authors would like to acknowledge Universiti Kebangsaan

Malaysia (UKM, Bangi), Malaysia and Ministry of Higher Education
Malaysia, for the financial support grant no. FRGS/1/2018/TK05/UKM/
02/4 and GUP-2017-041.

Supplementary materials
Fig. 7. Removal of different heavy metal ions with each cycle of adsorption
and desorption. Supplementary material associated with this article can be found, in
the online version, at doi:10.1016/j.carpta.2024.100516.
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