Herbicide diuron removal from aqueous solution by bottom ash: Kinetics, isotherm, and thermodynamic adsorption studies

Journal Pre-proof Herbicide Diuron Removal from Aqueous Solution by Bottom Ash: Kinetics, Isotherm, and Thermodynamic Adsorption Studies Mohamed Zbair, Abdelouahab El Hadrami, Amal Bellarbi, Mohamed Monkade, Abdellah Zradba, Rachid Brahmi

PII:

S2213-3437(20)30015-4

DOI:

https://doi.org/10.1016/j.jece.2020.103667

Reference:

JECE 103667

To appear in:

Journal of Environmental Chemical Engineering

Received Date:

12 November 2019

Revised Date:

26 December 2019

Accepted Date:

5 January 2020

Please cite this article as: Zbair M, El Hadrami A, Bellarbi A, Monkade M, Zradba A, Brahmi R, Herbicide Diuron Removal from Aqueous Solution by Bottom Ash: Kinetics, Isotherm, and Thermodynamic Adsorption Studies, Journal of Environmental Chemical Engineering (2020), doi: https://doi.org/10.1016/j.jece.2020.103667

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Herbicide Diuron Removal from Aqueous Solution by Bottom Ash: Kinetics, Isotherm, and Thermodynamic Adsorption Studies Mohamed Zbair1,*, Abdelouahab El Hadrami2, Amal Bellarbi3, Mohamed Monkade3, Abdellah Zradba3, Rachid Brahmi4 1

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Laboratory of Catalysis and Corrosion of Materials, Chouaïb Doukkali University, Faculty of Sciences El Jadida, BP. 20, El Jadida 24000, Morocco 2 Department of Chemistry, Laboratory of Physical Chemistry of Materials (LPCM), Faculty of Science, Chouaib Doukkali University, El Jadida, Morocco 3 Physics of Condensed Matter Laboratory, physics department, Faculty of Science, Chouaib Doukkali University, El Jadida Morocco 4 Laboratory of Coordination and Analytical Chemistry (LCCA), University Chouaïb Doukkali, El Jadida Morocco.

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Corresponding author: [email protected]; Tel: +212.6.65.03.78.08

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Graphical Abstract

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Abstract The current research reports an efficient methodology of valorizing bottom ash waste generated from the combustion of coal in a local thermal power plant. Where in this work we have used bottom ash waste (BAW-200) as an inexpensive adsorbent for herbicide diuron removal. The BAW200 was characterized by XRD, FTIR, SEM and mapping analyses. The adsorption kinetics, equilibrium isotherms and regeneration potential of diuron removal by BAW-200 was investigated

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in batch tests. Pseudo-first order model described well the kinetic data and Langmuir model show a high correlation with equilibrium data, which suggested monolayer adsorption of diuron onto BAW-200 with a higher adsorption capacity (349.52 mg/g) compared to other adsorbents. The

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thermodynamic behavior revealed that adsorption phenomenon of diuron onto BAW-200 ensued spontaneously and endothermic in nature. The regeneration method show that BAW-200 can be

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recycled easily from wastewater using ethanol as solvent. The outcomes show that BAW-200 adsorbent

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could be used in improving the quality of wastewater as providing a waste disposal option for the industry.

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1. Introduction

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Keywords: Diuron; Herbicide; Adsorption; Bottom ash; Regeneration; Wastewater treatment

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Diuron (by name IUPAC, 3- (3,4-dichlorophenyl) -1,1-dimethyl-urea) is a phytosanitary product (pesticide) with an herbicidal effect. Diuron is usually practiced as a nonselective pre-emergent and post-emergent herbicide in agricultural and nonagricultural sites [1,2]. Though, once pesticides/herbicides are used in extremely, they would leach into the soil and also degrade or persist in their original form for a longer time [3]. Generally, a diuron molecule is a persistent pollutant present in the soil, surface water and groundwater. It is also slightly toxic to mammals 2

and birds as well as moderately toxic to aquatic invertebrates and its main product of biodegradation, 3,4-dichloroaniline (3,4-DCA) has higher toxicity and is also persistent in soil, surface water and groundwater[4]. Recently, diuron molecule has been identified in groundwater and surface water [1]. Approximately 70 % of samples gotten from the European streams had a maximum concentration of diuron (864 ng/L) [5]. Rendering to the European Union (EU) rules, the maximum allowed concentration of an herbicide such as diuron in the drinking water is 0.1 µg/L [6]. Henceforth, concurrent removal of this noxious pollutant from wastewater is an imperative

