β-cyclodextrin composite

Journal Pre-proof Effective removal of acetaminophen from aqueous solution using Ca (II)-doped chitosan/β-cyclodextrin composite

Nafisur Rahman, Mohd Nasir PII:

S0167-7322(19)34889-5

DOI:

https://doi.org/10.1016/j.molliq.2020.112454

Reference:

MOLLIQ 112454

To appear in:

Journal of Molecular Liquids

Received date:

1 September 2019

Revised date:

6 December 2019

Accepted date:

2 January 2020

Please cite this article as: N. Rahman and M. Nasir, Effective removal of acetaminophen from aqueous solution using Ca (II)-doped chitosan/β-cyclodextrin composite, Journal of Molecular Liquids(2020), https://doi.org/10.1016/j.molliq.2020.112454

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© 2020 Published by Elsevier.

Journal Pre-proof

Effective removal of acetaminophen from aqueous solution using Ca (II)doped chitosan/β-cyclodextrin composite Nafisur Rahman* and Mohd Nasir Department of Chemistry Aligarh Muslim University Aligarh (U.P.), India Email: [email protected]

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Abstract

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The aim of this study was to synthesize Ca(II)-doped chitosan/β-cyclodextin and to investigate its potential as a sorbent for removal of acetaminophen from aqueous solution. The material was

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characterized by Fourier transform infrared spectroscopy, scanning electron microscopy coupled

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with energy dispersive x-ray spectroscopy, X-ray diffraction and thermogravimetric-differential

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thermal analysis. The effects of experimental parameters such as pH, adsorbent dose and initial concentration on the adsorption of acetaminophen were optimized by response surface

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methodology using central composite design. The obtained results revealed that 0.01 g of

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adsorbent was able to remove 99.88% of acetaminophen from 20.0 ml of 20.0 mg/L aqueous solution at pH 7.2. The experimental adsorption capacity for acetaminophen was found to be 200.86 mg/g. The study of isothermal adsorption data indicated that the data were best fitted to Freundlich model with high correlation coefficient (R2 = 0.999) and lower error values (

2

≤

1.70×10-5 and average percentage error ≤ 2.0×10-5) as compared to Langmuir and Temkin isotherm models. The experimental kinetic data were analyzed by pseudo first-order, pseudo second-order, Elovich and double exponential models. The kinetic data were best fitted to pseudo second order with R2 of 0.999 at all temperatures studied. The fitting of kinetic data with Elovich model (R2 > 0.99) indicted the chemisorption process whereas double exponential model suggested that the uptake of acetaminophen was governed by both film and particle diffusion processes. Negative values of ΔGo confirmed the spontaneous nature of

Journal Pre-proof acetaminophen adsorption onto Ca (II)-doped chitosan/ β-cyclodextrin composite. Positive values of ΔHo (116. 404 kJ/mole) and ΔSo (0.438 kJ/mole) confirmed the endothermic nature of adsorption

process

and

randomness

at

solid

/liquid

interface,

respectively.

The

adsorption/desorption cycling test revealed that the prepared composite material had good reusability performance upto 6 cycles. The results demonstrated that the material could be a promising adsorbent for removal of acetaminophen from aqueous solution.

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Keywords

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Chitosan; β-cyclodextrin; acetaminophen; adsorption; central composite design

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1. Introduction

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The presence of pharmaceuticals in the aquatic system has become an environmental issue

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throughout the world. Pharmaceuticals have been recognized as emerging pollutants. These emerging pollutants have been detected at trace level in water samples but their adverse effect

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on humans and animals is very high. Acetaminophen is commonly used as analgesic and antipyretic drug with some anti-inflammatory activity for humans and animals. Therapeutic dose

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in adults is 1-4 g/day. At therapeutic dosage acetaminophen is excreted in urine as glucuronide (45-55%), sulphate (20-30%) and cystien (15-55%). Approximately 2% of acetaminophen is excreted unchanged [1]. Most of the pharmaceuticals including acetaminophen are introduced into the aquatic environment through domestic sewage [2], industrial wastewater [3] and hospitals [4, 5]. In addition, pharmaceuticals were found in the vicinity of municipal wastewater discharge and livestock agricultural facilities [6]. Acetaminophen is generally found in wastewaters at a concentration of about 30-40 µg/L [7]. It was also detected at high concentration (about 400 µg/L) in wastewaters originating from pharmaceutical industries and hospitals [8]. Acetaminophen (0.11-10.0 µg/L) has been found in the surface water in the United States [9]. The concentration of acetaminophen in Canadian wastewater treatment plant effluents

Journal Pre-proof was found to be as high as 62 µg/L [10]. The toxic effect was studied by exposing rainbow trout to acetaminophen (10 µg/L–30 µg/L). This study revealed that the changes occurred in kidney, gill and liver functions [11]. Therefore, wastewater containing acetaminophen must be treated before its discharge. The unique cavity structure of β-cyclodextrin is helpful in recognizing a variety of guest molecules and form specific host-guest inclusion complexes [12]. β-Cyclodextrin has excellent-

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biocompatibility and powerful functionalization capacity which make them attractive for

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tailoring functional materials for removal of organic pollutants [13, 14]. Chitosan is widely used as sorbent and having the ability to be grafted with various functional groups using a variety of

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cross-linking agents [15]. Chitosan/waste coffee-grounds based composite was prepared and

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examined its performance in the removal of pharmaceuticals from water [16]. Chitosan modified

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vermiculate was examined for adsorption of As (III) and reusability performance was determined [17]. Wilson et al. have developed an adsorbent by crosslinking chitosan and β-

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cyclodextrin with glutaraldehyde. This material was used to remove p-nitrophenol from aqueous

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solution [18]. Jiang et al. have synthesized chitosan/β-cyclodextrin polymer by crosslinking with glutaraldehyde. The adsorption behaviour of crosslinked chitosan/β-cyclodextrin was studied for removal of methyl orange from water [19]. Recently, magnetite nanoparticles modified βcyclodextrin polymer was used to adsorb acetaminophen at pH 7.0. The adsorption capacity for acetaminophen was 128.90 mg/g [20]. Chitosan coated granular activated carbon showed adsorption capacity of 16.67 mg/g for acetaminophen [21]. To enhance the adsorption capacity, attempt was made to prepare cross-linked chitosan/β-cyclodextrin polymer. Therefore, it is important to investigate the adsorption performance of such type of materials.

