Journal Pre-proof

Optimization of removal of sulfonamide antibiotics by magnetic nanocomposite from

water samples using central composite design

Ahmed Hjazi, Yasir Qasim Almajidi, Wesam R. Kadhum, Mohammed Aly, Jitendra
Malviya, Mohammed N. Fenjan, Ahmed Alawadi, Ali Alsaalamy, Awadhesh
Chandramauli, Leila Baharinikoo
PII: S2212-3717(23)00029-X
DOI: https://doi.org/10.1016/j.wri.2023.100229
Reference: WRI 100229

To appear in: Water Resources and Industry

Received Date: 27 August 2023

Revised Date: 7 October 2023
Accepted Date: 15 October 2023

Please cite this article as: A. Hjazi, Y.Q. Almajidi, W.R. Kadhum, M. Aly, J. Malviya, M.N. Fenjan,
A. Alawadi, A. Alsaalamy, A. Chandramauli, L. Baharinikoo, Optimization of removal of sulfonamide
antibiotics by magnetic nanocomposite from water samples using central composite design, Water
Resources and Industry (2023), doi: https://doi.org/10.1016/j.wri.2023.100229.

This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition
of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of
record. This version will undergo additional copyediting, typesetting and review before it is published
in its final form, but we are providing this version to give early visibility of the article. Please note that,
during the production process, errors may be discovered which could affect the content, and all legal
disclaimers that apply to the journal pertain.

© 2023 Published by Elsevier B.V.

 1 Optimization of removal of sulfonamide antibiotics by magnetic nanocomposite from water samples using

2 central composite design

3 Ahmed Hjazia, Yasir Qasim Almajidib, Wesam R. Kadhumc,d, Mohammed Alye, Jitendra Malviyaf, Mohammed N.

4 Fenjang, Ahmed Alawadih,i,j, Ali Alsaalamyk, Awadhesh Chandramaulil, Leila Baharinikoom,*

6 a
Department of Medical Laboratory Sciences, College of Applied Medical Sciences, Prince Sattam bin Abdulaziz

7 University, Al-Kharj 11942, Saudi Arabia.

8 b
Department of Therapeutic and Clinical Pharmacy, Baghdad College of Medical Sciences, Baghdad, Iraq.

of
9 c
Department of Pharmacy, Kut University College, Kut 52001, Wasit, Iraq.

ro
10 d
Advanced Research Center, Kut University College, Kut 52001, Waist, Iraq

11
-p
e
Department of Artificial Intelligence, Faculty of Artificial Intelligence, Egyptian Russian University, Badr City
re
12 11829, Egypt.

13 f
lP

Department of Life Sciences and Biological Sciences, IES University, Bhopal, India.

14 g
College of Health and Medical Technology, Al-Ayen University, Thi-Qar, Iraq.
na

15 h
College of Technical Engineering, The Islamic University of Najaf, Najaf, Iraq.

16 i
College of Technical Engineering, The Islamic University of Al Diwaniyah, Al Diwaniyah, Iraq.
ur

17 j
College of Technical Engineering, The Islamic University of Babylon, Babylon, Iraq.
Jo

18 k
College of Technical Engineering, Imam Ja’afar Al‐Sadiq University, Samawah, Iraq.

19 l
Department of Civil Engineering, Uttaranchal Institute of Technology, Uttaranchal University, Dehradun 248007,

20 India.

21 m
Department of Analytical Chemistry, Faculty of chemistry, University of Mazandaran, Babolsar, Iran. Email:

22 nazaninheydari1996@gmail.com, bahari.leila@razichemical.com

23

24 Abstract

25 The present study aimed to remove sulfonamide antibiotics from water samples using magnetic Fe3O4-bentonite

26 nanocomposite (Fe3O4-Bt) as an adsorbent. The adsorbent has a surface area of 74.27 m2 g-1, a pore size of 87.53 nm,

27 and a pore volume of 0.146 cm3 g-1. A central composite design (CCD) matrix was employed to model and optimize
28 the process. The optimal conditions for removing sulfonamide antibiotics were determined using Fe3O4-Bt adsorbent

29 at an antibiotic concentration of 20 mg L-1, the amount of nanoparticles of 0.23 g, pH of 6, and ultrasonication time of

30 17 min. The reusability study of the Fe3O4-Bt adsorbent showed that the Fe3O4-Bt could be used five times in

31 adsorption/desorption processes. Also, applying the Fe3O4-Bt adsorbent on real samples revealed that Fe3O4-Bt

32 adsorbent could remove sulfonamide antibiotics in the range of 86.85-97.47% with RSD (n= 5) < 4.

33 Keywords: Sulfonamide antibiotics, Magnetic nanocomposite Removal, Response surface methodology.

34

35 1. Introduction

of
36 Nowadays, the indiscriminate use of antibiotics and their subsequent introduction into the environment has raised

ro
37 global concerns [1-3]. Approximately one hundred thousand to two hundred thousand tons of antibiotics are used

38

-p
worldwide annually. Typically, after consumption and metabolism in the body, the residual parts of these

39 pharmaceuticals, along with their metabolites, enter the environment through human and animal urine and feces [4,5].
re
40 The presence of antibiotics has been detected in surface waters, wastewater, and even in drinking water, at
lP

41 concentrations ranging from nanograms to micrograms per liter. These antibiotics enter the water through various
na

42 sources, such as hospital discharges, pharmaceutical industry wastewater, and human and animal excreta. While the

43 individual entry of these substances into the aquatic environment may be low, their continuous introduction can pose
ur

44 potential risks to aquatic ecosystems and the microorganisms present in them due to cumulative effects [6,7].
Jo

45 Sulfonamides are a common group of antibiotics used to treat infectious diseases in humans and animals. These

46 compounds cannot be easily removed from the aquatic environment through conventional wastewater treatment

47 processes [8]. When these antibiotics enter the sewage and water sources, because they remain unchanged in the

48 environment for a long time, they cause the microbial resistance of some pathogens or the destruction of the microbial

49 community involved in wastewater treatment and disruption of the biological cycle of wastewater treatment [9].

50 Antibiotic-resistant bacteria may be transmitted to humans through agricultural products (animal and plant) and cause

51 diseases that cannot be treated with common antibiotics. Therefore, the removal of antibiotics from environmental

52 water samples before discharge into water sources is very important [10,11].

53 On the other hand, it is vital to develop cost-effective methods to remove contaminants from wastewater. There are

54 various methods to remove contaminants from water samples, including chemical sedimentation, ion exchange,

55 reverse osmosis, surface adsorption, membrane filtration, coagulation, and flocculation [12-17]. The application of
56 conventional purification processes requires substantial costs and using chemicals. Hence, it is essential to use easy,

57 effective, economical, and efficient purification processes [18]. The surface adsorption method is better than other

58 techniques regarding its high efficiency, flexibility, simplicity of design, low cost, easy operation, and minimal sludge

59 [19,20].