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environmental issue. Adsorption approach has been recognized to be superior to other methods for wastewater treatment due to its low-cost, highly proficient and the simplicity of process [7– 15]. Quite a lot of research has been explored the use of different adsorbents for diuron removal

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through adsorption, a surface phenomenon in which the diuron molecules adhere to the surface

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of the adsorbent [16,17]. Generally, the adsorbents used in these works are derived from waste biomass. The use of different industrial wastes has gained attractiveness in latest years such

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as eggshell [18], sepia shell [19], marine algal [20], fly and bottom ash [21,22], slag [23,24], tailings [25], have been explored in the uptake of contaminants. The value related to industrial by-

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products is their abundance as wastes and hence gamely available and inexpensive. Lack of utilization of these resources causes waste disposal problems. Consequently, using these available

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wastes as adsorbent materials is a substantial step to resolving the problem produced by high

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levels of diuron in wastewaters.

The bottom ash waste (BAW-200) that concerns the present work, are from the combustion of coal in a local thermal power plant. Their high adsorbent capacity has been proven in industrial and domestic wastewater filtration systems, particularly in the removal of certain heavy metals and dyes [22,26]. Their valorization in different fields remains a major challenge, given their huge quantity, the problems related to their storage and their impact on the environment. In this sense, 3

the present work proposes the reuse of these by-products in solving the problem posed by the high levels of diuron in wastewater. This is a new way that will importantly benefit the environment.

2. Materials and methods 2.1 Sample preparation

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Bottom ash waste (BAW) was randomly collected and mixed from landfill sites at the El Jadida region. The BA was washed with hot distilled water to remove any materials loosely adhered to particles and any soluble materials. After washing and drying at 90 °C for 12 hours, the BAW was

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calcined at 200 °C for 1 hour (Water content has been found equal 0.2 %). The treated material

2.1 Characterization methods

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was labeled: BAW-200.

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XRD patterns of BAW-200 were collected using a Bruker eco D8 Advance diffractometer operating at 45 kV/35mA, using CuKα radiation, with a step size of 0,02. Data were collected over a range of

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05-70°. The morphological characteristics of BAW-200were analyzed using a Field Emission Scanning Electron Microscopy ZEISS ULTRA plus. The PZC (point of zero charges) of BA-200 was

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determined using the pH drift method[7,10,27]. BAW-200 (0.20 g) was mixed with 50 mL of 0.01 M NaCl solution. The pH of the starting solutions (2.0 to 12.0) was attuned using HCl and NaOH. After 24 h, the final pH was measured. The functional surface groups of BAW-200 were determined using a Fourier transformed infrared spectroscopy (FTIR–8400S, Shimadzu).

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2.2 Adsorption experiments The adsorption tests of diuron onto BAW-200 were performed in a batch mode. The effect of BAW200 mass on diuron removal was carried out by changing the adsorbent dosage in the range (10– 100 mg) blended with 100 mL of dye solutions separately (C0 20 mg/L) at 20 ± 1 °C for 180 min. To investigate the solution pH effect, 100 mL of 20 mg/L of diuron solution at different initial pH values

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(1–12) was individually mixed with 10 mg of BAW-200 sorbent for 180 min at 20°C ± 1 °C, and the stirring speed was adjusted at 150 rpm using a reciprocal agitator. pH values were controlled by the addition of 0.1 M HCl and 0.1 M NaOH solutions. Kinetic studies were done with a fixed amount of

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10 mg of BAW-200 and an initial diuron concentration of 20 mg/L. The volume of 100 mL diuron solutions was agitated (200 rpm) at different temperatures (20, 30, and 40°C) for 180 min and the

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solution was filtered to remove the BAW-200. Residual diuron concentrations were determined

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by spectrophotometry at the maximum absorbance wavelength (λmax) of 248 nm. For adsorption isotherms, 10 mg of BAW-200 sorbent was mixed with 100 mL of diuron solution at different initial

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concentrations (C0, ranging between 5 and 40 mg/L) at 20, 30, and 40°C for 180 min. After solid/ liquid separation, the residual concentrations of diuron were determined.

