Journal Pre-proof

Tuning tetracycline removal from aqueous solution onto activated 2:1

layered clay mineral: characterization, sorption and mechanistic studies

Ali Maged, Jibran Iqbal, Sherif Kharbish, Ismael Sayed Ismael, Amit
Bhatnagar

PII: S0304-3894(19)31274-9
DOI: https://doi.org/10.1016/j.jhazmat.2019.121320
Reference: HAZMAT 121320

To appear in: Journal of Hazardous Materials

Received Date: 30 July 2019

Revised Date: 23 September 2019
Accepted Date: 24 September 2019

Please cite this article as: Maged A, Iqbal J, Kharbish S, Ismael IS, Bhatnagar A, Tuning
tetracycline removal from aqueous solution onto activated 2:1 layered clay mineral:
characterization, sorption and mechanistic studies, Journal of Hazardous Materials (2019),
doi: https://doi.org/10.1016/j.jhazmat.2019.121320

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© 2019 Published by Elsevier.

 Tuning tetracycline removal from aqueous solution onto activated 2:1 layered clay
mineral: characterization, sorption and mechanistic studies

Ali Maged1,2,*, Jibran Iqbal3, Sherif Kharbish2, Ismael Sayed Ismael2, Amit Bhatnagar1

1
Department of Environmental and Biological Sciences, University of Eastern Finland, P.O. Box

1627, FI-70211 Kuopio, Finland

2
Geology Department, Faculty of Science, Suez University, El Salam City, P.O. Box 43518, Suez

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Governorate, Egypt

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3
College of Natural and Health Sciences, Zayed University, P.O. Box 144534, Abu Dhabi, United

Arab Emirates
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*Corresponding author: Ali Maged

Email address: Ali.Maged@suezuni.edu.eg

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Graphical abstract
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 Raw Bentonite Pre-treatment 500 C

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O O

O O
Si Si

- O
-
O

TC+

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After Adsorption Tetracycline
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Thermal Activated Bentonite
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Highlights
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 Egyptian bentonite clays (raw (BC) and modified (TB)) were studied for TC adsorption.

 The BET surface area of TB increased more than two-fold after modification.
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 Adsorption capacity of BC and TB was 156.7 and 388.1 mg g-1, respectively for TC.
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 Fixed-bed column studies for TC removal showed satisfactory results.

 The mechanism of TC adsorption by TB was successfully explored.

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Abstract

Water pollution due to emerging contaminants (especially pharmaceuticals) is a major environmental

threat which results in the development of antibiotic-resistant bacteria/resistance genes in the aquatic

environment. Therefore, robust and cost-effective methods are required to address this problem. In

this study, thermal activation was opted for the modification of natural bentonite clay (BC) and

utilized to investigate the adsorptive removal of tetracycline (TC) from aqueous solution. The

physicochemical surface properties of the raw and modified bentonite samples were also investigated.

The BET analysis revealed that the thermally activated bentonite (TB) has better properties than BC.

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The surface area of TB was found to be more than two-fold higher compared to that of BC. The FTIR

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spectra exhibited the existence of Al—OH, Si—O and Si—O—Si functional groups in the samples,

confirming the presence of hydrated aluminosilicate in the clay. The effects of various operating
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parameters were analyzed via optimization studies. The maximum monolayer adsorption capacity

estimated by Langmuir model was found to be 156.7 and 388.1 mg g-1 for BC and TB, respectively.
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Furthermore, fixed-bed column studies were performed to get insights into the adsorption behavior
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of TB in a dynamic system. The mechanism of TC adsorption by TB was successfully explored.

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Keywords: Tetracycline; Clay; Bentonite; Adsorption; Water treatment

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1. Introduction

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Currently, more than two billion people do not have accessibility to clean drinking water and more

than four billion people are without safe sanitation (Hokkanen et al., 2018). A large number of health

problems have emerged due to the arbitrary discharge of pollutants into the environment. Therefore,

the demand for sufficient clean water is increasing around the world. World Health Organization

(WHO) has shown concerns about contaminated water with pharmaceutical compounds (WHO,

1997). Pharmaceutical compounds are one of the emerging contaminants, which have existed in low

concentrations in the environment and can have negative effects on the human health and ecosystems,

e.g. development of antibiotic-resistant bacteria/resistance genes in the aquatic environment (Singh

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et al., 2019). While the concentrations of pharmaceutical compounds in raw domestic wastewater are

usually reported in the range of 100 ng L-1 to 10 μg L-1, their concentration in hospital and

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pharmaceutical industry effluents can reach up to 100-500 mg L-1 (Cetecioglu et al., 2013).
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Consequently, the effective control and removal of these compounds would provide greatly beneficial

stability in water treatment.

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Tetracyclines (TCs) which include tetracycline (TC), chlortetracycline and oxytetracycline are a
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group of broad-spectrum antibiotics extensively used for human therapy, aquaculture and veterinary

medicines in the treatment of various bacterial infectious diseases (Chang and Ren, 2015), and also
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as one of the growth promoters in livestock-farming (Nasseri et al., 2017). TCs are poorly absorbed

(up to 50 %) in the humans and digestive tracts of animals, the unadsorbed fraction of TCs are
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excreted through urine and stool as an unmetabolized original compound (Sarmah et al., 2006). TCs

are excessively hydrophilic, amphoteric and ionizable compounds (Wang et al., 2008). The attraction
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of TC towards solid surface strongly depends on the solution pH. Moreover, TC molecule contains

different ionizable groups depending on the solution pHs as shown in Fig. 1 (a,b). In strongly acidic

conditions (below 3.3), TC becomes positively charged (TCH3+ ) and exists as a cationic species as

shown in Fig. 1 (b). This behavior could be attributed to the dimethyl ammonium group protonation.