60 Over the last few decades, the search has increased for low-cost and available adsorbents [21,22]. Fast adsorption and

61 high capacity are the main characteristics of a good adsorbent. Generally, these characteristics can be achieved when

62 the adsorbent has a high surface area with numerous adsorption sites [23,24]. Most adsorbents rarely have these two

63 properties simultaneously. Therefore, considering the mentioned characteristics, there is a need for research on new

of
64 adsorbents for better adsorption of contaminants. Based on these characteristics, the Fe3O4-bentonite magnetic

ro
65 nanocomposite has found various applications in wastewater treatment processes [25]. Magnetic Fe3O4-bentonite

66

-p
nanocomposites have several properties, such as chemical stability, large surface area, selectivity, cost-effectiveness,

67 and recyclability. Accordingly, they are considered attractive options for water and wastewater treatment [26].
re
68 Optimization aims to improve the performance of a system or process to achieve maximum efficiency. Classical
lP

69 optimization (one-factor-at-a-time or OFAT) cannot assess the interactions between parameters. In fact, in the OFAT
na

70 method, only one factor is changed while keeping the rest of the parameters constant [27]. Additionally, conducting

71 many experiments in OFAT leads to increased time, cost, and material consumption. To address these issues, statistical
ur

72 techniques such as response surface methodology (RSM) are suggested [28]. RSM is a collection of statistical and
Jo

73 mathematical methods that, by selecting influential parameters in the process and conducting experiments based on a

74 designed matrix, can obtain optimal values for each variable [29].

75 This study focuses on the synthesis of Fe3O4-Bt as an adsorbent. The synthesized Fe3O4-Bt adsorbent was

76 characterized using SEM, pHPZC, XRD, EDX, and VSM to investigate their properties. Furthermore, the modeling and

77 removal efficiency of sulfonamide antibiotics utilizing Fe3O4-Bt adsorbent was evaluated using the RSM approach.

78

79 2. Experimental

80 2.1. Materials and Methods

81 In the synthesis method, iron (II) chloride tetrahydrate (FeCl2·4H2O), hydrochloric acid (HCl), iron (III) chloride

82 hexahydrate (FeCl3·6H2O), sodium hydroxide (NaOH), ammonia (NH3), sulfamethoxazole (SMX, C10H11N3O3S),
 83 sulfadimethoxine (SDM, C12H13N4NaO4S), and sulfamerazine (SMR, C11H12N4O2S) was prepared from Merck or

84 Aldrich, were used. Bentonite was ready from the Fangzi Bentonite Plant (China). All experiments were performed

85 using distilled water. UV/Vis spectrophotometer (Philips PU 8700) was used to determine the concentration of

86 antibiotics. An ultrasonic device (Powersonic 505) was used to disperse the prepared solids in the solution. Metrohm

87 913 pH meter was used for pH measurements. The surface area, pore volume, and pore size of the Fe3O4-Bt adsorbent

88 was measured by Brunauer-Emmett-Teller (BET, Belsorp mini, MicrotracBEL corp.). The X-ray diffraction (XRD)

89 pattern of the prepared adsorbent was obtained using Philips X-Pert 1710 with Cu Kα radiation source to ascertain the

90 sample structure, particle size determination, and phase purity. The morphology of the Fe3O4-Bt adsorbent was

91

of
investigated by Philips XL 30 scanning electron microscopy (SEM). The magnetization was measured on a 7400

92 vibrating sample magnetometer (VSM). Design-Expert® software (V10) was used to optimize the variables and

ro
93 analyze the experimental data.

94
-p
re
95
lP

2.2. Synthesis of Fe3O4-Bt adsorbent

96 To synthesis of Fe3O4-Bt adsorbent, 1 g of bentonite was dispersed in 50 mL of double distilled water by an ultrasonic
na

97 bath, and then the solution was stirred for 1 h. After the desired time, the solution of the previous step was added to
ur

98 50 mL of solution containing 0.85 g of FeCl2·4H2O and 2.3 g of FeCl3·6H2O. The sample was stirred at 90 °C for 30
Jo

99 min under N2 gas. Then, 25 mL of 25% (W/W) NH3·H2O was added to the mixture and stirred for 1 h under N2 gas.

100 The precipitate obtained was separated by a magnet. Finally, the prepared adsorbent was washed with double distilled

101 water and dried at 80 °C for 12 h in the oven.

102

103 2.3. Central composite design (CCD) analysis

104 CCD is one of the designs used in the RSM and serves as a suitable alternative to the OFAT method. The advantage

105 of employing CCD over OFAT lies in extracting more information with fewer experiments and required repetitions

106 for each test. Additionally, CCD allows the determination of various combinations of independent variables in the

107 experiment [30]. Another benefit of CCD is its rotatability, which can be achieved by selecting an appropriate value

108 for the α coefficient through Equation 1 and determining the number of levels.
 1
109 α= (𝑁𝐹 )4 (1)

110 NF =2K (2)

111 where K represents the number of primary factors. The total number of conducted experiments is determined according

112 to Equation 3.

113 N= 2𝑛 + 2𝑛 + 𝑛𝑐 (3)

114 In this equation, 2n represents the factorial points, 2n represents the star points, and nc represents the center points.

115 With the help of CCD, all the coefficients of the second-degree model and the interaction effects of the parameters

of
116 can be estimated. In the CCD method, the relationship between the response (Y) and the parameters is expressed

ro
117 through a second-degree polynomial equation, as shown in Equation 4.

118 Y = 𝛽0 + ∑𝑘𝑖=1 𝛽𝑖 𝑋𝑖 + ∑𝑘𝑖=1 𝛽𝑖𝑖 𝑋𝑖2 + ∑𝑘𝑖≤𝑗 ∑𝑘𝑗 𝛽𝑖𝑗 𝑋𝑖 𝑋𝑗

-p
re (4)

119 In this equation, k represents the parameters. Xi and Xj denote the independent variables. β₀, βᵢ, βᵢᵢ, and βᵢⱼ represent the

120 constant, linear, quadratic, and interaction coefficients, respectively [31]. For the purpose of the design, four factors
lP

121 were examined at five levels. The factors examined in this research include antibiotic concentration, adsorbent amount,
na

122 ultrasonic time, and pH, which are shown in Table 1. Moreover, based on Equation 3, it is necessary to conduct 30

123 experiments for each antibiotic in this research (Table 2).

ur

124 Table 1. The CCD matrix.

Jo

125
Range and levels
Variables Symbol Unit
-α -1 0 +1 126
+α
Adsorbent amount A G 0.10 0.15 0.20 0.25 0.30
127 pH of the solution B --- 3 5 7 9 11
Antibiotic concentration C mg L-1 10 20 30 40 50
128 Sonication time D Min 5 10 15 20 25