Journal Pre-proof Various treatment methods are available for the removal of pollutants such as advanced oxidation [22-25], photocatalytic degradation [26], electrochemical discharge [27], membrane filtration [28], biological process [29] and adsorption [30-34]. These methods, except adsorption, required high experimental setup and hence more expensive. Adsorption is considered as one of the most potential and promising technique as well as ecofriendly. Villaescusa et al [35] have investigated the potential use of grape stalk waste as adsorbent for removal of acetaminophen. The feasibility of coconut shell waste was tested for uptake of

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acetaminophen from synthetic solution [21]. Hexadecyl trimethylammonium modified kaolinite

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was used for the removal of acetaminophen [36]. Activated carbon derived from chicken bone

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was found to be effective in the removal of acetaminophen from water [37, 38]. Graphene

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nanoplates have been studied as sorbent for uptake of acetaminophen [39].

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Response surface methodology (RSM) is used to investigate relative significance of several independent variables, even in the presence of complex interactions and predict the optimum

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operating conditions for desirable response [40-42]. The applications of RSM approach in

and overall cost.

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adsorption process development is helpful in reducing the process variability, development time

The objective of this study was to synthesize and characterize the Ca (II)-doped chitosan/βcyclodextin composite and to investigate its potential in the removal of acetaminophen. The combined effects of adsorbent dose, initial concentration and pH on the removal of acetaminophen by Ca (II)-doped chitosan/β-cyclodextin were investigated using central composite design (CCD) under RSM. Isotherm models were tested to fit the adsorption data. The experimental kinetic data were analyzed to understand the mechanism of adsorption process. Thermodynamic parameters were also calculated.

Journal Pre-proof 2. Experimental 2.1. Materials β-Cyclodextrin (99%, Sigma-Aldrich, St. Louis,USA), chitosan (high molecular weight, deacetylation: > 75%, Himedia Laboratories, India), glutaraldehyde (Merck Specialties, India) and acetic acid (Merck Specialties, India) were used for the synthesis of chitosan/β-cyclodextrin composite material. Calcium chloride dihydrate was obtained from Merck Life Science, India.

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Acetaminophen was purchased from Sigma- Aldrich (St. Louis, USA).

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2.2. Instruments

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UV-VIS spectrophotometer (Model UV-1800, Shimadzu, Japan) was used to determine

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acetaminophen concentration in UV range. Fourier transform infrared (FTIR) spectra were

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recorded on FTIR spectrophotometer (Spectrum 2, Perkin-Elmer, USA) Simultaneous thermogravimetry-differential thermal analyses were done on thermal analyser (DTG 60H,

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Shimadzu, Japan) at the heating rate of 10oC/min. X-ray powder diffractometer (Bruker AXS D8 Advance, Germany) with a Cu X-ray source kα (λ = 0.154 Ao) was employed to investigate

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the sample. SEM with EDX (JEOL JSM-6510LV, Japan) was used as a tool to study the surface morphology and determine the elemental composition of the adsorbent. 2.3. Synthesis of Ca (II) doped chitosan/β-cyclodextrin composite material. Synthesis of the material was performed in two steps. First step involves the formation of chitosan/β-cyclodextrin composite. In this step, 2.0 g chitosan flakes (high molecular weight) were dissolved in 100 mL of acetic acid (2% v/v) and stirred at room temperature for 6h. To this, β-cyclodextrin (1.0 g) was added and stirred further for next 90 minutes. 20.0 mL of 5% glutraldehyde as a crosslinking agent was added in the resulting mixture and stirred until whitish

Journal Pre-proof mixture turned into light yellow hydrogel. To ensure complete crosslinking between chitosan

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and β-cyclodextrin the resulting light yellow hydrogel was kept at 4oC for 24h (Scheme 1).

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Scheme 1: Synthesis route of chitosan/β-cyclodextrin composite

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In the second step, the doping of Ca2+ was carried out by adding 50.0 mL of 0.10M calcium

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chloride solution in the light yellow hydrogel of chitosan/β-cyclodextrin and stirred for 2 h. A dark yellow precipitate was obtained and then filtered, washed thoroughly and dried at 50oC for 8 h. The composite material was sieved to obtain particles of uniform size (Scheme 2).

Scheme 2: synthesis of Ca (II) doped chitosan/β-cyclodextrin composite.

Journal Pre-proof 2.4. Chemical Stability In order to determine the chemical stability, 200 mg portions of Ca (II)-doped chitosan/βcyclodextrin were placed in 25.0 ml of different concentrations of HCl (0.01-0.5M), and NaOH (0.01-0.2M) and water. The resulting mixture was agitated for 1 h. The supernatant liquid was analyzed for Ca(II) by flame photometry, chitosan and β-cyclodextrin were determined by spectrophotometry using ninhydrin [43] and phenolphthalein [44] as reagents, respectively,

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2.5. Adsorption study

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2.5.1. Effects of contact time and temperature

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A fixed amount of adsorbent (0.01 g) was added to acetaminophen solution (20.0 mL) having an

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initial concentration of 20.0 mg/L and pH 7.2. The resulting mixture was agitated on a shaker

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for different time intervals (10-170 min) at four different temperatures (300, 305, 310 and 3015 K). The adsorption capacity was calculated at each time interval.