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Table 1S summarizes the equations used in this work

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2.3 Regeneration protocol

The regeneration of the BAW-200 after diuron adsorption was performed by mixing diuron loaded BAW-200 with 30 mL of ethanol for 5 h and then filtered and dried at 90 °C. Five cycles of diuron adsorption/desorption studies were carried out accordingly. The regeneration studies were executed after completion of the adsorption process by separate contact of 10 mg of BAW-200 with 100 mL of diuron solution (C0 20 mg/L) at 20 ± 1 °C for 180 min. 5

The loaded adsorbent was collected from diuron solution by centrifugation and washed by deionized water. Then, it was mixed with 30 mL of ethanol at 20 ± 1 °C for 5 h in order to desorb diuron. The regenerated sorbent was carefully washed by deionized water for reuse in the next cycle. The procedure was repeated for 5 cycles. 3. Results and discussion 3.1 X-Ray diffraction (XRD) and Fourier-Transform Infrared Spectroscopy (FTIR)

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The XRD spectra of the BAW-200 (Figure 1a) reveals different mineral phases that were present in the BAW-200 namely quartz (SiO2; JCPDS 5-0490) and mullite (Al6Si2O13; JCPDS 15-0776). Furthermore, we identified the presence of anorthite (Ca Al2 Si2 O8), calcite (JCPDS 86-2334), belite

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(Ca2SiO4; JCPDS 9-351), hematite (Fe₂O₃; JCPDS 33-0664), and wustite (FeO; JCPDS 43-1312).

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FTIR spectra of BAW-200 (Figure 1b) show a broadband at about 3363 cm-1 result from hydration water. In addition, a strong Si-O stretching vibration at about 1080-1100 cm-1 and Si-O bending

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vibration at about 450-470 cm-1. Moreover, the bands between 600-800 cm-1 are due to Al-O-Si vibrations[28]: in particular, the peak at 1045 cm−1 which corresponds to the Si–O–Si asymmetric

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vibration and due to the greater ionic character of the Si–O group [29,30]. The bands at 798 cm-1 are due to Al-O stretching vibrations. while Si-OH bending vibrations, at 879 cm-1.The absorption bands

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at ∼1427 cm−1 correspond to stretching vibrations of C=O, confirming the presence of carbonate

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groups[31,32]. The bands at 451 and 559 cm-1 are also characteristic of stretching vibrations of Si– O bonds.

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3.1 Scanning electron microscopy (SEM)

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Figure 1: (a) XRD pattern of adsorbent and (b) FTIR spectra of BAW-200

The SEM images of BAW-200 (Figure 2) display a porous structure and various shapes like sphere

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agglomerate, angular, and also some non-uniform particles. The elemental analysis of BAW-200 enabled by SEM-EDS elemental mapping show that BAW-200 contains a significant amount of C

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2S).

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(74.84%), O (16.14%), and Si (4.2%) and low amount of N (0.92%), S (0.53%), and P (0.38%) (Table

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Figure 2: SEM image and mapping analysis of BAW-200

3.2 Effect of BAW-200 mass Adsorbent mass is an essential parameter in wastewater treatment processes as this factor determines the capacity of an adsorbent (BAW-200) for a given initial concentration of the 8

adsorbate (Diuron)[33]. Figure 3aillustrates the effect of BAW-200 mass on adsorption effectiveness of diuron. Diuron uptake proficiency on BAW-200 decreased with the increasing of BAW-200 mass. The highest Diuron uptake ability looked when the BAW-200 mass is about 10 mg as shown. So, under a low mass of BAW-200, the BAW-200 presented good adsorption properties toward diuron due to the availability of an active site on BAW-200. However, the adsorption removal of diuron weakened progressively with the increasing of BAW-200 mass, it's maybe recognized to the increase

selected and used in the subsequent batch experiments. 3.3 Effect of pH

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of unsaturated adsorption active sites during the uptake of diuron. Therefore, 10 mg of BAW-200 was

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The effect of pH values on the uptake ability of BAW-200 for diuron was measured in distinct solutions with pH values ranging from 1 to 12. The adsorption removal of Diuron by BAW-200 (Figure

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3b) remains stable between pH = 6.7 and pH = 12.0 analogous to a yield of 80.28 % and decreases