While, TC exists as a zwitterion (TCH2±) due to loss of a proton from the phenolic diketone moiety in

4
the range between pH 3.3 to 7.7. However, TC at pH more than 7.7 exists as monovalent (TCH − ) or

divalent (TC2− ) anions. This is due to the proton loss from tricarbonyl system and phenolic diketone

(Wang et al., 2010).

Many technologies have been developed for removing different pollutants from water including

adsorption (Alqadami et al., 2017), electrochemical technology (Gatsios et al., 2015), membrane

separation (Giacobbo et al., 2017) and hybrid technologies (Hokkanen et al., 2018). Among these

technologies, the adsorption method has gained wide attention for their effectiveness, efficiency, low

operational cost and has a wide range of source materials. Numerous adsorbents, for instance,

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activated carbon (Choi et al., 2008), carbon nanotubes (Ncibi and Sillanpää, 2015), biochar (P. Liu et

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al., 2012), ion exchange resins (Wang et al., 2017) and clay minerals (N. Liu et al., 2012) have been

reported for the removal of antibiotics. However, the separation and discharge of small colloidal
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adsorbents from treated water could induce another separation problem which must be addressed. In
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this regard, clay adsorbents present a good alternative adsorbent material option because of the ease

of their separation from aqueous media (López-Montilla et al., 2005).

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Clays are considered as important adsorbents for the removal of pharmaceutical compounds from

aqueous medium due to their high specific surface area, sorption capacity and cation exchange
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capacity (CEC). Several clays and clay minerals such as smectite, illite, zeolite, kaolinite, and

bentonite have been extensively used as adsorbents for the removal of various pollutants from
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contaminated water. Bentonite is a 2:1 type layered-structure clay mineral consisting mostly of

montmorillonite. Its basic structure includes one alumina (Al3+) octahedral sheet and two silica (Si4+)
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tetrahedral sheets. Naturally, bentonite possesses negative surface charge owing to the cation’s

substitution (isomorphic) in its crystal lattice, for e.g. substitution of Mg2+ for Al3+ in the alumina

octahedral sheet and Al3+ for Si4+ in the silica tetrahedral sheet. Owing to its properties, bentonite has

been utilized for the removal of both anionic (Chen et al., 2018) and cationic (Sen Gupta and

Bhattacharyya, 2014) pollutants.

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In ancient times, heat-treated bentonite and clays were used as bricks for construction buildings and

soil stabilization. Thermal treatment changes several physicochemical properties of bentonite, such

as particle size, permeability, water content, cohesion and specific gravity (Abu-Zreig et al., 2001).

Dehydration and dehydroxylation processes during the thermal treatment of bentonite could be

attributed to the octahedral cation movements within the octahedral sheet (Odom, 1984).

The aim of this study was to prepare and characterize the Egyptian raw and modified bentonite, and

to evaluate the possibility of using bentonite as an inexpensive adsorbent for the effective

decontamination of water polluted with tetracycline antibiotics. Thermal activation technique was

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applied for bentonite modification, in order to increase and attain maximum adsorption capacity.

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Additionally, investigation of adsorbent’s structural characteristics (raw and modified forms) was

also conducted. In batch mode, the effect of various operating conditions such as adsorbent dosage,
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initial solution pH, contact time, initial TC concentration, and ionic strength was studied. The column

experiments were carried out to examine the influence of flow rate, adsorbent loading, and influent
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TC concentration. The adsorption kinetics and isotherms were determined using widely-used models.
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The possible adsorption mechanism of tetracycline on the activated bentonite was also successfully

explored.
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2. Materials and methods

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2.1. Clay mineral

The Egyptian bentonite clay sample was obtained from Al-Hammam area, Matrouh city, Egypt, and
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used as an adsorbent. The bentonite sample was crushed, ground and sieved to a particle size less

than 160 µm. The clay mineral was washed with Milli-Q water and dried.

2.2. Reagents
The pharmaceutical solution was prepared using tetracycline (TC, purity grade ≥98.0 %). Hydrogen

peroxide (H2O2; 30% w/w), acetic acid (Acc), sodium hydroxide (NaOH), silver nitrate (AgNO3),

6
sodium acetate (Na-Ac) and sodium chloride (NaCl) were of analytical grade and purchased from

Sigma-Aldrich in purities of at least 98% and used without further treatment. The TC solutions were

prepared by diluting TC stock solution. Milli-Q water (18.2 MΩ.cm) (MQW) was used to prepare all

solutions throughout the experiments. Fig. 1 (d) summarizes the physicochemical properties of TC

(Wang et al., 2010).