129 Table 2. CCD matrix for removal of SMX, SDM, and SMR.

Variables %Removal-SMX %Removal-SDM %Removal-SMR

-1
Run A (g) B C (mg L ) D (min) Actual Predicted Actual Predicted Actual Predicted
1 0 0 0 0 88.28 88.24 87.44 88.31 93.22 93.38
2 1 -1 1 1 63.68 63.51 68.47 68.83 64.00 63.47
3 -2 0 0 0 36.97 36.24 48.01 47.65 51.72 52.42
4 2 0 0 0 81.05 78.78 84.24 84.25 82.02 80.90
5 1 -1 1 -1 44.33 46.84 51.19 51.56 54.20 54.73
6 -1 1 1 -1 36.87 37.69 39.40 40.59 51.94 52.64
7 -1 -1 1 -1 28.29 27.10 39.44 38.23 47.53 45.60
 8 0 0 0 0 88.15 88.24 88.88 88.31 91.36 93.38
9 0 0 0 0 86.62 88.24 88.22 88.31 95.78 93.38
10 0 2 0 0 67.37 64.83 62.12 60.21 72.68 71.23
11 -1 -1 -1 1 59.01 59.09 66.33 66.04 68.14 67.05
12 0 0 0 -2 51.29 49.39 54.90 55.19 65.59 65.36
13 1 1 1 -1 57.78 58.22 59.23 59.25 66.43 66.86
14 -1 1 1 1 58.17 59.96 50.44 51.91 60.85 60.47
15 -1 1 -1 1 76.49 76.45 70.42 70.67 73.66 74.22
16 1 1 -1 1 97.53 99.25 93.00 93.94 92.29 93.57
17 -1 -1 -1 -1 43.29 45.60 57.41 58.14 63.07 63.96
18 1 -1 -1 1 79.45 81.11 84.55 83.98 80.93 81.31
19 -1 1 -1 -1 57.64 58.34 63.70 63.07 69.50 69.38
20 0 0 0 0 89.38 88.24 87.99 88.31 91.19 93.38
21 0 0 2 0 53.84 53.16 50.06 49.41 52.81 53.31

of
22 0 0 0 0 89.95 88.24 90.52 88.31 94.02 93.38
23 0 0 0 2 85.26 84.16 80.69 80.06 79.13 78.94

ro
24 0 0 0 0 87.03 88.24 86.80 88.31 94.73 93.38
25 1 1 -1 -1 79.64 82.12 79.64 80.70 85.39 86.07
26
27
-1
0
-1
0
1
-2
1
0
44.75
93.73
-p
44.74
91.41
50.31
86.74
49.87
87.04
51.27
88.82
51.68
87.89
re
28 1 -1 -1 -1 69.87 68.60 72.17 70.43 75.84 75.56
29 1 1 1 1 79.34 79.51 76.33 76.22 77.16 77.35
lP

30 0 -2 0 0 36.55 36.09 46.32 47.89 50.91 51.93

130
na

131 2.4. Batch experiments

ur

132 Surface adsorption experiments were conducted in a batch system to investigate the influence of different factors on
Jo

133 the removal of sulfonamide antibiotics at room temperature. In each experiment, the solution containing 50 mL of

134 antibiotic with a concentration of 20 mg L-1 was used. The solution's pH was adjusted to 6 using 0.1 M HCl and 0.1

135 M NaOH. A quantity of 0.23 g of the adsorbent was added to the solution and subjected to ultrasonic bath for 17 min.

136 After the specified time, the adsorbent was separated from the mixture using an external magnetic field (a magnet),

137 and the absorption of antibiotics was measured using a UV/Visible Spectrophotometer. The efficiency of antibiotic

138 removal was determined as the percentage change in their concentration in the solution before and after adding the

139 adsorbent, according to Equation 5.

co −ce
140 %R=
co
× 100 (5)

141 In this equation, R, C0 (mg L-1), and Ce (mg L-1) represent the removal percentage, initial concentration, and final

142 concentration of antibiotics in the solution, respectively.

143 3. Results and discussion

144 3.1. Characterization of the prepared magnetic Fe3O4-Bt adsorbent

145 Figs. S1a and S1b represent the XRD patterns of raw bentonite and the synthesized adsorbent, respectively. In Fig.

146 S1a, the peaks at angles 19.85°, 22.13°, 29.33°, 34.98°, 36.21°, 61.83°, and 65.94° correspond to the diffractions of

147 planes (101), (101), (104), (107), (112), (2011), and (0012), respectively. According to this pattern, the main

148 components of the raw material include montmorillonite, SiO2, and CaCO3. The peak at 65.94° on the plane (0012)

149 indicates the presence of SiO2 (JCPDS card No. 003-0019) [32]. Based on this pattern, montmorillonite has a

150 hexagonal structure. After synthesizing the studied adsorbent, its XRD pattern was analyzed (Fig. S1b). According to

of
151 Fig. S1b, the peaks at angles 20.03°, 21.93°, 28.07°, 32.14°, 35.51°, 39.48°, 54.29°, and 61.98° correspond to the

ro
152 diffractions of planes (101), (012), (104), (006), (311), (200), (0013), (310), and (204), respectively. In this pattern,

153
-p
there is a prominent peak at 21.93°, corresponding to SiO2 and montmorillonite. Another peak at 35.51° on the plane
re
154 (311) is attributed to Fe3O4 (JCPDS card No. 190629) [33]. According to this pattern, Fe3O4 has a cubic crystal

155
lP

structure. The presence of the iron peak in this pattern indicates the infiltration of iron on the bentonite surface.

156 The results of surface and morphological measurements of raw bentonite and Fe3O4-Bt adsorbent are presented in Fig.
na

157 S2. Fig. S2a shows the SEM image of raw bentonite, while Fig. S2b displays the SEM image of the Fe3O4-Bt

158 adsorbent. As evident from Figs. S2a and S2b, raw bentonite consists of larger particles with a smoother surface. After
ur

159 synthesizing the desired adsorbent, these particles have transformed into flatter particles with a higher cross-sectional
Jo

160 surface area. The surface of the adsorbent, as shown in Fig. S2b compared to the raw sample, exhibits more defects,

161 larger pores, and better grain distribution. These characteristics enhance the adsorbent's efficiency for the absorption

162 and trapping of pollutant particles.

163 The saturation magnetization of the Fe3O4-Bt adsorbent was investigated through VSM analysis (Fig. S3). According

164 to Fig. S3, the saturation magnetization increased with an increasing magnetic field and reached a value of 20 emu/g.

165 As evident from Fig. S3, the VSM graph depicts the paramagnetic behavior of the material, indicating that the

166 magnetic property of the substance is terminated upon the removal of the external magnetic field.

167 EDX is used as a technique to prove the presence of elements in a compound. EDX analysis was performed to

168 characterize the bentonite and Fe3O4-Bt adsorbent, as shown in Figs. S4a and S4b. Based on Figs. S4a and S4b, the
169 percentage of iron increased from 0.7% in the raw bentonite to 7.2% in the synthesized adsorbent, indicating iron

170 infiltration onto the bentonite surface.