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below pH = 6.7. Indeed, Diuron is a cationic molecule at pH lower than 6.7 and is a neutral molecule at pH superior to 6.0[7]. Whereas, the surface of BAW-200 is charged positively at pH lower than

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the pHPZC (Figure 3c). So, at pH< 6.7, repulsive electrostatic interactions occurred between the surface of BAW-200 and Diuron molecules, which explain the decrease in uptake efficiency of

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diuron. Additionally, at a pH = 6.7, the BAW-200 and diuron are neutral, which favors nonelectrostatic interactions. At higher pH, the BAW-200 is negatively charged and diuron is neutral,

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which does not favor electrostatic interactions and therefore maintains the relatively constant diuron adsorption rate [16,34]. 3.4 Effect of temperature and time The evolution with time of diuron uptake by BAW-200 was evaluated using constant BAW-200 amount (10 mg; Diuron concentration = 20 mg/L) and various temperatures. Figure 3d shows that 9

in the first 30 min the diuron adsorption rate increased upon an increase in temperature of reaction from 20 to 40 °C. The uptake amount of Diuron increased from 156.85 mg/g (20°C) to 198.60 mg/g (40°C). This can be explained by the fact that the adsorbed Diuron molecule moves easily at a higher temperature. Then, the contact area between diuron and BAW-200 increases, which results in increases in the uptake capacity and the removal efficiency of BAW-200 for diuron. 90

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15 30 45 60 75 90 105 120 135 150 165 180

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Figure 3: (a) Effect of BAW-200 mass on adsorption efficiency (T 20 ± 1 °C; C0 20 mg/L; contact time 180 min), (b) pH effect on adsorption capacity (T 20 ± 1 °C; C0 20 mg/L; adsorbent mass 10 mg; contact time 180 min), (c) Point of zero charges of the BAW-200, and (d) Effect of temperature and contact time (C0 20 mg/L; adsorbent mass 10 mg; contact time 180 min; pH 6.7).

3.5 Adsorption kinetics To further study the rate-controlling mechanism in the uptake of diuron onto BAW-200, four kinetic models including the pseudo-first-order model (PFO), the pseudo-second-order model (PSO), the intra-particle diffusion model (IPD), and Elovich model were employed to fit the experimental data

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(Figure 4). As shown in Table 1, the agreement between experimental data and applied models was assessed by determination of coefficient (R2) as well as standard deviation (SD) to evaluate the best models describing diuron adsorption on the BAW-200 adsorbent. By comparing the calculated R2

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and SD values of diuron adsorption, it can be noted that the best coefficient of determination and the smallest SD value agreed with the PFO model compared to the PSO model. Besides, the amount

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of diuron adsorbed onto BAW-200 noticeably increased as temperature increased. However, the

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adsorption rate (K1) increased as a function of temperature, with the following order: 0.165 (1/min) at 20 °C > 0.249 (1/ min) at 30 °C > 0.395 (1/ min) at 40 °C.

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For more insight about the adsorption mechanism, intraparticle diffusion and Elovich models were used to understand the adsorption process and its rate-controlling step. In the solid-liquid

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adsorption system, mass transport can be defined by three steps: (i) external mass transfer from the solution matrix to the adsorbent surface, (ii) intraparticle diffusion, and (iii) adsorption onto

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adsorbent surface binding sites [19]. The graphical illustration of the adsorption of diuron onto BAW-200 shows that linear plots did not pass through the origin, signifying that the intraparticle diffusion steps of diuron are not the rate-controlling step. It may be related to other effects such as a boundary layer effect [19]. The C parameter gives an idea about the thickness of the boundary layer surrounding the adsorbent surface. The larger the value of C, the greater the effect of the

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boundary layer on the adsorption process [19]. Finally, the kinetic model proposed by Elovich was studied. The Elovich equation assumes that active sites of the adsorbent are heterogeneous in nature and possess different adsorption energies [35]. The parameters resulting from the Elovich equation are reported in Tables 2. This confirms the availability of numerous binding sites on the

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BAW-200 surface for the removal of diuron.

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Figure 4: Kinetics Non-linear models for fitting diuron adsorption onto BAW-200 data at a different temperature.

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(C0 20 mg/L; adsorbent mass: 10 mg; pH 6.7).