2.3. Adsorbent preparation

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In order to remove the organic matters and carbonates, 25 g of bentonite clay was treated with 400

mL of 0.1 N Na-Ac and Acc (pH=5.0) and 100 mL H2O2 was added gradually. The slurry was stirred

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with magnetic stirring for 12 h at 70 ± 1 °C followed by 24 h at room temperature. The suspension

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was centrifuged at 5000 rpm for 5 min. The residue was washed three times with 0.01 N NaCl

solution. Thereafter, the suspension was centrifuged again at 5000 rpm for 15 min (model 5430,
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Eppendorf AG, Germany) and filtered. Next, the residue was washed three times with 0.01 N NaCl

solution followed by three times with MQW and then dried at 105 ± 1 °C for 24 h. Thereafter, the
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bentonite (labeled as ‘BC’) was ground, sieved using 100 µm sieve and stored in a desiccator until

further use. The BC sample was heated (muffle furnace) at 500 ±1 °C for 4 h. The optimization
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condition for the thermal activation of bentonite sample has been given in supplementary material

(section S1 and Fig. S1). The aim of the thermal activation was to increase the adsorbent’s stability
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and ion exchange capacity (Oliveira et al., 2019). Thereafter, the sample was cooled down to room
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temperature in a desiccator over silica gel overnight. Afterwards, the sample was labeled as TB and

stored in a desiccator until further use.

2.4. Physicochemical analysis

X-ray diffraction (XRD) analysis of BC and TB samples was conducted using Shimadzu, LabX XRD-

6100 with Cu-Kα radiation. The accelerating voltage was set as 40 kV, and the current was 30 mA,

7
with a monochromatic Cu Kα radiation wavelength (λ = 1.5405 Å). The scanning was limited from

3 to 70° on the 2θ angle. In order to determine the interlayer space of bentonite, the d-values was

calculated according to Bragg´s law (Bragg and Bragg, 1913) using the following eq. (1).

𝑛 𝜆 = 2𝑑 sin 𝜃 (1)

Fourier transform infrared (FT-IR) analysis of BC and TB samples was performed using Cary 660

FTIR spectrometer, Agilent technologies, USA, in order to determine the changes in the functional

groups before and after thermal treatment. The FTIR spectra of the samples were obtained within the

range of 4000–600 cm-1 with 256 scans per sample at 4 cm-1 resolution. Scanning electron microscopy

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(SEM) analysis (TESCAN VEGA (LMU) SEM), was used for the determination of surface

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morphology of BC and TB at different magnifications ranging from 500 x to 5 kx. Energy-dispersive

X-ray (EDX) analysis was conducted for investigating the chemical composition of samples and to
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determine the alteration in chemical composition before and after the thermal activation using

INCAx-act (Oxford Instruments, UK) EDX operating at 20 kV. X-ray fluorescence (XRF) analysis
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was done to gain insight into the chemical composition of BC and TB samples using Philips PW
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1410. The N2 adsorption/desorption measurements for the evaluation of the textural properties

(surface area, total pore volume, and pore diameter) were performed at -196 °C using a Belsorp Mini
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II (Japan). The point of zero charge (pHzpc) of BC and TB was determined by pH drift method. The

initial pH of 10 mM NaCl solution was adjusted in the range of 2 – 10. A measured amount of 0.05
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g adsorbent was dispersed in 25 mL of pH adjusted solution and agitated at 200 rpm in the shaker

(multi-functional orbital shaker, Grant-Bio, UK), at constant temperature 25 ± 1 °C for 24 h in glass
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bottles. The deviation in solution pH was recorded as the final pH after the aforementioned time. The

pHzpc of the adsorbents was determined by plotting the change in pH versus the initial pH. The cation

exchange capacity (CEC) of the samples was evaluated according to the ASTM C 837-81 (Standard

Test Methods of Methylene Blue (MB) Index of Clay)) (Calábria et al., 2013).

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2.5. Batch Adsorption studies

Batch experiments were conducted with BC and TB adsorbents to determine their potential towards

TC removal from aqueous solution. Equilibrium studies were carried out using a known volume of

30 mg L-1 TC solution to which 0.4 g L-1 adsorbent was added and the adsorbent-adsorbate solution

was agitated at 200 rpm in a shaker for 300 min at ambient temperature. Optimization studies were

conducted to gain insights into the effect of various experimental conditions on the adsorption of TC

onto BC and TB. The effect of pH (3 - 9), adsorbent dosage (0.1 - 1.0 g L-1), contact time (0 - 300

min), initial TC concentration (5 - 200 mg L-1) and ionic strength (0.05 - 0.5 M) was analyzed during

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the adsorption process. The solution pH was adjusted by the addition of 0.1 M NaOH and/or 0.1 M

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HCl before the adsorbents were added. All the experiments were done in duplicate. After

equilibration, the suspension was filtered with 0.45 μm cellulose acetate membrane syringe driven
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filter (Sartorius, Germany). The residual concentration of TC was analyzed by UV-visible

spectrophotometer (UV-V) (UV-2401PC, Shimazdu Corporation, Japan) at 357 nm wavelength

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(Daneshvar et al., 2018; Guo et al., 2018). The calibration plot of absorbance versus TC concentration
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level exhibits a linear relationship (R2 = 0.9998) over 0.05-30 mg L-1 concentration range. The amount

of TC adsorbed per unit mass of adsorbent (𝑞𝑒 ; mg g-1) and removal efficiency (𝑅; %) were obtained
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by using the following equations; Eq. (2-3):

𝐶𝑖 −𝐶𝑒
𝑞𝑒 = ∗𝑉 (2)
𝑚
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𝐶𝑖 −𝐶𝑒
𝑅 (%) = ∗ 100 (3)
𝐶𝑖
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For regeneration studies, the experiments were performed with BC and TB at the optimum conditions

based on the optimization studies. The adsorbents were added to a solution containing 30 mg L-1 TC

and shaken for 5 h to achieve equilibrium. Then, the separated adsorbents were dried at 60 °C for 4 h.