171 Fig. S5 illustrates the nitrogen adsorption/desorption isotherms and pore size distribution of the adsorbent. According

172 to the analyses and results obtained from BET analysis, the presence of hysteresis in the adsorption/desorption

173 isotherms in Fig. S5 indicates the existence of mesopores in the material. The nitrogen adsorption isotherms are

174 classified according to the IUPAC classification as Type IV, characterized by a large hysteresis loop of H2 type. This

175 type of hysteresis indicates a solid material composed of particles with almost cylindrical channels or formed by

176 agglomerates of non-uniform particles (spherical particles with varying sizes or shapes). The results revealed that the

of
177 surface area, pore size, and pore volume of the adsorbent were 74.27 m2 g-1, 87.53 nm, and 0.146 cm3 g-1, respectively.

ro
178

179 3.2. Determination of Point of Zero Charge (pHPZC)

-p
re
180 One of the most important parameters determining the removal is the electric charge of the absorbent. pH of point of

181
lP

zero charge (pHPZC) suggests at which pH the absorbent surface has zero or neutral electrical charge. When the pH of

182 the solution is higher than pHPZC, the absorbent surface has a negative electrical charge and when it is lower than
na

183 pHPZC, the absorbent surface in the solution has a positive electrical charge. Therefore, 10 vials containing 2-11 buffers

184 were prepared as pH0 and 0.03 g of absorbent was added to the samples. Then the vials were placed on a stirrer at
ur

185 room temperature and after 24 h, the pH of each solution was measured by a pHmeter. ΔpH was calculated from the
Jo

186 difference of pH - pH0 and by plotting the graph of ΔpH versus pH0, pHPZC was obtained. Based on the obtained

187 information, it was determined that the Fe3O4-Bt adsorbent surface has zero electric charge at pH= 4.5 (Fig. 1).

188

1.5
1
0.5
0
∆pH

-0.5 1 2 3 4 5 6 7 8 9 10 11 12
-1
-1.5
-2
-2.5
189 Initial pH

190 Fig. 1. pHpzc of Fe3O4-Bt adsorbent.

191 3.3. Analysis of variance (ANOVA)

192 The accuracy and validity of the model were evaluated through ANOVA, and the results are presented in Tables 3-5.

193 The p-value determines the statistical significance of the relationship between the response and the parametersin the

194 model. A smaller p-value indicates the rejection of insignificant values. The interaction effects are considered

195 significant when p< 0.05 [34]. In this study, nearly all p-values for the responses are less than 0.05, indicating the high

196 significance of the model conditions. Here, the high value of determination coefficient R² (0.99) and R² Adjust (0.99)

197 indicates the conformity of the data obtained from the model and the second-order model’s high prediction power.

198 The closer the R² value is to 1, the more powerful the model is in describing result changes as a function of parameters.

of
199 Another useful measure to assess the model is Lack of Fit, which compares the residual values with the pure error

ro
200 from replicated center points of the variable design [35]. The p-values of Lack of Fit were determined as 0.1023,

201

-p
0.4670, and 0.8520 for SMX, SDM, and SMR, respectively, indicating that this test is not significant for the model

202 (non-significance of this test is desirable for the model). Additionally, the Adequate Precision (used to compare the
re
203 predicted range with the average expected error, with a value above 4 being desirable) was 49.98, 58.14, and 45.77
lP

204 for SMX, SDM, and SMR, respectively, which is also favorable for the model. Based on the calculated coefficients
na

205 in Tables 3-5, second-degree polynomial equations for SMX, SDM, and SMR removal can be written according to

206 Equations 6-8, respectively.

ur

207
Jo

208 Table 3. ANOVA for removal of SMX.

Source Sum of Squares DF* Mean Square F-value p-value

Model 11946.04 14 853.29 204.76 < 0.0001 significant
A-Adsorbent amount 2715.12 1 2715.12 651.55 < 0.0001
B-pH of the solution 1238.84 1 1238.84 297.29 < 0.0001
C-Antibiotic concentration 2194.40 1 2194.40 526.59 < 0.0001
D-Sonication time 1813.95 1 1813.95 435.30 < 0.0001
AB 0.61 1 0.61 0.15 0.7069
AC 10.58 1 10.58 2.54 0.1319
AD 0.98 1 0.98 0.23 0.6356
BC 4.59 1 4.59 1.10 0.3105
BD 21.37 1 21.37 5.13 0.0388
CD 17.28 1 17.28 4.15 0.0597
A2 1618.29 1 1618.29 388.34 < 0.0001
B2 2446.15 1 2446.15 587.00 < 0.0001
 C2 436.10 1 436.10 104.65 < 0.0001
D2 789.45 1 789.45 189.45 < 0.0001
Residual 62.51 15 4.17
Lack of Fit 54.19 10 5.42 3.26 0.1023 not significant
Pure Error 8.32 5 1.66
Cor Total 12008.55 29
209 *Degree of freedom, R2= 0.9948, R2-adj= 0.9899.

210

211 Table 4. ANOVA for removal of SDM.

Source Sum of Squares DF* Mean Square F-value p-value

Model 8483.32 14 605.95 330.05 < 0.0001 significant

of
A-Adsorbent amount 2009.16 1 2009.16 1094.36 < 0.0001
B-pH of the solution 227.49 1 227.49 123.91 < 0.0001

ro
C-Antibiotic concentration 2123.84 1 2123.84 1156.82 < 0.0001

-p
D-Sonication time 928.15 1 928.15 505.55 < 0.0001
AB 28.49 1 28.49 15.52 0.0013
re
AC 1.07 1 1.07 0.58 0.4579
AD 31.84 1 31.84 17.34 0.0008
lP

BC 6.64 1 6.64 3.62 0.0765

BD 0.095 1 0.095 0.052 0.8235
CD 13.89 1 13.89 7.57 0.0149
na

A2 856.74 1 856.74 466.65 < 0.0001

B2 2012.19 1 2012.19 1096.01 < 0.0001
ur

C2 691.24 1 691.24 376.51 < 0.0001

D2 733.52 1 733.52 399.54 < 0.0001
Jo

Residual 27.54 15 1.84

Lack of Fit 19.18 10 1.92 1.15 0.4670 not significant
Pure Error 8.36 5 1.67
Cor Total 8510.86 29
212 *Degree of freedom, R2= 0.9968, R2-adj= 0.9937.

213

214 Table 5. ANOVA for removal of SMR.

Source Sum of Squares DF* Mean Square F-value p-value

Model 7187.46 14 513.39 233.81 < 0.0001 significant
A-Adsorbent amount 1216.67 1 1216.67 554.11 < 0.0001
B-pH of the solution 558.54 1 558.54 254.38 < 0.0001
C-Antibiotic concentration 1793.32 1 1793.32 816.74 < 0.0001
D-Sonication time 276.62 1 276.62 125.98 < 0.0001
AB 25.91 1 25.91 11.80 0.0037
 AC 6.10 1 6.10 2.78 0.1163
AD 7.08 1 7.08 3.22 0.0928
BC 2.66 1 2.66 1.21 0.2887
BD 3.06 1 3.06 1.39 0.2560
CD 8.94 1 8.94 4.07 0.0619
A2 1224.69 1 1224.69 557.77 < 0.0001
B2 1733.92 1 1733.92 789.68 < 0.0001
C2 889.85 1 889.85 405.27 < 0.0001
D2 773.26 1 773.26 352.17 < 0.0001
Residual 32.94 15 2.20
Lack of Fit 16.04 10 1.60 0.47 0.8520 not significant
Pure Error 16.89 5 3.38
Cor Total 7220.40 29

of
215 *Degree of freedom, R2= 0.9954, R2-adj= 0.9912.