Qe,exp (mg/g) 156.85 186.04 198.60

Pseudo-First-Order (PFO) Qe,cal K1 (mg/g) (1/min) 154.78 ± 1.77 0.165 184.95 ± 0.58 0.249 198.61 ± 0.76 0.395

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T(°C)

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Table 1: Parameters of PFO, PSO, Elovich, and Intraparticle diffusion models for the adsorption of diuron (C0 20 mg/L; adsorbent mass: 10 mg; pH 6.7).

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Elovich model T(°C) 20 30

α (mg/g.min) 421.65 ± 579.61 2.77 ± 1.22

B (g/mg) 0.064 ± 0.01 0.090 ± 0.02

R2 0.988 0.999 0.998

Pseudo-Second-Order (PSO) Qe,cal K2 R2 (mg/g) (g/mg.min) 163.86 ± 2.90 0.002 0.986 192.46 ± 2.84 0.003 0.991 202.61 ± 1.66 0.007 0.997 Intra-particle diffusion model (IPD)

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Kip

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R2

0.966 0.963

8.61 ± 2.77 8.82 ± 3.75

75.64 105.35

0.489 0.408 13

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4.96 ± 6.86

0.194 ± 0.07

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8.34 ± 4.30

124.84

0.319

3.6 Adsorption isotherm In this study, we applied three commonly useful adsorption isotherm models to describe the diuron uptake characteristics onto BAW-200 (Figure 5). Exactly, the Langmuir, Freundlich, and DubininRadushkevich models (Table 1S). The matching parameters of those models are abridged in Table

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2. Rendering to the coefficient determination and standard deviation (SD), the experimental data of diuron uptake equilibrium were better described by the Langmuir model (R2 = 0.95–0.97) and Dubinin-Radushkevich model (0.92–0.95) than the Freundlich model (0.81–0.91), respectively.

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Because the Langmuir model has a higher coefficient determination and lowest standard deviation as presented in Table 2. Suggesting that homogenous active sites existed on the BAW-200 surface

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and adsorption of Diuron was monolayer [7]. Noticeably, the uptake amount of diuron increased

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when the temperature increased. The Langmuir adsorption capacity of BAW-200 presented the increasing order as follows: 232.02 mg/g (20°C) < 339.94 mg/g (30°C) < 349.52 mg/g (40°C).

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The Dubinin–Radushkevich (D–R) isotherm model was suitable to differentiate between the physical and chemical uptake of diuron on BAW-200, as exposed in Table 2. The values of E (mean energy

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of adsorption) ranging between 1 and 8 kJ mol−1 from DR isotherm postulate that the adsorption is due to physical nature between adsorbent and adsorbate [36,37]. In our situation, the value of E

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was ranged from 0.6 to 4.0 kJ mol−1 signifying that weak physical interactions are the driving force of diuron onto BAW-200 which might be hydrogen bond formation and π–π interactions as elucidated by Harnish et al [36]. By comparing our results with previous works, the BAW-200 adsorbent (232.02 mg/g (20°C), 339.94 mg/g (30°C), and 349.52 mg/g (40°C)) exhibited a relatively higher maximum adsorption 14

capability compared to granular activated carbon (316 mg/g) [16], powder activated carbon (279.4 mg/g) [17], and wheat carbon (34.1 mg/g) [17]. Therefore, BAW-200 is a talented and low-cost

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adsorbent for removing toxic contaminants.

Figure 5: Non-linear adsorption isotherms models for fitting diuron adsorption onto BAW-200 data at a different temperature (C0 5-40 mg/L; contact time 180 min; adsorbent mass 10 mg; pH 6.7).

Table 2: Parameters of Langmuir, Freundlich, and Dubinin–Radushkevich Isotherms of diuron (C0 5-40 15

mg/L; contact time 180 min; adsorbent mass 10 mg; pH 6.7).