NaOH (0.1 M) was selected as the regeneration agent. Five cycles of adsorption/desorption were

carried out accordingly.

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2.6. Theoretical models

2.6.1. Adsorption kinetic modeling

Kinetic studies of pharmaceutical removal by an adsorbent are important for evaluating the rate and

mechanism of adsorption. In this study, pseudo-first-order kinetic model (PFO) (Lagergren, 1898)

(Eq. (4)), pseudo-second-order kinetic model (PSO) (Ho and McKay, 1999) (Eq. (5)) and Avrami

kinetic model (AV) (Avrami, 1939) (Eq. (6)) were applied to the experimental data using non-linear

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regression in MATLAB software (R2018b).

𝑞𝑡 = 𝑞𝑒 (1 − 𝑒 −𝑘1 𝑡 )

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(4)

𝑘2 𝑞𝑒2 𝑡
𝑞𝑡 = -p (5)
1+𝑘2 𝑞𝑒 𝑡

𝑛
𝑞𝑡 = 𝑞𝑒 (1 − 𝑒 (−(𝑘𝐴𝑣 𝑡) 𝐴𝑉)
) (6)
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where, 𝑞𝑒 and 𝑞𝑡 (mg g-1) are the adsorption capacity at equilibrium at time t (min) respectively, 𝑘1
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(min-1) is the rate constant of PFO, 𝑘2 (g mg-1min-1) is the rate constant of PSO and 𝑘𝐴𝑣 is the constant

of AV (min-1).
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2.6.2. Adsorption isotherm modeling

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The adsorption isotherm represents adsorbent and adsorbate interaction at variable initial
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concentrations. Experimental adsorption data were fitted to Langmuir (Langmuir, 1918), Freundlich

(Freundlich, 1924), Sips (Sips, 1948) and Redlich-Peterson (Redlich and Peterson, 1959) (Eqs 7-11),

which using non-linear regression in MATLAB (R2018b).

𝑞𝑚 𝐾𝐿 𝐶𝑒
𝑞𝑒 = 1+𝐾𝐿 𝐶𝑒
(7)

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 1⁄
𝑛
𝑞𝑒 = 𝐾𝐹 𝐶𝑒 (8)

𝛽𝑠
𝐾𝑠 𝐶𝑒
𝑞𝑒 = 𝛽𝑠 (9)
1+𝑎𝑠 𝐶𝑒

𝐾 𝐶𝑒
𝑞𝑒 = 1+𝛼𝑅 𝑔 (10)
𝑅 𝐶𝑒

where, 𝑞𝑒 (mg g-1) is the adsorption capacity of BC and TB at the equilibrium time, 𝐶𝑒 is the

equilibrium concentration (mg L-1), 𝑞𝑚 (mg g-1) is the Langmuir constant associated with adsorption

capacity at its maximum adsorption capacity (mg g-1), 𝐾𝐿 is the constant of Langmuir (L mg-1), 𝐾𝐹 is

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the constant of Freundlich (mg g-1), 𝑛 is the exponent of Freundlich related to adsorption intensity

and 𝐾𝑠 (L mg−1) is the Sips constant. 𝐾𝑅 is the Redlich-Peterson constant (L g-1), 𝛼𝑅 is the Redlich-

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Peterson constant (mg-1), and g is the Redlich-Peterson exponent.
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The correlation coefficient (R2) was used to designate the best fit of the experimental data with the
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models. R2 and root mean square error (RMSE) were used for comparing the performance of different

models. The lower RMSE value defines the data more precisely for this model. The RMSE can be
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calculated using Eq. (11) (Hafshejani et al., 2017).

∑𝑁
1 ( 𝑞𝑒𝑥𝑝 −𝑞𝑚𝑜𝑑𝑒𝑙 )
2
𝑅𝑀𝑆𝐸 = √ (11)
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where, 𝑞𝑒𝑥𝑝 and 𝑞𝑚𝑜𝑑𝑒𝑙 are the experimentally measured value and model prediction for TC
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adsorption, respectively.
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2.7. Fixed-bed column adsorption studies

2.7.1. Column preparation

The fixed-bed column studies were conducted with TB using laboratory-scale glass column (column

length of 130 mm and an internal diameter of 5 mm) assembly. The adsorbent was sandwiched by

glass wool layer to prevent the adsorbent loss, and tightly closed for good distribution of the liquid

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phase. Two different adsorbent loadings of 25 and 50 mg were employed to study the effect of varying

column beds, respectively. Two different flow rates (1.5 and 3 mL min-1) were operated to elucidate

the effect of influent flow. Similarly, two different solutions having TC concentration of 5 and 10 mg

L-1 were utilized to explicate the effect of influent concentration (Co). During the experiment, effluent

samples were collected at different time intervals. Thereafter, the samples were analyzed in order to

determine the final TC concentration in the effluent solutions. Finally, the column operation was

stopped when there was no further TC adsorption, i.e. when the influent and effluent TC

concentrations appeared similar.