ro
216

-p
217 %Removal-SMX= +88.23 +10.63*A +7.18*B -9.56*C +8.69*D +0.19*AB -0.81*AC -0.24*AD -0.53*BC
218 +1.15*BD +1.03*CD -7.68*A2 -9.44*B2 -3.98*C2 -5.36*D2 (6)
re
219 %Removal-SDM = +88.30 +9.14*A +3.07*B -9.40*C +6.21*D +1.33*AB +0.25*AC +1.41*AD -0.64*BC -
lP

220 0.07*BD +0.93*CD -5.58*A2 -8.56*B2 -5.02*C2 -5.17*D2 (7)

221
na

%Removal-SMR = +93.38 +7.12*A +4.82*B -8.64*C +3.39*D +1.27*AB -0.61*AC +0.66*AD +0.40*BC
222 +0.43*BD +0.74*CD -6.68*A2 -7.95*B2 -5.69*C2 -5.30*D2 (8)
ur

223 In this equation, A, B, C, and D represent the amount of adsorbent, solution pH, antibiotic concentration, and
Jo

224 sonication time, respectively. Positive regression coefficients estimated from the model indicate a direct effect of the

225 variables on the response. In contrast, negative coefficients indicate an indirect result of the variables on the response.

226 The magnitude of the coefficients indicates the extent to which each independent variable influences the response.

227 Figs. S6a-c illustrates the experimental data results compared with the model-calculated results. As seen in Figs. S6a-

228 c, the clustering of points around the centerline indicates good agreement between the laboratory results and the model-

229 derived results, demonstrating that the proposed model adequately covers the data. The probability plot of residuals,

230 shown in Figs. S6d-f depicts the distribution of errors, representing the discrepancies between actual and predicted

231 response values by the model. According to the probability plot of residuals (Figs. S6d-f), the proper and normal

232 distribution of points around the straight line indicates a suitable distribution of errors. Considering this plot and the

233 usual scattering of errors, the proposed model is statistically significant and demonstrates a good fit with the actual

234 data.
235 3.4. Response surface plots

236 The impact of two variables on response sensitivity can be demonstrated using response surface plots while holding

237 other variables at their central values. The variables that yield second-order terms with the most significant absolute

238 coefficients in the fitted model were selected for the axes of the three-dimensional response surface plots (Fig. 2).

239 The ability of the adsorbent to remove antibiotics from the solutions depends on the immersion time in the solution.

240 The impact of sonication time on the removal process can be illustrated by the relationship between the removal

241 efficiency and the time plot for antibiotics. Fig. 2a demonstrates the variations in SMX removal efficiency using

242 Fe3O4-Bt adsorbent at different time intervals (5-25 min). The SMX removal efficiency is at a minimum after 5 min.

243

of
The removal efficiency gradually increases with time until it reaches its maximum value. The maximum removal

244 efficiency for SMX using Fe3O4-Bt adsorbent was recorded at 93.5% after 17 min. The reason may be the rapid

ro
245 saturation of active surfaces on the adsorbent [36]. The results of Zhou et al.'s study, which was conducted on the

246
-p
removal of norfloxacin antibiotics, were consistent with the results of our study [37].
re
247 In addition, pH is another important and influential factor in removing pollutants from aqueous solutions. In this
lP

248 regard, pH changes are highly effective in the chemical activity of antibiotics in aqueous solutions, the activity of

249 basic groups on the adsorbent surface, and the competition of antibiotics. Fig. 2b presents the result of pH’s effect on
na

250 removing SMX from aqueous solutions. According to Fig. 2b, SMX removal efficiency increased with increasing pH.
ur

251 These antibiotics have positive and negative charges in acidic and alkaline pH, respectively. Also, pHpzc of the Fe3O4-

252
Jo

Bt adsorbent was 4.5. In solutions with acidic pH (pH lower than the pHpzc of the adsorbent), the surface of the

253 adsorbent usually has a positive charge. This positive surface can adsorb negatively charged ions. As a result, in acidic

254 solutions, the adsorbent is usually suitable for removing negatively charged ions. In contrast, in solutions with alkaline

255 pH (pH higher than the pHpzc of the adsorbent), the surface of the adsorbent is usually positively charged. As a result,

256 repulsion is developed between the adsorbed ion and the positive charge, thereby lowering the removal efficiency

257 [38]. The results of the present study showed that the highest removal efficiency occurs at neutral pH. Ahile et al.

258 (2020) reported similar results regarding pH influence on removing Ampicillin using rice husk adsorbent [39].

259 The concentration of antibiotics plays a crucial role in the removal efficiency and the amount of adsorbed antibiotics

260 from the solution. Fig. 2e depicts the simultaneous effect of two parameters, SDM concentration and the amount of

261 Fe3O4-Bt adsorbent, on the SDM removal. At low concentrations (20 mg L-1), the removal of SDM reached the highest

262 level. However, at higher SDM concentrations, the efficiency decreased. This is because at higher concentrations, the
263 surface of Fe3O4-Bt adsorbent becomes saturated at certain values, and active sites become blocked. At lower

264 concentrations, the surfaces of Fe3O4-Bt adsorbent do not reach saturation. According to Fig. 2e, the optimum

265 concentration for SDM was found to be 20 mg L-1. Similar results regarding the impact of antibiotic concentration on

266 the removal rate were reported by Yang et al. (2022) and Zhang et al. (2020) [40,41].

267 Fig. 2f displays the changes in SMR removal efficiency as a function of solution pH and the amount of Fe3O4-Bt

268 adsorbent. As depicted in Fig. 2f, an increase in the adsorbent amount results in a higher percentage of SMR removal.

269 This phenomenon can be attributed to the enlarged surface area of the adsorbent, allowing for more accessible

270 adsorption sites. However, at higher adsorbent amounts, when the adsorption process reaches equilibrium, the rate of

271

of
SMR removal slows down. This decline is due to unoccupied adsorption sites persisting throughout the saturation

272 process. These unoccupied sites may lead to an overlap of adsorption sites, ultimately reducing the overall accessible

ro
273 surface area for SMR and increasing the diffusion path length inside the adsorbent [42].

274
-p
re
lP

b)
na
ur
Jo
 c) d)

of
ro
e) f)

-p
re
lP
na
ur

Fig. 2. Three-dimensional plots showing the effects of the interactions between two variables.
Jo

275

276

277 3.5. Optimization of process conditions using the CCD method

278 The selection of optimal conditions depends on industrial, and economic factors and the quality of the final product.

279 In the present research, optimization was done to find points for higher removal efficiency. Therefore, the experimental

280 conditions were optimized to achieve the maximum removal of SMX, SDM, and SMR antibiotics. According to the

281 results, the maximum removal of more than 95.49% for SMX, SDM, and SMR antibiotics was achieved in adsorbent

282 amount, antibiotic concentration, sonication time, and pH of 0.23 g, 20 mg L-1, 17 min, and 6, respectively (Table 6).