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2.5.2. Effects of pH, adsorbent dose and initial concentration of acetaminophen

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Experiments were performed according to experimental design generated from CCD. HCl or NaOH solution was used to adjust the pH of acetaminophen solution ranging from 1.82 to 12.58. A known amount of Ca (II) doped chitosan/β-cyclodextrin (0.01 to 0.03 g) was added to the acetaminophen solution (20.0 mL) of varying concentrations ranging from 3.18 to 36.88 mg/L in 50.0 mL conical flasks. The resulting mixture was agitated on a shaker for 130 min. at desired temperature (300K, 305K, 310K and 315K). After shaking, it was filtered and acetaminophen concentration was determined by measuring absorbance at 243 nm. The percentage removal and adsorbed amount of acetaminophen (qe; mg/g) onto Ca (II) doped chitosan/β-cyclodextrin were computed by using the following equations:

Removal efficiency (%) =

(1)

Journal Pre-proof (

)

(2)

where qe, Co and Ce are the adsorption capacity (mg/g), initial and equilibrium concentrations (mg/L) of acetaminophen, respectively. M and V are the mass of Ca (II) doped chitosan/βcyclodextrin (g) and volume of solution (L), respectively. The contact time was fixed at 130 min. according to the results obtained from preliminary studies.

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2.6. Experimental design and optimization

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RSM is applied under different classes such as CCD, Box-behnken design (BBD) and three level factorial design to correlate different variables with their responses. CCD is one of the

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most widely used optimizing technique which provides the limited number of experimental runs

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to modeling of optimizing parameters and their interactions [45, 46]. In CCD the total number of

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experimental runs is based on three operations such as 2k axial runs, 2k factorial runs and Cp which can be calculated by using the equation [47]:

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Total number of experiments = 2k + 2k + Cp

(3)

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where k and Cp are the number of factors and center points, respectively. Experimental design involves 6 axial points, 8 factorial points and 6 replicate number of central point. Hence a total of 20 experiments were performed involving 3 factors (A: pH, B: adsorbent dose and C: initial concentration) with each five levels (-1, +1, 0, -α and +α) design (Table S1).\ The design matrix and removal of acetaminophen (%R) as response are presented in Table 1. The approximate distance between axial point and central point represented by α is used to check the rotatablilty and orthogonality. The values of α can be obtained from equation 4 [48]: (4)

Journal Pre-proof The multiple regression analysis of adsorption data provided the second-order polynomial equation to predict the response (equation 5) [49]: ∑

∑

∑

∑

(5)

where Y, Xi and Xj are the predicted removal (%); and coded values of factors. β0, βi, βii and βij are the regression coefficients for the intercept, linear, quadratic and interaction terms, respectively. Design Expert program (free trial 12.0.1.0 version) was used to process the

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adsorption data for equation 5.

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2.7. Desirability function approach

Desirability function was used to optimize several responses simultaneously to achieve the

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desired performance of the adsorption process [50, 51]. In this approach, each measured

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response is converted to desirability value di. The scale of individual desirability function is 0 ≤ di ≤ 1. For completely undesired response, the value of di = 0 whereas di = 1 for fully desired

)

⁄

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(

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response. The overall desirability function (D) was computed using the following expression:

(6)

where p denotes the number of responses. In order to achieve the goal of maximum, the individual desirability function is expressed as:

[

(

)

]

(7)

where Ri is the response value, Rmin and Rmax are the minimum and maximum acceptable values for response and w is the weight used to estimate desirability scale.

Journal Pre-proof 2.8. Error function analysis Error functions such as Chi-square (χ 2), and the average percentage error (APE) are used to judge the fitness of the isotherm and kinetic models to the experimental data.

and APE can be

calculated using the following equations:

∑

)

∑

|(

(8) )

|

(9)

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( )

(

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wher N is the number of observations in the experimental data.

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2.9. Real water samples

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In order to study the efficiency of Ca (II) doped chitosan/β-cyclodextrin for removal of

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acetaminophen, two water samples (tap water and municipal wastewater) were collected locally. Both samples were filtered through 0.45 µm Millipore filter paper and kept in Teflon bottles.

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The properties of water samples are given in Table 2.

3. Results and discussion

The cross-linking of chitosan and β-cyclodextrin was carried out by glutraldehyde. The crosslinking occurs between amino groups of chitosan and glutaraldehyde [52]. Glutaraldehyde and β-cyclodextrin was crosslinked through aldol condensation [53]. In this study, Ca (II) was doped into cross-linked chitosan/ β-cyclodextrin composite through Ca-O and Ca-N linkages to adsorb acetaminophen due to the presence of numerous functional groups and inclusion binding sites. Scheme 2 shows the idealized view of the structure of cross-linked chitosan and β-cyclodextrin doped with ca (II) ions. The chemical stability of the sorbent is an important parameter that is needed for batch operation. The chemical stability of Ca (II)-doped chitosan/β-cyclodextrin composite was

Journal Pre-proof examined in different concentration of HCl and NaOH along with distilled water. The results revealed that the sorbent is fairly stable in 0.5 M HCl, distilled water and 0.2 M NaOH. Moreover, no leaching of any component of Ca (II)-doped chitosan/β-cyclodextrin was observed in these solutions. 3.1. Characterization: FTIR spectrum of Ca (II)-doped chitosan/β-cyclodextrin is shown in Fig. 1a. The absorption

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band peaking at 3441cm-1is ascribed to the O-H and –NH stretching vibrations. The absorption

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bands centered at 2930 cm-1 and 2847 cm-1 pointed towards symmetric and asymmetric

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stretching vibrations of C-H bond [19, 54]. A strong absorption peak at 1591 cm-1 corresponds to the N-H deformation vibrations associated with chitosan part of the material [55]. The

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absorption band appearing at 1685 cm-1 is assigned to C=N which confirmed the cross linking

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between amine groups of chitosan and aldehyde groups of glutaraldehyde [18].