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2.7.2. Column data analysis

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The effluent samples were analyzed for TC concentration using UV-visible spectrophotometer. The

performance of fixed-bed column is represented by the breakthrough curve. The determination of the
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operation and dynamic response of the column adsorption depends on the time of breakthrough

appearance and the breakthrough shape. The breakthrough point (tb) is reached when the effluent
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concentration (Ct/Co) > 0.05 of Co occurs. The point of column exhaustion (te) is reached when the

effluent concentration reaches 95 % at a constant value of Ct/Co (Kundu et al., 2004). Ct/Co as a
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function of time is used to elucidate the breakthrough curve. While, the total effluent volume ( 𝑉𝑒𝑓𝑓

(mL)) passed through column can be calculated using Eq. (12). The total quantity of TC adsorbed
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(𝑞𝑡𝑜𝑡𝑎𝑙 (mg)) by fixed-bed column, can be estimated using Eq. (13) from the area under the
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breakthrough curve (Chen et al., 2012). From 𝑞𝑡𝑜𝑡𝑎𝑙 value, the experimental maximum uptake

capacity (𝑞𝑏𝑒𝑑 , mg g-1) of the column can be calculated as shown in Eq. (14).

𝑉𝑒𝑓𝑓 = 𝑄 ∗ 𝑡𝑡𝑜𝑡𝑎𝑙 (12)

𝑄 𝑡=𝑡𝑜𝑡𝑎𝑙
𝑞𝑡𝑜𝑡𝑎𝑙 = 1000 ∫𝑡=0 𝐶𝑎𝑑 𝑑𝑡 (13)

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 𝑞𝑡𝑜𝑡𝑎𝑙
𝑞𝑏𝑒𝑑 = (14)
𝑚

where, 𝑄 is flow rate (mL min-1), 𝑡𝑡𝑜𝑡𝑎𝑙 is total flow time (min) and 𝐶𝑎𝑑 is the adsorbed TC

concentration (mg L-1) and 𝑚 is TB dry mass (g).

The total amount of TC molecules passed throw the column system (𝑚𝑡𝑜𝑡𝑎𝑙 ) is calculated using Eq.

(15). While the removal percentage (𝑅𝐸, %) of TC molecules can be calculated from Eq. (16). At

equilibrium, the unadsorbed TC concentration (𝐶𝑒𝑞 ; mg L-1) during the column process can be

obtained using Eq. (17):

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𝐶𝑜 𝑄𝑡𝑡𝑜𝑡𝑎𝑙
𝑚𝑡𝑜𝑡𝑎𝑙 = (15)
1000

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𝑞
𝑅𝐸(%) = 𝑚𝑡𝑜𝑡𝑎𝑙 × 100 (16)
𝑡𝑜𝑡𝑎𝑙

𝐶𝑒𝑞 =
𝑚𝑡𝑜𝑡𝑎𝑙 − 𝑞𝑡𝑜𝑡𝑎𝑙
𝑉𝑒𝑓𝑓
× 1000
-p (17)
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2.8. Adsorption mechanism study

The adsorption mechanism of TC onto thermally activated bentonite was studied based on the
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characterization of the adsorbent before and after TC adsorption process. TB adsorption experiments

were conducted according to the optimum conditions of the batch experiments. The contaminated TB
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sample (after sorption) was filtered. Subsequently, the samples were dried overnight without any

further treatment at 70 ± 1 °C in an air oven. The contaminated TB sample then characterized with
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the assist of XRD, FTIR and SEM analysis. Thereafter, the characterization data then compared with

the uncontaminated TB.

3. Results and Discussion

13
3.1. Characterization studies

3.1.1. XRF analysis

The chemical composition of the bentonite clay before and after thermal treatment are presented in

Table 1. The chemical analysis showed that SiO2 and Al2O3 were the major constituents of studied

adsorbents. In addition to these, Fe2O3, K2O, CaO, MgO, TiO2, and P2O5 occur as minor metallic

oxides. The ratio of Al2O3/SiO2 was found to be around 0.36 and 0.37 for BC and TB, respectively.

These values indicated that the bentonite used in this study contained mainly montmorillonite mineral

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(Chinoune et al., 2016). Fe2O3 content was high in BC and TB samples, and this could explain the

brownish and reddish colors in the raw and thermally treated bentonite, respectively (Table 1). After

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the thermal treatment, there was a decrease in loss on ignition (L.O.I.) from 9.93 % (BC) to 2.84 %

(TB). The high L.O.I. value in BC could be due to organic matter and anhydrous material content,
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which was expelled from the sample during ignition. However, lower L.O.I. value in TB could
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indicate that high loss on ignition happened during the thermal treatment (Saikia and Parthasarathy,

2010). Overall, the presence of high SiO2, Al2O3, and L.O.I. values in the clay adsorbent proved that
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the main constituent of the studied bentonite clay is silica, alumina, and water (Aytas et al., 2009).
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3.1.2. XRD analysis

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In this study, XRD diffractograms were obtained to evaluate the changes in the layered structure of

the clay adsorbent before and after thermal activation. The XRD patterns of BC and TB are illustrated
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in Fig. 2 (a). Natural bentonite is a member of the smectite clay family which is mainly composed of

montmorillonite minerals (Choo and Bai, 2016). The XRD peaks confirmed the presence of

montmorillonite and quartz. Kaolinite peak was also found in BC, while this peak disappeared in the

thermally activated bentonite. The main characteristic pattern of the montmorillonite peak was

detected at 2θ value of 5.5°. The montmorillonite peaks also appeared in the natural bentonite at 2θ