283
284 Table 6. Optimum conditions of variables.

%Removal ± RSD (n= 3)

Optimal conditions
SMX SDM SMR

A (g) B C (mg L-1) D (min) Actual Predicted Actual Predicted Actual Predicted

0.23 6 20 17 98.06 ± 1.1 97.94 95.49 ± 1.9 96.49 96.52 ± 2.3 97.25

285

286 3.6. Desorption of antibiotics

287 To achieve good desorption efficiency, selecting the appropriate solvent is crucial for the process. Different solvents

288 will yield varying desorption efficiencies. In this study, four solvents, including acetonitrile, chloroform, methanol,

of
289 and toluene, were chosen for desorbing antibiotics. The experimental results in Fig. 3 demonstrated that the desorption

ro
290 of sulfonamide antibiotics from the adsorbent surface was higher when using methanol. Therefore, in subsequent

291 experiments, methanol was employed as the solvent for desorbing the analyte.
-p
re
292
lP

100
% Desorption efficiency

90
80 SMX
na

SDM
70
SMR
60
ur

50
40
30
Jo

20
10
0
Methanol Acetonitrile Toluene Chloroform

293 Solvent

294 Fig. 3. Effect of solvent on the removal efficiency of SMX, SDM, and SMR.

295

296 3.7. Interferents

297 The study investigates the selectivity of the sulfonamide antibiotics removal process by the Fe3O4-Bt adsorbent in

298 competition with other ions and molecules that could be present in the solution. Validation experiments were

299 performed under optimal conditions and in different concentrations of external ions and molecules. The study aims to
300 determine the acceptable threshold of the external species concentration that would cause a ≤10% change in antibiotics

301 removal. The impact of the external ions and molecules is presented in Table 7. As observed from the results, most of

302 the examined species exhibited no interference or adverse effects, even at higher concentrations, demonstrating the

303 exceptional selectivity of the adsorbent.

304

305 Table 7. Effect of foreign species on the removal of sulfonamide antibiotics.

Foreign species Tolerance (mg L-1)

Li+, Mg2+, Bi3+, K+, Al3+, F-, Cl-, Cd2+, Na+, NO3¯ 1000

of
Vitamin B1, Vitamin C, Gallic acid 10
306

ro
307 3.8. Reusability of the Fe3O4-Bt adsorbent

308 -p
re
The reusability of the Fe3O4-Bt adsorbent is considered an essential aspect of operational and environmental

309 objectives, as the ability to reuse and regenerate the adsorbent is crucial for economic feasibility. The process of
lP

310 reversible adsorption allows for the regeneration of the adsorbent. As shown in Fig. 4, which illustrates the
na

311 regeneration efficiency of the Fe3O4-Bt adsorbent, the removal of sulfonamide antibiotics after initial cycles was

312 nearly above 95%. At the same time, in the final cycles, it was around 85%. The reduction in the removal process
ur

313 during the last cycles can be attributed to the loss of the adsorbent in consecutive stages, incomplete washing
Jo

314 procedures, and failure to achieve complete adsorption. The adsorption/desorption experiments demonstrated that the

315 Fe3O4-Bt adsorbent can be effectively used multiple times to purify samples containing sulfonamide antibiotics.

316

100 SMX Sorption

a)
SMX Desorption
% Sorption/Desorption

90

80

70

60

50
1 2 3 4 5 6 7
Regeneration cycle
 100 SDM Sorption
b) SDM Desorption

% Sorption/Desorption
90

80

70

60

50
1 2 3 4 5 6 7
Regeneration cycle

100 SMR Sorption

c)

of
SMR Desorption
90
% Sorption/Desorption

ro
80

-p
70 re
60

50
lP

1 2 3 4 5 6 7
Regeneration cycle
na

Fig. 4. Sorption/Desorption of a) SMX, b) SDM, and c) SMR.

317
ur

318 3.9. Analysis of real samples

Jo

319 Fe3O4-Bt adsorbent was used for the removal of sulfonamide antibiotics in environmental water samples, which

320 included tap water, wastewater, lake water, and river water (Table 8). To accomplish this, sewage samples were

321 diluted, and the experiments were conducted following the method described in Section 2.4. The average removal

322 efficiency of SMX, SDM, and SMR antibiotics ranged from 97.47% to 86.85%. The results demonstrate that the

323 Fe3O4-Bt adsorbent exhibits efficient performance in the complete removal of sulfonamide antibiotics in various water

324 samples and indicates that water matrices have a negligible influence on the extent of sulfonamide antibiotics removal

325 by the Fe3O4-Bt adsorbent.

326

327 Table 8. Results of removal of sulfonamide antibiotics in environmental water samples under the optimum conditions (n= 5).

Real samples %Removal-SMX ± RSD %Removal-SDM ± RSD %Removal-SMR ± RSD

 Tap water 97.32 ± 1.8 95.83 ± 2.4 97.47 ± 2.1

Lake water 94.25 ± 1.4 91.27 ± 1.1 93.19 ± 1.6

Wastewater 90.30 ± 3.0 86.85 ± 2.2 91.68 ± 2.6

River water 93.06 ± 2.3 90.84 ± 1.5 91.65 ± 2.1

328

329 4. Conclusion

330 This work reported the application of magnetic Fe3O4-Bt adsorbent to remove SMX, SDM, and SMR from wastewater.

331 The precise structural properties of this magnetic Fe3O4-Bt adsorbent were characterized via different analytical

332 approaches, such as EDX, SEM, BET, XRD, VSM, and pHPZC. The XRD results of Fe3O4-Bt adsorbent were

of
333 consistent with the XRD data reported in the literature. The Fe3O4-Bt adsorbent showed paramagnetic properties, and

ro
334 the adsorbent had a magnetic saturation value equal to 20 emu/g. This variable is an important indicator of the

335
-p
adsorbent’s ability for magnetic separation. The surface area, pore size, and pore volume of Fe3O4-Bt adsorbent were
re
336 obtained as 74.27 m2 g-1, 87.53 nm, and 0.146 cm3 g-1, respectively. Besides, the Fe3O4-Bt adsorbent had a point of
lP

337 zero charge at a pH of 4.5. The removal efficiency of the SMX, SDM, and SMR in an aqueous solution was calculated.

338 The removal efficiencies obtained using SMX, SDM, and SMR were 98.06%, 95.49%, and 96.52% in optimum
na

339 conditions, respectively. Also, the optimum conditions derived via CCD were Fe3O4-Bt amount of 0.23 g, pH of 6,
ur

340 sonication time of 17 min, and antibiotics concentration of 20 mg L-1. Among different solvents, methanol showed the

341 most efficiency in desorbing antibiotics from the adsorbent. The reusability study showed that Fe3O4-Bt adsorbent
Jo

342 could be reused up to five times without any significant loss in the removal efficiency of sulfonamide antibiotics. The

343 removal efficiency of sulfonamide antibiotics was obtained in the range of 86.85-97.47% for environmental water

344 samples.

345

346 Data availability

347 The datasets used and/or analyzed during the current study are available from the corresponding author on reasonable

348 request.