The

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characteristic band associated with free aldehyde group near 1720 cm-1 is absent which further confirmed the cross linking of amino group with aldehyde of glutraldehyde [56]. The absorption

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peak at 1423 cm-1 and 1322 cm-1 indicated the >CH2 bending vibration in CH2OH group and CH bending in pyranose ring [58]. The C-O stretching vibration of –CH2-OH is presented by the absorption band centered at 1091 cm-1. The absorption bands at 1174 cm-1 and 1015 cm-1 correspond to symmetrical and asymmetrical C-O-C glycosidic linkage [57]. The absorption bands appearing at 932 cm-1 and 852 cm-1 are assigned to α-pyranyl and α-(1,4) glycopyranose of β-cyclodextrin, respectively [58]. The absorption bands at 682 cm-1 and 629 cm-1 arise from N-H out of plane and O-H out of plane vibrations, respectively. Two distinct peaks appearing at 549 cm-1and 474 cm-1 were assigned to Ca-O and Ca-N stretching vibrations [59, 60], respectively. This demonstrated that the calcium was incorporated into chitosan/β-cyclodextrin composite.

Journal Pre-proof SEM image of Ca (II)-doped chitosan/β-cyclodextrin composite is shown in Fig. 1b. The surface of the material is more rough and heterogeneous. Pores of varying dimensions are seen on the surface which may provide high surface area for adsorption of acetaminophen. The presence of calcium peak in EDX spectrum (Fig. S1) confirmed the successful incorporation of calcium onto chitosan/β-cyclodextrin. Fig. 1c shows the X-ray diffraction pattern of Ca (II)doped chitosan/β-cyclodextrin. The X-ray diffractogram displayed a strong peak at 2ϴ = 19.361

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with d-spacing of 4.581 Ao.

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The thermal characteristics of the Ca (II)-doped chitosan/β-cyclodextrin were investigated using thermogravimetric-differential thermal analysis (TGA-DTA). Fig. 1d shows two degradation

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steps. The first step (110oC-210oC) was due to the elimination of water molecules bound onto

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the adsorbent. The weight loss of about 46.37% was observed in this region. DTA curve (Fig.

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1d) showed an endothermic peak at 208oC which confirmed the elimination of water molecules. The second thermal event extended from 220oC-525oC was assigned to the degradation of

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crosslinking among the chitosan, β-cyclodextrin and Ca (II) moieties. The weight loss in this region was 55.4%. The destruction of organic moiety is also confirmed by the presence of an

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exothermic peak in DTA curve. After 525oC, no appreciable weight lost was noticed which indicated the formation of calcium oxide. 3.2. Effects of contact time and temperature Adsorption experiments were performed as a function of contact time. The results are shown in Fig. S2. As can be seen in the Fig. S2, that equilibrium was attained at 130 min. Similar results were reported for adsorption of methyl orange and rhodamine B onto carbon obtained from waste tires [34, 61]. The effect of temperature on the adsorption capacity is shown in the Fig. S2. The results revealed that adsorption capacity increases with increasing temperature from 300

Journal Pre-proof to 315K. The increase in temperature favors the interaction of acetaminophen with Ca (II)-doped chitosan/β-cyclodextrin. 3.3. Statistical analysis and model fitting The experimental adsorption data were analyzed by linear, two-factor interaction and quadratic models to find the appropriate regression equation. The statistical parameters of the polynomial models are given in Table S2. The fitness of the model was deduced on the basis of R2 and its

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significance was confirmed by F-test [62]. The value of F for quadratic model is larger (33.72),

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indicating its significance. The values of R2 are 0.6606, 0.6905 and 0.9998 for linear, 2-factor

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interaction and quadratic models, respectively. The higher the value of R2, better will be the model. Moreover, the quadratic model has maximum adjusted R2 and predicted R2 values

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compared to linear and 2-factor interaction models. The results demonstrated that the quadratic

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expressed by the following equation:

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model is able to predict the response accurately. The quadratic model in the coded units is

16.13B2 -6.46C2.

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Removal (%) = +99.88 -0.4065A+1.05B+0.2815C +0.9075AB +0.0650AC+1.81BC -33.15A2 (10)

The results of analysis of variance (ANOVA) are summarized in Table S3. The F-value of 40546.33 demonstrated the statistically significance of quadratic model. In addition, the model terms are considered significant only when p < 0.05 and therefore, A, B, C, AB, BC, A2, B2 and C2 are significant model terms. The model term AC is insignificant because its p-value is 0.4314. In order to improve the predictability of the responses, the insignificant term AC determined by ANOVA was eliminated from the equation (10). The reduced quadratic equation in terms of coded factors is expressed as: Removal (%) = +99.88 -0.4065A +1.05B +0.2815C +0.9075AB +1.81BC -33.15A2 -16.13B26.46C2.

(11)

Journal Pre-proof The percent removal as predicted by equation (10) is summarized in Table 1. The standard deviation of the quadratic model is 0.244 which further confirmed the goodness of fit. The plot of the experimental and predicted percent removal of acetaminophen (Fig. S3) shows that the data points are almost lying on the straight line (R2 = 0.9999) which demonstrated the good relationship between experimental and predicted values of the percent removal of acetaminophen.

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3.4. Response surface analysis

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The three dimensional surface plot is used to study the interaction between two variables by

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keeping the third factor at its center level. The effect of pH and adsorbent dose on removal (%) with initial acetaminophen concentration of 20.0 mg/L is shown in Fig. 2 (a). The downward

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curvatures for both adsorbent dose and pH trend are agreement with negative quadratic terms A2

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and B2 of the reduced model. When the pH is increased from 2.0 to 7.2 (keeping initial

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concentration of acetaminophen constant at center level), then acetaminophen removal was enhanced from 13.58% to 99.88%. Above pH 7.2, the removal efficiency (%) decreases.