14
value of 20° and 36°; similar observations have been previously reported in the literature (Terzić et

al., 2016). Concurrently, some non-clay minerals were also recorded at 2θ value of 22° and 26° for

quartz. After the thermal activation of bentonite (TB), no significant difference was found in XRD

pattern compared to BC pattern (Fig. 2 (a)). However, the appearance of the patterns differed only in

the main montmorillonite peak at 2θ value of 5.5°, where the intensity of this peak was reduced

significantly, and a slight shift occurred towards the right at 2θ value of 8.3°. The shift of 001 lattice

plane led to decrease in the interlayer space of TB. According to Bragg's law, the interlayer distance

decreased from 1.61 nm for BC to 1.07 nm for TB. This result could be attributed to the water

of
molecule removal from the crystal lattice sheets. Moreover, this result also indicates that the high

temperature which was used for the thermal activation process, caused distortions in crystalline

ro
structure (Cantuaria et al., 2016). This phenomenon has been verified in other studies where it has
-p
been reported that during the process of calcination (temperature ≥ 400 °C), the edges of the bentonite

layers get damaged, while the layer structure remains intact (Bertagnolli et al., 2011). Therefore, TB
re
becomes more stable in the aqueous media compared to BC, making TB a better alternative for a
lP

fixed-bed column studies and solving the expansion problem of natural bentonite (Danková and

Dolinská, 2012). Based on the XRD analysis, it can be deduced that thermal activation of bentonite

increases the binding adsorption sites and the specific surface area of bentonite without changing the
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layer structure.
ur

3.1.3. FT-IR analysis

Fig. 2 (b) shows the FTIR spectra of BC and TB adsorbents. The main characteristic bands of the
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natural bentonite were observed at 3620, 993, 910, and 794 cm-1 (Zazoua et al., 2013). The bands at

3620 and 3386 cm-1 could be attributed to the O–H stretching vibration of the silanol (Si-OH) groups

from the solid and HO–H vibration of the water molecules adsorbed on the silicate, respectively

(Yaming et al., 2016). The Si-O-Si stretching vibration was observed as a strong band at 993 cm-1.

The presence of a band at 910 cm-1 represents Al–OH–Al hydroxyl bending vibration (Tyagi et al.,

15
2006). The band at 794 cm-1 could be attributed to the stretching vibration of Si–O–Fe (Zuo et al.,

2017). The existing band at 1634 cm-1 reflects the bending of HO–H bond of water molecules, which

is retained in the silicate matrix. After the thermal activation, the significant difference between the

two spectra was in the bands around 900, 1600 and 3600 cm-1. The TB spectra peaks at those

wavelengths were significantly decreased compared to the BC spectra peaks. This reduction indicated

the loss of water content in TB. However, the band at 3702 cm-1 completely disappeared after the

thermal activation for TB. The reduced band at 1634 cm-1 indicates the reduction of the H-O-H

deformation group, while the decrease in the bands at 3386 and 3702 cm-1 revealed the reduction of

of
the O-H stretching group. This phenomenon occurred due to the dehydration and dehydroxylation

processes which were triggered during the calcination process (Aytas et al., 2009).

ro
3.1.4. The nitrogen adsorption/desorption measurements
-p
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The nitrogen adsorption-desorption isotherms of BC and TB are presented in Fig. 2 (c). The BC and

TB adsorbents were of IV-type isotherm (Thommes et al., 2015). This isotherm type is characteristic
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of mesoporous materials (average pore diameter 2-50 nm) (Budsaereechai et al., 2012). There is no

significant difference in both curves for BC and TB. This indicates that the mesoporous character is
na

preserved in the natural bentonite after the thermal treatment. In addition, the similar hysteresis loops

were also observed for both BC and TB, which indicates occupation and evacuation of the mesopores
ur

by capillary condensation (Thommes et al., 2015). Table 2 summarizes the textural properties of BC
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and TB using the standard BET method, Langmuir and BJH equations. The obtained results

demonstrated that the thermal activation process has significantly elevated the surface properties of

raw bentonite. The TB was found to have more than two-fold higher surface area than BC (Table 2).

This increase in TB surface area could be attributed to the removal of adsorbed water molecules and

volatile organic compounds attached on the bentonite surface (Toor et al., 2015).

16
3.1.5. pHzpc measurements

The presence of an excess of H+ ions or OH- ions in the solution may alter the surface charge

characteristics of the adsorbent. The adsorbent carries positive surface charge below its point of zero

charge (pHzpc) and attracts negatively charged species. On the contrary, the adsorbent carries negative

surface charge above the pHzpc and is suitable for adsorption of positively charged species (Divband

Hafshejani et al., 2016). The pHzpc as depicted in Fig. 2 (d), of bentonite (BC) and thermally treated

of
bentonite (TB) was found to be 6.01 and 5.82, respectively.

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3.1.6. EDX and SEM analysis
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As shown in Fig. 3 (a,b), the most abundant constituents in BC and TB are O, Si, and Al; which are
re
the basic constituents of smectite clay group (Araujo et al., 2013). Additionally, the presence of Fe,

K, Ca, Mg and Na could be observed. The presence of these cations in the bentonite samples could
lP

be designated as polycationic bentonite which was favorable for the adsorption process (Bertagnolli

et al., 2011). The results confirmed that there were no significant differences in the adsorbent’s
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composition before and after thermal activation.