349
350 Acknowledgements

351 The authors are grateful to University of Mazandaran, for kind support.

352

353 Author contributions

354 L.B. conceived and planned the study. Y.A., W.K., Ah.A., and M.F. performed experiments and data analysis. A.H.,

355 Al.A., and A.C. contributed to interpretation of the results. J.M. wrote the manuscript in consultation with M.A. All

356 authors have given approval to the final version of the manuscript.

of
357

ro
358 Declaration of Competing Interest

359 -p
The author declare that they have no known competing financial interests or personal relationships that could have
re
360 appeared to influence the work reported in this paper.
lP

361
na

362 References
ur

363 [1] P. Arabkhani, A. Asfaram, The potential application of bio-based ceramic/organic xerogel derived from the plant
Jo

364 sources: A new green adsorbent for removal of antibiotics from pharmaceutical wastewater. J. Hazard. Mater. 429

365 (2022) 128289.

366 [2] K. Laugesen, J.F. Ludvigsson, M. Schmidt, M. Gissler, U.A. Valdimarsdottir, A. Lunde, H.T. Sørensen, Nordic

367 health registry-based research: a review of health care systems and key registries. Clin. Epidemiol. (2021) 533-554.

368 [3] M. Nemati, M.R.A. Mogaddam, M.A. Farazajdeh, M. Tuzen, J. Khandaghi, In-situ formation/decomposition of

369 deep eutectic solvent during solidification of floating organic droplet-liquid-liquid microextraction method for the

370 extraction of some antibiotics from honey prior to high performance liquid chromatography-tandem mass

371 spectrometry. J. Chromatogr. A. 1660 (2021) 462653.

372 [4] M.F. Lanjwani, N. Altunay, M. Tuzen, Preparation of fatty acid-based ternary deep eutectic solvents: Application

373 for determination of tetracycline residue in water, honey and milk samples by using vortex-assisted

374 microextraction. Food Chem. 400 (2023) 134085.

375 [5] D. Mangla, A. Sharma, S. Ikram, Critical review on adsorptive removal of antibiotics: Present situation, challenges

376 and future perspective. J. Hazard. Mater. 425 (2022) 127946.

377 [6] Y. Jiang, J. Ran, K. Mao, X. Yang, L. Zhong, C. Yang, X. Feng, H. Zhang, Recent progress in Fenton/Fenton-like

378 reactions for the removal of antibiotics in aqueous environments. Ecotoxicol. Environ. Saf. 236 )2022( 113464.

379 [7] E.A. Dil, M. Ghaedi, A. Asfaram, L. Tayebi, F. Mehrabi, A ferrofluidic hydrophobic deep eutectic solvent for the

380 extraction of doxycycline from urine, blood plasma and milk samples prior to its determination by high-performance

381 liquid chromatography-ultraviolet. J. Chromatogr. A. 1613 (2020) 460695.

382 [8] W. Duan, H. Cui, X. Jia, X. Huang, Occurrence and ecotoxicity of sulfonamides in the aquatic environment: A

383

of
review. Sci. Total Environ. 820 (2022) 153178.

384 [9] S. Cui, Y. Qi, Q. Zhu, C. Wang, H. Sun, A review of the influence of soil minerals and organic matter on the

ro
385 migration and transformation of sulfonamides. Sci. Total Environ. 861 (2023) 160584.

386
-p
[10] X. Xie, S. Huang, J. Zheng, G. Ouyang, Trends in sensitive detection and rapid removal of sulfonamides: A
re
387 review. J. Sep. Sci. 43(9-10) (2020) 1634-1652.
lP

388 [11] S. Rana, A. Kumar, P. Dhiman, G.T. Mola, G. Sharma, C.W. Lai, Recent advances in photocatalytic removal of

389 sulfonamide pollutants from waste water by semiconductor heterojunctions: a review. Mater. Today Chem. 30 (2023)
na

390 101603.
ur

391 [12] P. Arabkhani, N. Saeedi, H. Sadeghi, S. Nouripour-Sisakht, M. Gharaghani, A. Asfaram, Plant extracts-mediated

392
Jo

green synthesis of zinc oxide/carbon nanofiber nanocomposites with highly efficient photocatalytic and antimicrobial

393 properties for wastewater treatment. J. Water Process Eng. 54 (2023) 104020.

394 [13] F.A. Janjhi, I. Ihsanullah, M. Bilal, R. Castro-Muñoz, G. Boczkaj, F. Gallucci, MXene-based materials for

395 removal of antibiotics and heavy metals from wastewater–A review. Water Resour. Ind. (2023) 100202. Water Resour.

396 Ind.

397 [14] Z. Honarmandrad, X. Sun, Z. Wang, M. Naushad, G. Boczkaj, Activated persulfate and peroxymonosulfate based

398 advanced oxidation processes (AOPs) for antibiotics degradation–A review. Water Resour. Ind. (2022) 100194.

399 [15] S.R. Aqdam, D.E. Otzen, N.M. Mahmoodi, D. Morshedi, Adsorption of azo dyes by a novel bio-nanocomposite

400 based on whey protein nanofibrils and nano-clay: Equilibrium isotherm and kinetic modeling. J. Colloid Interface

401 Sci. 602 (2021) 490-503.

402 [16] S. Shojaei, S. Shojaei, A. Nouri, L. Baharinikoo, Application of chemometrics for modeling and optimization of

403 ultrasound-assisted dispersive liquid–liquid microextraction for the simultaneous determination of dyes. NPJ Clean

404 Water. 4(1) (2021) 23.

405 [17] Z. Mokhtari-Shourijeh, S. Langari, L. Montazerghaem, N.M. Mahmoodi, Synthesis of porous aminated

406 PAN/PVDF composite nanofibers by electrospinning: Characterization and Direct Red 23 removal. J. Environ. Chem.

407 Eng. (4) (2020) 103876.

408 [18] A.A. Bazrafshan, M. Ghaedi, S. Hajati, R. Naghiha, A. Asfaram, Synthesis of ZnO-nanorod-based materials for

409 antibacterial, antifungal activities, DNA cleavage and efficient ultrasound-assisted dyes adsorption. Ecotoxicol.

410

of
Environ. Saf. 142 (2017) 330-337.

411 [19] M.E. Mahmoud, S.E. Adel, I.E. ElSayed, Development of titanium oxide-bound-α-aminophosphonate

ro
412 nanocomposite for adsorptive removal of lead and copper from aqueous solution. Water Resour. Ind. 23 (2020)

413 100126.
-p
re
414 [20] Z. Hosseinabadi-Farahani, N.M. Mahmoodi, H. Hosseini-Monfared, Preparation of surface functionalized
lP

415 graphene oxide nanosheet and its multicomponent dye removal ability from wastewater. Fibers Polym. 16 (2015)
na

416 1035-1047.