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Simultaneously, the removal (%) also increases with increasing adsorbent dose. The maximum removal was obtained with 0.01 g of the adsorbent. The combined effect of adsorbent dose and initial concentration of acetaminophen on removal efficiency (%) with a pH of 7.2 is displayed in Fig. 2 (b). Slight downward curves of both acetaminophen concentration and adsorbent dose are in accordance with negative quadratic terms B2 and C2 of the reduced model. The increase in adsorbent dose causes increase in removal efficiency whereas percent removal decreases with increasing initial concentration of acetaminophen.

Journal Pre-proof 3.5. Optimization using desirability function Fig. S4 shows the ranges used for pH (4-10.4), adsorbent dose (0.005-0.015 g) and initial concentration of acetaminophen (10-30 mg/L) while the percentage removal was designed to achieve the maximum value. The maximum removal (99.88%) was achieved with an initial acetaminophen concentration of 20.0 mg/L, initial pH of 7.2 and adsorbent dose of 0.01g. Experiments were performed in duplicate using the optimum values of input variables. The experimental results are in good agreement with the predicted responses. This demonstrated the

Equilibrium modeling

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3.6.

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suitability and adequacy of the model.

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The experimental data for the uptake of acetaminophen by Ca (II)-doped chitosan/β-

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cyclodextrin were studied using Langmuir, Freundlich and Temkin isotherm models.Table S4 shows the linear equations of these isotherm models. Langmuir (Fig. S5), Freundlich (Fig. 3)

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and Temkin (Fig. S6) isotherm plots were used to calculate the isotherm parameters (Table 2).

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The adsorption capacity for acetaminophen was found to be 200.0, 200.79 and 187.14 mg/g from Langmuir, Freundlich and Temkin isotherm plots ,respectively. APE and

2

values were

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calculated which are given in Table 3. The values of R2 for Freundlich isotherm (0.999) are greater than that for Langmuir (0.977-0.990) and Temkin isotherm (0.916-0.968) models at all temperatures studied. Moreover, APE (1.1×10-5 – 2.0×10-5) and

2

(2.3×10-5 -1.7×10-5) values

for Freundlich isotherm model as compared to Langmuir model (APE = 0.004-0.020; 0.099) and temkin model (APE = 0.068-0.107;

2

2

=0.003-

= 0.937-2.646). Therefore, it is concluded that

the Freundlich isotherm model could fit the adsorption data better than other models. 3.7.

Adsorption kinetics

Kinetic behavior of acetaminophen adsorption onto Ca (II)-doped chitosan/β-cyclodextrin was investigated at a fixed concentration of acetaminophen (100 mg/L) and at temperatures 300,

Journal Pre-proof 305, 310 and 315 K. The data were investigated by pseudo-first order, pseudo-second order Elovich, and double exponential models. The pseudo-first order kinetic model is given as [63]: (

)

(

)

(12)

The pseudo-second order kinetic model is expressed as [64]: ( )

(13)

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where qt and qe are the amount of pollutant adsorbed (mg/g) at time t and at equilibrium,

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respectively; k1 and k2 represent rate constants for pseudo-first order (min-1) and pseudo-second

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order (g/ mg/ min), respectively. Fig S7 shows the linear plots of log (qe- qt) vs t. The kinetic parameters were calculated from the straight line plot and summarized in Table 4. The linear

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plots of t/qt vs t at 300, 305, 310 and 315 K are shown in Fig 4. The values of qe (simulated) and

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k2 were computed from the intercept and slope of the straight line, respectively (Table 4). In case of pseudo-first order kinetic model, the values of R2 varies from 0.963 to 0.991 over the

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temperature range of 300-315 K. The calculated qe values deviated to a great extent from the

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experimental values (qe) at all temperatures studied. The calculated qe is very close to experimental qe values for the pseudo-second order kinetic model. Moreover, values of R2 proved that the adsorption of acetaminophen was well explained by pseudo second order kinetic model. Similarly, the adsorption of Sb (III) onto polyamide-graphene composite was best explained by pseudo second order kinetic model [65] Elovich model has been applied to describe the adsorption of pollutants on energetically heterogeneous surface of sorbent from aqueous solution. Elovich model is expressed as [66]: (

)

(14)

where α is the initial acetaminophen sorption rate (mg/g/min) and β is adsorption constant (g/ mg). Fig. 5 shows the plots of qt vs ln t at different temperatures and kinetic parameters were

Journal Pre-proof calculated and presented in Table 4. It is evident that the experimental data at all temperatures fitted well to the Elovich model. This is confirmed by high values of correlation coefficient. The value of α increases with increasing temperature. The results of this study are in agreement with those obtained from the pseudo-second order model. It can be concluded that the interaction of acetaminophen with Ca (II)-doped chitosan/β-cyclodextrin is chemisorption. Double-exponential model is mathematically expressed as [67]:

(

)

of

)

(15)

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(

where D1 and D2 are the adsorption rate parameters of rapid and slow steps, respectively (mg/L).

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KD1 and KD2 are the diffusion parameters (min-1) controlling the rapid and slow sorption process,

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respectively. ma is the mass of adsorbent (g/L). When KD1>> KD2 then the exponential term

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corresponding to rapid step is considered negligible on overall kinetics and equation (14) is simplified as: )

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(

(16)

(

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The linearization of the above equation gives )

(17)

The values of D2 and kD2 can be evaluated from the intercept and slope of linear plot of ln (q e-qt) vs t (Fig. 6). The parameters D1and kD1 can be obtained from the equation given below and summarized in Table 5. (

)

(18)

Rapidly and slowly adsorbed fraction (RF and SF) can be calculated using the equations: (

)

(19)

(

)

(20)

Journal Pre-proof Double exponential model parameters for rapid and slow step along with the regression coefficient (R2) are summarized in Table 5. It is evident that the values of D1 increases from 134.289 to 160.000 with increasing temperature from 300 to 315 K whereas the values of kD1 changes from 0.10 to 0.017 over this temperature range for the rapid step. In rapid step major fraction of acetaminophen was adsorbed on Ca (II)-doped chitosan/β-cyclodextrin (82.82983.803%). In slow step, the values of D2 were much lower than that for the rapid step and fraction of acetaminophen adsorbed on the adsorbent was also lower (17.710-16.197%). The

of

rapid step involves external and internal diffusion and is mainly dependent upon the affinity of

ro

acetaminophen for the Ca (II)-doped chitosan/β-cyclodextrin. Moreover, the slow step is

Adsorption mechanism

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3.8.