The SEM micrographs at various magnifications are illustrated in Fig. 3 (c) for BC and Fig. 3 (d) for
ur

TB. Both adsorbents exhibit individual particles having recognizable contours, fluff appearance, and

irregular platelets which formed large and thick agglomerates. No other significant difference in the
Jo

surface morphology of the materials could be observed. However, a small increase in the particle

roughness and little loss of foliated structure could be seen after the thermal activation as shown in

Fig. 3 (d). This morphological change after calcination can be attributed to the origin and composition

of the natural bentonite.

17
3.2. Tetracycline adsorption studies

3.2.1. Effect of initial pH on TC removal

The solution pH is one of the significant parameters that affect the TC adsorption and the degree of

ionization of functional groups on clay mineral surfaces. The removal efficiency of TB was higher

than that of BC as presented in Fig. 4 (a). The highest removal efficiency of 98.39 % was observed

at pH 3, whereas only 51.90% removal was achieved with BC for the given dosage and TC

of
concentration at the same pH. The removal efficiency further kept on decreasing less markedly with

the increase in solution pH for both adsorbents. On the other hand, the removal efficiency of TB

ro
decreased steadily with increasing pH throughout the studied pH range. However, the decrease was

-p
considerable at pH ≥ 7 for both adsorbents. The adsorption of TC onto clay minerals is pH-dependent

which is mainly because of the interaction between the clay surface and cationic species of TC
re
(TCH3+ ) (Browne et al., 1980). The concentration of cationic species of TC was found to decrease

with the increase in solution pH (Fig. 1 (b)). In literature, the affinity of different TC species has been
lP

reported as TCH3+ >TCH2± > TCH− (Parolo et al., 2008) which is in agreements with the pH-dependent

adsorption behavior observed in this study. Similar research findings have been reported by other
na

authors for TC adsorption on clay minerals (N. Liu et al., 2012; Parolo et al., 2008). Although, TC

adsorption onto the adsorbents was found better at acidic pH, further experiments were carried out at
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original solution pH (pH ~ 5), as it is highly unlikely to have highly acidic pH conditions in real
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wastewater treatment systems.

3.2.2. Effect of adsorbent dosage on TC removal

The influence of adsorbent dosage on TC removal was studied by utilizing various amounts of the

adsorbents (0.1- 1.0 g L-1). It could be noted that TB attained total removal (95.05 %) at a relatively
18
lower dose of 0.4 g L-1 whereas BC could only attain a removal efficiency of 50.29 % at the same

dosage (Fig. 4(b)). However, after increasing dose beyond 0.4 g L-1, the adsorption sites are higher

than the adsorbate molecules available in the solution for a given concentration resulting in total

removal and leaves the adsorbent unsaturated. Therefore, an adsorbent dosage of 0.4 g L-1 was chosen

as an optimum dose for further studies. Similar research results were also reported by other authors

(Ahmed et al., 2015).

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3.2.3. Effect of ionic strength on TC removal

The effect of electrolyte (NaCl) concentration in the aqueous solution has a significant role on TC

ro
adsorption by BC and TB. Fig. 4 (c) shows that there was a decrease in the removal efficiency of BC

-p
and TB for TC with increasing electrolyte concentrations from 0 to 0.5 M. Moreover, the removal

efficiency of BC decreased from 50.29 % (0 M NaCl) to 15.04 % (0.5 M NaCl), and from 95.05 %
re
(0 M NaCl) to 57.46 % (0.5 M NaCl) for TB. The decrease in removal efficiency with increasing

ionic strength indicated that the Na+ competed with TC species for adsorption sites. The NaCl solution
lP

of concentration ≥ 0.01 M has plentiful of Na+ ions to compete with TC species (Parolo et al., 2008).

Therefore, a decrease in the adsorption efficiency with increasing electrolyte concentration would
na

make the bentonite surface less negatively charged, which would decrease the TC adsorption. Similar

observations were also reported by Parolo et al., (2008).

ur
Jo

3.2.4. Effect of contact time and the adsorption kinetics

Fig. 5 (a, b) shows the effect of contact time on the adsorption efficiency of TC onto BC and TB.

The kinetic studies were conducted for 5–300 min under optimized experimental conditions (pH~ 5,

dose: 0.4 g L-1, initial concentration: 30 mg L-1). The adsorption kinetic modeling of TC onto BC and

TB were assessed with AV, PFO, and PSO kinetic models (Fig. 5 (a, b)). The computed parameters

19
for fitting different models are presented in Table 3. Comparison of the fitted curves and computed

model parameters suggested that PSO describes the adsorption process superior to other models, with

a high coefficient of determination (R2 = 0.99 for both BC and TB) and relatively low RMSE for both

the adsorbents (Table 3). This fact confirms that TC adsorption onto BC and TB is rate-determined

by chemisorption (Nigri et al., 2017).

3.2.5. Effect of initial TC concentration and isotherm modeling

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The influence of initial TC concentration on the adsorption capacities of the clay adsorbents was

estimated by varying concentration of TC in the range 5 – 200 mg L-1. The non-linear form of

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Langmuir, Freundlich, Sips and Redlich-Peterson isotherm models were studied to understand the

-p
adsorption equilibrium. The corresponding model parameters along with the R2, RMSE, and SSE

from the fitting of different isotherm models are listed in Table 4. The maximum monolayer
re
adsorption capacity obtained by Langmuir isotherm was 156.7 mg g-1 (BC) and 388.1 mg g-1 (TB).