417 [21] Z. Mokhtari-Shourijeh, S. Langari, L. Montazerghaem, N.M. Mahmoodi, Synthesis of porous aminated
ur

418 PAN/PVDF composite nanofibers by electrospinning: Characterization and Direct Red 23 removal. J. Environ. Chem.
Jo

419 Eng. 8(4) (2020) 103876.

420 [22] N.M. Mahmoodi, B. Karimi, M. Mazarji, H. Moghtaderi, Cadmium selenide quantum dot-zinc oxide composite:

421 Synthesis, characterization, dye removal ability with UV irradiation, and antibacterial activity as a safe and high-

422 performance photocatalyst. J. Photochem. Photobiol., B. 188 (2018) 19-27.

423 [23] N.M. Mahmoodi, S. Keshavarzi, M. Ghezelbash, Synthesis of nanoparticle and modelling of its photocatalytic

424 dye degradation ability from colored wastewater. J. Environ. Chem. Eng. 5(4) (2017) 3684-3689.

425 [24] Z. Hosseinabadi-Farahani, H. Hosseini-Monfared, N.M. Mahmoodi, Graphene oxide nanosheet: preparation and

426 dye removal from binary system colored wastewater. Desalin. Water Treat. 56(9) (2015) 2382-2394.
427 [25] K. Oukebdane, I.L. Necer, M.A. Didi, Binary comparative study adsorption of anionic and cationic Azo-dyes on

428 Fe3O4-Bentonite magnetic nanocomposite: Kinetics, Equilibrium, Mechanism and Thermodynamic

429 study. Silicon. 14(15) (2022) 9555-9568.

430 [26] H.X. Linh, N.T. Trung, D. Van Thanh, N.N. Huy, N.Q. Dung, T.Q. Toan, N.T. Mai, N.T. Thuy, N.M. Khai, A

431 one‐stage sono‐coprecipitation synthesis of porous Fe3O4/bentonite nanocomposite as an adsorbent for methylene

432 blue removal in water. Vietnam J. Chem. 60 (2022) 41-45.

433 [27] R. Subramaniam, S.K. Ponnusamy, Novel adsorbent from agricultural waste (cashew NUT shell) for methylene

434 blue dye removal: Optimization by response surface methodology. Water Resour. Ind. 11 (2015) 64-70.

of
435 [28] A. Asfaram, M. Ghaedi, A. Goudarzi, M. Rajabi, Response surface methodology approach for optimization of

ro
436 simultaneous dye and metal ion ultrasound-assisted adsorption onto Mn doped Fe 3 O 4-NPs loaded on AC: kinetic

437

-p
and isothermal studies. Dalton Trans. 44(33) (2015) 14707-14723.
re
438 [29] M. Tuzen, A. Sarı, T.A. Saleh, Response surface optimization, kinetic and thermodynamic studies for effective

439
lP

removal of rhodamine B by magnetic AC/CeO2 nanocomposite. J. Environ. Manage. 206 (2018) 170-177.

440 [30] E.A. Dil, M. Ghaedi, A. Ghaedi, A. Asfaram, M. Jamshidi, M.K. Purkait, Application of artificial neural network
na

441 and response surface methodology for the removal of crystal violet by zinc oxide nanorods loaded on activate carbon:
ur

442 kinetics and equilibrium study. J. Taiwan Inst. Chem. Eng. 59 (2016) 210-220.

[31] T.A. Saleh, A. Sarı, M. Tuzen, Optimization of parameters with experimental design for the adsorption of mercury
Jo

443

444 using polyethylenimine modified-activated carbon. J. Environ. Chem. Eng. 5(1) (2017) 1079-1088.

445 [32] A. Mishra, A. Mehta, S. Kainth, S. Basu, Effect of different plasmonic metals on photocatalytic degradation of

446 volatile organic compounds (VOCs) by bentonite/M-TiO2 nanocomposites under UV/visible light. Appl. Clay

447 Sci. 153 (2018) 144-153.

448 [33] Q. Huang, L. Zou, D. Chen, Phase and morphology controlled in the synthesis of iron oxide particles: dimension-

449 based carbonaceous materials as modifiers. RSC Adv. 6(85) (2016) 82294-82297.

450 [34] B. Ekka, M.K. Sahu, R.K. Patel, P. Dash, Titania coated silica nanocomposite prepared via encapsulation method

451 for the degradation of Safranin-O dye from aqueous solution: Optimization using statistical design. Water Resour.

452 Ind. 22 (2019) 100071.

453 [35] P. Asaithambi, E. Alemayehu, B. Sajjadi, A.R.A. Aziz, Electrical energy per order determination for the removal

454 pollutant from industrial wastewater using UV/Fe2+/H2O2 process: optimization by response surface

455 methodology. Water Resour. Ind. 18 (2017) 17-32.

456 [36] F. Chen, J. Ma, Y. Zhu, X. Li, H. Yu, Y. Sun, Biodegradation performance and anti-fouling mechanism of an

457 ICME/electro-biocarriers-MBR system in livestock wastewater (antibiotic-containing) treatment. J. Hazard.

458 Mater. 426 (2022) 128064.

459 [37] H. Zhou, Z. Wang, C. Gao, Q. Sun, J. Liu, D. She, Synthesis of honeycomb lignin-based biochar and its high-

460 efficiency adsorption of norfloxacin. Bioresour. Technol. 369 (2023) 128402.

of
461 [38] B. Rabeie, M. Mahkam, N.M. Mahmoodi, C.Q. Lan, Graphene quantum dot incorporation in the zeolitic

ro
462 imidazolate framework with sodalite (SOD) topology: Synthesis and improving the adsorption ability in liquid

463 phase. J. Environ. Chem. Eng. 9(6) (2021) 106303.

-p
re
464 [39] U.J. Ahile, H.N. Iorav, L. Dooga, D. Terungwa, S.D. Igbawase, K. Asemave, Preparation, Characterization and
lP

465 Application of Rice Husk Adsorbent in the Removal of Ampicillin from Aqueous Solution. Int. J. Mod. Chem, 11(1)
na

466 (2019) 28-39.

467 [40] J. Yang, S. Shojaei, S. Shojaei, Removal of drug and dye from aqueous solutions by graphene oxide: Adsorption
ur

468 studies and chemometrics methods. NPJ Clean Water. 5(1) (2022) 5.
Jo

469 [41] S. Zhang, Y.L. Yang, J. Lu, X.J. Zuo, X.L. Yang, H.L. Song, A review of bioelectrochemical systems for

470 antibiotic removal: Efficient antibiotic removal and dissemination of antibiotic resistance genes. J. Water Process

471 Eng. 37 (2020) 101421.

472 [42] A.M. Awad, S.M. Shaikh, R. Jalab, M.H. Gulied, M.S. Nasser, A. Benamor, S. Adham, Adsorption of organic

473 pollutants by natural and modified clays: a comprehensive review. Sep. Purif. Technol. 228 (2019) 115719.
L.B. conceived and planned the study. Y.A., W.K., Ah.A., and M.F. performed experiments and data analysis. A.H.,

Al.A., and A.C. contributed to interpretation of the results. J.M. wrote the manuscript in consultation with M.A. All

authors have given approval to the final version of the manuscript.

of
ro
-p
re
lP
na
ur
Jo
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.

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

of
ro
-p
re
lP
na
ur
Jo