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governed by intraparticle diffusion.

Adsorption was carried out in the pH range of 1.81-12.58 to ascertain the effect of pH on the

lP

adsorption of acetaminophen. Acetaminophen is a weak electrolyte which coexists in both non-

na

ionized and ionized forms of acetaminophen. The extent of interaction of the species with adsorbent determines the adsorption capacities. The non-ionized and ionized species of

Jo ur

acetaminophen depends on the solution pH and pka of acetaminophen (pka ≈ 9.38). It was observed that approximately 90% of acetaminophen remains in non-ionized form upto pH 7.2 [68]. The ionization of acetaminophen occurs in basic medium and approximately 90% of the acetaminophen is ionized at pH 11 [68]. At acidic pH, the amino groups of chitosan can undergo protonation to form –N+H3. The extent of protonation depends on the pH of solution as pka of chitosan is 6.5 [69]. Additionally, the –OH groups of β-cyclodextrin may also be protonated [70]. In acidic medium, β-cyclodextrin is mainly positively charged which hinders the interaction of acetaminophen with surface of the adsorbent and reduce the adsorption capacity. As the pH increases from 2.0 to 7.2 the percentage removal of acetaminophen increases from 13.84 to 99.88%. At pH 7.2, the fraction of non-charged –NH2 group is 0.888 [68] which favors

Journal Pre-proof the hydrogen bond formation with acetaminophen. Additionaly, Ca2+ forms complex with acetaminophen [71]. Moreover, the interior cavity of β-cyclodextrin which is hydrophobic in nature takes up acetaminophen through hydrogen bonding with hydroxyl groups of βcyclodextrin. In addition, the uptake of acetaminophen is also favored by π-π

interaction

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between phenolic ring of acetaminophen and glucose monomer (Scheme 3).

3.9.

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cyclodextrin composite

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Scheme 3: Mechanism for the adsorption of acetaminophen onto Ca (II)-doped chitosan/β-

Thermodynamic studies

The thermodynamic parameters for the acetaminophen adsorption onto Ca (II)-doped chitosan/β-cyclodextrin composite were evaluated by using the following equations: ΔG0 = -RT lnkc

(21) (22)

Where kc is the equilibrium constant. Thermodynamic studies were performed at 300K, 305K, 310K and 315K, The values of kc were calculated following the method reported by Milonjic [72]. The values of negative value of

and

were calculated from the plots of ln kc vs 1/T (Table S5). The

indicated towards the feasibility and spontaneity of adsorption of

acetaminophen onto Ca (II)-doped chitosan/β-cyclodextrin composite. The value of

Journal Pre-proof decreases from -34.107 to -39.812 k J/mol as the temperature increases from 300 K to 315 K (Fig. S5). The value of

was found to be 116.404 k J mol-1 which indicated that the

adsorption of acetaminophen on Ca (II)-doped chitosan/β-cyclodextrin composite was endothermically driven process. In a similar fashion, thermodynamic parameters exposed the endothermic nature for adsorption of methylene blue onto magnetic loaded activated carbon [73]. The value of

was found to be 0.438 k J/ mol which suggested the randomness on the

sorbent/ solution interphase.

of

3.10. Comparison of Ca (II)-doped chitosan/β-cyclodextrin composite with other

ro

adsorbents

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Table 6 shows the comparison of adsorption capacity of Ca (II)-doped chitosan/β-cyclodextrin

re

composite for acetaminophen with that of the other sorbents used earlier. The adsorption

lP

capacity of Ca (II)-doped chitosan/β-cyclodextrin for acetaminophen is higher than that of other sorbents except colloidal particles [87]. The drawback associated with colloidal particles is that

na

it required 720 minutes to achieve the equilibrium. Therefore, it can be concluded that the prepared Ca (II)-doped chitosan/β-cyclodextrin is a promising and useful adsorbent for removal

Jo ur

of acetaminophen from aqueous solution. 3.11. Environmental applications

The application of Ca (II)-doped chitosan/β-cyclodextrin in the removal of acetaminophen was explored using real environmental water samples: tap water and municipal wastewater. Acetaminophen was not detected in the selected water samples. Therefore, real water samples were spiked with 0.4 mL of 1000 mg/L acetaminophen solution to 20.0 mL of real water samples to obtain a final concentration of 20.0 mg/L. The 0.01g of adsorbent was added to the spiked samples and agitated for 130 min. The amount of remaining acetaminophen was determined in aqueous phase. The percentage removal of acetaminophen was found to be 97.4% and 96.8% for tap water and municipal wastewater, respectively.

Journal Pre-proof 3.12. Reuse and regeneration Desorption of acetaminophen from acetaminophen loaded Ca (II)-doped chitosan/β-cyclodextrin was carried out by treating with 20.0 mL of 0.3M HCl solution for 1h. The adsorbent was removed by filtration and regenerated by treating with 0.1M NaOH solution. The adsorption of acetaminophen onto Ca (II)-doped chitosan/β-cyclodextrin followed by desorption with 0.3M HCl solution upto 6 cycles were investigated. Results (Fig. 7) revealed that the adsorption of

of

acetaminophen on the regenerated adsorbent was negligibly affected upto 2 cycles. Similar

ro

results were reported for reuse of titania-incorporated polyamide [88]. Moreover, percent adsorption gradually decreased from 99.80% to 96.00% with increasing regeneration cycles

-p

from 2 to 6. The adsorption/desorption tests demonstrated that Ca (II)-doped chitosan/β-

Conclusions

lP

4.