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3.7 Thermodynamics study

Thermodynamic examination acting a crucial part in the forecast of adsorption mechanisms (i.e.,

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physical or chemical)[38,39]. The thermodynamic parameters (ΔG°, ΔH°, and ΔS°) can be intended

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according to the thermodynamic laws through the Van’t Hoff and Gibbs free energy equations presented in Table 1S. Principally, the equilibrium constant (KC) requisite be dimensionless. In this

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work, the KC derived from the Langmuir constant (KL) was employed for calculation of the thermodynamic parameters of diuron uptake. The KC can be obtained as a dimensionless parameter by multiplying KL by the molecular weight of Diuron (233.1 g/mol), 1000, and then 55.5

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20 30 40

[38,40]. The R2 value is higher than 0.99, indicating that the diuron uptake data fitted well the Van’t Hoff equation (Figure 6a). The thermodynamic parameters for adsorbing diuron onto the BAW-200

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20 30 40

are presented in Table 3S. The equilibrium constant (KC) increased considerably with an increase in

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T(°C)

Langmuir isotherm Freundlich isotherm Qmax KL KF R2 R2 n n (mg/g) (L/mg) ((mg/g)/(mg/L) ) 232.02 ± 8.86 0.65 0.975 99.19 ± 9.14 3.39 0.919 339.94 ± 12.63 7.89 0.956 285.83 ± 15.12 5.13 0.889 349.52 ± 13.10 90.63 0.970 329.27 ±28.42 6.63 0.811 Dubinin Radushkevich isotherm QDR (mg/g) KDR(mol2/kJ) R2 E (kJ/mol) 193.41 ± 15.45 1.09 0.923 0.67 327.53 ± 15.02 0.13 0.951 1.96 360.36± 16.35 0.03 0.955 4.08

the diuron solution temperature, which endorses that the adsorption process of diuron onto BAW200 was more favorable at a higher temperature and endothermic in nature. This conclusion matches well with the outcomes obtained from adsorption isotherms, the maximum Langmuir adsorption amount of diuron designated an increasing tendency at a higher temperature. Additionally, the negative values of ΔG° at all examined temperatures advise that the diuron 16

adsorption phenomenon onto BAW-200 happened spontaneously. In the meantime, the positive ΔH° (188.196 kJ/mol) reveals the endothermic nature of the diuron adsorption process, which was verified by an increase in the diuron adsorption capacity (Figure 5 and Table 2) and the equilibrium constant Kc (Table 3S) at a higher temperature. Moreover, the positive ΔS° (0.774 kJ/mol) values propose that the organization of diuron molecules at the solid/solution interface becomes more

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random during the adsorption process.

Figure 6: (a) Linear dependence of ln Kc on 1/T based on the adsorption thermodynamics; (b) Regeneration and

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recyclability of BAW-200 over five cycles of use.

3.8 Regeneration and recyclability

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Figure 6b shows the removal efficiency of BAW-200 for the uptake of diuron after five stages of recycling. The removal proficiency of BAW-200 in the first cycle was found to be 99.05%. The adsorption removal of BAW-200 slightly decreased with an increase in the number of cycles: after four cycles of diuron uptake onto BAW-200, the adsorption efficiency for diuron was around 96.45%. This indicates that the BAW-200 can be used at least five times with high adsorption proficiency. It can be deduced that the BAW-200 has excellent desorption ability and can be recycled easily from wastewater using ethanol as solvent. All these deductions illuminate that the BAW-200 can be used as a high-performance adsorbent for application in

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the field of removal of herbicides molecules.

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Conclusion

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The proficiencies of waste clinker ash (BAW-200) in the removal of diuron from aqueous solutions were investigated. The results displayed that BAW-200 had a higher diuron removal capacity (349.52

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mg/g). The analysis of the kinetic data gotten in this work advises that diuron uptake fitted well by the pseudo-first-order model. Intra-particle diffusion was not the solely rate controlling mechanism

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of diuron uptake onto BAW-200. Equilibrium data followed Langmuir isotherm model signifying monolayer adsorption of Diuron on the surfaces of BAW-200. For practical purposes, the

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regeneration of BAW-200 shows an interesting result, therefore BAW-200 can be used several times

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before replacement, reducing replacement and disposal costs. In conclusion, BAW-200 exposed a better potential to be used as an economical alternative for diuron removal than commercial activated carbon.

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. 18

Author contributions

Author 1: Mohamed Zbair

Conceived and designed the analysis, Collected the data, Performed the analysis, Wrote the paper

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Author 2: Abdelouahab El Hadrami Performed the analysis, Wrote the paper

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Author 3: Amal Bellarbi

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Contributed data or analysis tools

Other contribution

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Author 5: Abdellah Zradba

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Author 4: Mohamed Monkade

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Wrote the paper, Other contribution

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Author 6: Rachid Brahmi Other contribution

Conflict of interest The authors declare no conflict of interest

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