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cyclodextrin can be effectively used for acetaminophen removal from contaminated water.

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Calcium(II) was successfully incorporated into crosslinked chitosan/β-cyclodextrin .The material showed enhanced adsorption capacity for acetaminophen. The incorporation of calcium

Jo ur

was confirmed by EDX spectrum. The adsorption of acetaminophen onto Ca (II)-doped chitosan /β-cyclodextrin was performed in batch mode and equilibrium was attained in 130 min. The optimization of adsorption process was carried out using three independent variables such as pH, adsorbent dose and initial concentration of acetaminophen. Central composite design under RSM was applied to get the optimum value of pH, adsorbent dose and initial concentration of acetaminophen. Under the optimized conditions, the removal efficiency was found 99.88%. The equilibrium data were analyzed by Langmuir, Freundlich and Temkin isotherm models. Among these ,Freundlich isotherm model was more appropriate with higher correlation coefficient value for acetaminophen removal. Thermodynamic studies at various temperatures pointed towards the spontaneous and endothermic nature of the adsorption process. The higher adsorption

Journal Pre-proof capacity (200.79 mg/g) and higher removal efficiency revealed that Ca (II)-doped chitosan/βcyclodextrin is a promising adsorbent for practical implication to meet the industrial need.

Acknowledgment Aligarh Muslim University, UGC (DRS-II) and DST (FIST and PURSE) are thankfully

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acknowledge for instrumentation and other facilities.

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Removal of analgesic paracetamol from wastewater using dried olive stone., Int. J. Mech. Eng. Technol., 19 (2018) 293-299. [83]

S. Parmar, D.S. Sharma, D.A. Sharma, D.S. Verma, Removal of acetaminophen from waste water using low cost adsorbent., Int. Res. J. Eng. Technol., 5 (2018) 1025-1031.

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Y. Zhao, S. Yang, G. Wang, M. Han, Adsorption Behaviors of Acetaminophen onto the Colloid in Sediment., Pol. J. Environ. Stud., 24 (2015), 853-861. I. Ali, S.A. AL-Hammadi, T.A. Saleh, Simultaneous sorption of dyes and toxic metals from waters using synthesized titania-incorporated polyamide, J. Mole. Liquids, 269

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(2018) 564–571.

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[88]

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Figures

Fig. 1: (a) FTIR spectrum of Ca (II)-doped chitosan/β-cyclodextrin composite.(b) SEM

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image of Ca (II)-doped chitosan/β-cyclodextrin composite. (c) X-ray diffraction pattern of Ca

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(II)-doped chitosan/β-cyclodextrin composite. (d) TGA and DTA curves of Ca (II)-doped chitosan/β-cyclodextrin composite.

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Fig. 2: 3D response surface plots showing the effect of (a) pH and adsorbent dose (keeping initial concentration at central level; Ce = 20 mg/L), (b) initial concentration and adsorbent dose (keeping pH at central level; pH = 7.2) on the removal of acetaminophen.

Fig. 3: Freundlich isotherm plots for the adsorption of acetaminophen onto Ca (II)-doped chitosan/β-cyclodextrin composite (pH = 7.2; dose = 0.01 g/20mL; contact time 130 min).

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Fig. 4: Pseudo-second order kinetic plots for the acetaminophen adsorption onto Ca (II)-

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doped chitosan/β-cyclodextrin composite (Co = 100 mg/L, pH = 7.2, dose 0.01g/20mL).

Fig.5: Elovich plots for the acetaminophen adsorption onto Ca (II)-doped chitosan/βcyclodextrin composite (Co = 100 mg/L, pH = 7.2, dose 0.01g/20mL).

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Fig.6: Double exponential plots for the acetaminophen adsorption onto Ca (II)-doped

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chitosan/β-cyclodextrin composite (Co = 100 mg/L, pH = 7.2, dose 0.01g/20mL).

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% Remval

95

85

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80 75

1

2

3

4

5

6

Cycles

Fig.7: Reuse and regeneration studies of Ca (II)-doped chitosan/β-cyclodextrin composite.

Journal Pre-proof Tables

Table 1: Central composite design matrix with experimental and predicted values of acetaminophen removal by Ca (II) doped chitosan/β-cyclodextrin. A

B

C

1

-1

+1

-1

Observed response (%) 42.68

2

0

0

0

99.88

99.88

3

-1

-1

0

46.15

45.99

4

-1

-1

+1

42.84

42.81

5

0

-α

0

6

0

0

0

7

0

+α

0

8

-1

+1

+1

9

0

0

10

0

0

11

-α

0

12

0

0

13

+1

+1

14

0

0

15

+1

16

+α

17

0

18

+1

19

+1

20

0

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Exp. Run

Predicted response (%) 42.66

52.48

99.88

99.88

56.21

56.01

46.45

46.71

0

99.88

99.88

0

99.88

99.88

0

6.85

6.79

-α

80.85

81.14

-1

43.57

43.53

0

99.88

99.88

-1

-1

43.57

43.24

0

0

5.25

5.42

0

+α

82.28

82.09

-1

+1

40.36

40.31

+1

+1

47.76

47.84

0

0

99.88

99.88

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52.18

Journal Pre-proof Table 2: Compositions of water samples

Tap water 6.80 460.00 210.00 315.00 240.40 65.00 35.40 0.21 62.40 71.50 ND

Wastewater 7.10 580.00 248.00 330.00 265.60 70.00 39.00 0.24 67.56 92.40 ND

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Parameters pH TDS (mg/L) Total alkalinity (mg/L) Total hardness (mg/L) Sodium (mg/L) Calcium (mg/L) Magnesium (mg/L) Fe3+ (mg/L) Chloride (mg/L) Sulphate (mg/L) Acetaminophen (mg/L)

Langmuir

300 305 310 315

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Temperature (K)

qm* (mg/g)

200.00 217.39 232.55 238.10

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Isotherm

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Table 3: Isotherm parameters for the acetaminophen adsorption by Ca (II)-doped chitosan/βcyclodextrin composite.

qm (mg/g)

Freundlich

300 305 310 315

300 305 310 315

Parameters KL (L/mg) R2

Error function 2 APE

0.725 0.638 0.672 0.913 Parameters n KF

0.004 0.012 0.020 0.015

200.79 4.66 214.29 4.38 227.52 234.50 qm (mg/g) 187.14 191.99 203.23 212.76

0.990 0.984 0.977 0.987

92.15 95.12

2

R

0.999 0.999

4.07 99.90 0.999 3.85 105.07 0.999 Parameters AT BT R2 161.74 469.65 351.77 278.94

21.35 19.92 22.27 24.30

0.968 0.916 0.917 0.933

0.003 0.033 0.099 0.053

Error Function 2 APE

2.0×10-5 1.0×10-5 1.2×10-5 1.1×10-5

1.3×10-5 1.5×10-5 1.7×10-5 1.3×10-5

Error Function 2 APE

0.068 0.937 0.105 2.400 Temkin 0.107 2.646 0.092 2.026 * The experimental values of adsorption capacity (qe) for acetaminophen are 200.86, 214.70, 227.78 and 234.56 mg/g at 300, 305, 310 and 315 K, respectively.

Journal Pre-proof Table 4: Kinetic parameters for acetaminophen adsorption onto Ca (II) doped chitosan/βcyclodextrin hybrid material

R2

58.14

0.016

0.963

305

70.58

0.021

0.986

310

57.81

0.020

0.971

315

73.01

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Parameters K1

300

0.025

0.991

qm(mg/g)

Parameters K2

310

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315

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305

R2

165.93

0.0006

0.999

169.50

0.0010

0.999

178.57

0.0015

0.999

0.0020

0.999

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300 Pseudo second-order

qm* (mg/g)

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Pseudo-first order

Temperature (K)

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Kinetic models

192.30

Parameters β

300

91.19

0.030

0.997

305

123.97

0.029

0.991

310

139.07

0.027

0.992

315

241.53

0.026

0.993

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Α

Elovich

R2

*The experimental values of adsorption capacity (qe) are 166.97, 170.02, 178.38 and 191.88 mg/g at 300, 305, 310 and 315 K, respectively, when Co = 100 mg/L.

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Table 5: Kinetic parameters with double exponential model at different temperatures:

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300 305 310 315

Parameters KD1 RF (%) 0.010 82.289 0.012 83.590 0.014 83.770 0.017 83.803 Parameters KD2 SF (%) 0.014 17.710 0.018 16.410 0.020 16.230 0.025 16.197

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D2 28.901 27.893 28.875 31.452

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Slow

D1 134.289 142.107 149.051 160.000

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Step

300 305 310 315 Temperatures (K)

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Rapid

Temperatures (K)

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Step

R2 0.999 0.998 0.999 0.999 R2 0.964 0.970 0.972 0.991

Journal Pre-proof Table 6: Comparison of Ca (II)-doped chitosan/β-cyclodextrin composite with other adsorbents. Adsorbents

pH

Magnetite nanoparticles modified β -

Adsorption Sample capacity (mg/g) 128.90 Aqueous

7.0

Ref

20

Cyclodextrin polymer Activated biochar

4.0

4.35

Municipal

74

solid wastes Thermal and chemical activated groundnut

-

13.85

Activated carbon modified with KOH

3.0

Carbon nanocomposites, activated with mixture

7.0

0.85

Aqueous

76

45.45

Aqueous

77

170.10

Aqueous

78

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Activated Carbon obtained from rice husk

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of iron(III)/cobalt(II) benzoates

Ozone-treated granular activated carbon

2.0

20.96

Aqueous

79

9.0

38.20

Synthetic

21

wastewater 55.60

Aqueous

80

Activated carbon of dende coconut mesocarp

6.5

90.81

Aqueous

81

Dried olive stone

7.0

1.47

Wastewater

82

150.84

Wastewater

83

6.5

17.48

Aqueous

84

-

0.15

Hospital

85

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2.0

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Natural Jordanian zeolite

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5.9

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Surfactant-Modified Zeolite (Clinoptilolite)

75

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shells.

Aqueous

Activated banana leaves modified residues of

Moringa oleifera Lam. seed husks Activated carbon filters

Wastewater Tea waste derived activated carbon

3.0

195.95

Aqueous

86

Colloid Particle

7.0

436.11

River

87

sediment water Granular activated carbon coated chitosan

9.0

16.67

Synthetic

21

solution Ca (II)-doped chitosan/β-cyclodextrin

7.2

200.86

Aqueous

This

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Journal Pre-proof Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

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☐The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:

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The research work entitled’ Effective removal of acetaminophen from aqueous solution using Ca (II)-doped chitosan/β-cyclodextrin composite’ was performed by two authors: (1) Prof. Nafisur Rahman (2) Dr Mohd. Nasir. The experimental work was carried out by Dr Mohd. Nasir.The drafting of manuscript including discussion was done by Prof. Nafisur Rahman.

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Graphical Abstract Effective removal of acetaminophen from aqueous solution using Ca (II)doped chitosan/β-cyclodextrin composite Nafisur Rahman* and Mohd Nasir Department of Chemistry Aligarh Muslim University Aligarh (U.P.), India

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Email: [email protected]

Journal Pre-proof Highlights

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 Ca (II)-doped chitosan/β-cyclodextrin was prepared.  The material showed affinity for acetaminophen.  The independent variables of the adsorption process was optimized using response surface methodology.  Freundlich isotherm and pseudo second order kinetic models described well the adsorption process.  The mechanism of the adsorption of acetaminophen on Ca (II)-doped chitosan/βcyclodextrin was described