The absence of saturation plateau in Fig. 5 (c,d) suggests that the conditions are not fulfilled for
lP

verifying the suitability of this model (Daneshvar et al., 2012). The high R2 (0.989 and 0.997 for BC

and TB, respectively) and n (2.079 and 1.944 for BC and TB, respectively) values of Freundlich
na

isotherm suggest the appropriateness of using Freundlich model to describe the experimental data.

The computed value of adsorption intensity n being within the range of 0 – 10 indicates the
ur

favorability of TC adsorption onto both the adsorbents (Santhana Krishna Kumar and Jiang, 2015).
Jo

Furthermore, the value of 1/n expresses the heterogeneity of the adsorption sites and affinity between

the adsorbate and adsorbent. The estimate of g obtained from Redlich-Peterson model lies within the

range of 0 – 1 indicating favorable adsorption (Nigri et al., 2017). The value of g is also useful in

determining the mechanism of adsorption. If g =1, the mechanism of adsorption is said to be physio-

sorption, while g = 0, indicates linear isotherm. The heterogeneity of adsorption is greater when the

value of g lies closer to [1-(1/n)] (Mane and Babu, 2011). The value of g in Table 4 is nearly the
20
same as [1-(1/n)], thus the adsorption of TC onto the clay adsorbents can be described as

heterogeneous in nature.

3.2.6. Reusability of BC and TB

Reusability of adsorbent materials is critical for the practical feasibility of adsorbents in water

treatment. The reusability of BC and TB was investigated by repeating the adsorption/desorption

process for five cycles with a known volume of a 0.1 M NaOH solution. As shown in Fig. 4 (d), BC

of
and TB exhibited good reusability with remarkable regeneration behavior. The sorption percent of

TC onto BC was decreased significantly from 50% to 30% after five cycles. This could be attributed

ro
to the loss of some active adsorption sites during solvent washing. However, the removal efficiency

-p
of TC onto TB was slightly decreased from 95% to 83% after five consecutive adsorption-desorption

cycles. These results suggest that TB can be successfully regenerated by NaOH treatment. The low-
re
cost regeneration of TB definitely would facilitate practical applications in water treatment.
lP

3.3. Fixed-bed column adsorption studies

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3.3.1. Effect of adsorbent loading

The effect of various adsorbent loadings on the breakthrough curve was studied using fixed-bed
ur

column. Based on the batch results, the adsorbate solution (pH ~ 5) with initial TC concentration of
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10 mg L-1 at 1.5 mL min-1 flow rate was passed through the column system with 50 and 25 mg

adsorbent loadings. The steepness of the breakthrough curve was found to be a function of adsorbent

loadings in the column system (Fig. 6 (a)). The breakthrough time was also found to decrease from

51 to 17 min with a decrease in the adsorbent loading from 50 mg to 25 mg. The column parameters

are presented in Table 5. The results exhibit that an increased adsorbent loading leads to an increase

21
in the removal efficiency (RE%) for TC from 29.44 % (25 mg) to 35.89 % (50 mg). Similarly, the TC

uptake in the column system (qbed) was found to be 48.42 and 71.28 mg g-1, when the adsorbent

loadings were 25 and 50 mg and the corresponding total TC adsorbed were 8.06 and 8.16 mg,

respectively. The increase in total TC adsorbed with the increase of adsorbent loadings in the fixed

bed column could be attributed to the increased surface area of the adsorbent and increased number

of available binding adsorption sites.

of
3.3.2. Effect of flow rate

Fig. 6 (b) shows the effect of different flow rates on the breakthrough curve. The fixed-bed column

ro
adsorption experiments were carried out at two different flow rates (1.5 and 3 mL min-1). During the

-p
experiment, the influent concentrations, solution pH and adsorbent loading were maintained as 10 mg

L-1, 5.0 and 50 mg, respectively. Breakthrough time, exhaustion time and the adsorption efficiency
re
exhibited higher values at lower flow rate (1.5 mL min-1) (Table 5). This behavior could be explained

by the fact that at higher flow rates, the adsorbate molecule does not get enough residence time (to be
lP

in contact) with the adsorbent. As a consequence, the columns operated at high flow rate show

decreased removal efficiency. On the other hand, the low flow rate provides more time for the
na

adsorbate molecule to interact with the adsorbent resulting in higher removal efficiency. Our

interpretations are in agreement with those of previous studies (Chen et al., 2012). Table 5 represents
ur

the experimental parameters calculated using the column data. It was evident that an increase in flow
Jo

rate from 1.5 to 3 mL min-1 led to a decreased removal (RE%) from 35.89 to 34.49 %, and

simultaneously decreased TC uptake in the column system (qbed) from 71.28 to 52.87 mg g-1,

respectively.

3.3.3. Effect of initial pollutant concentration

22
The column experiments were further conducted with TB to investigate the effect of initial TC

concentrations (5 and 10 mg L-1) on the breakthrough time. For this investigation, other parameters

such as flow rate (1.5 mL min-1), solution pH (pH~5) and adsorbent loading (50 mg) were kept

constant. Breakthrough time reduced with high TC concentration and the exhaustion time was

reached rapidly (Fig. 6 (c)). This behavior could be due to the quick saturation of available active

surface sites with an increase in influent TC concentration. Table 5 also reveals that increasing the

influent concentration from 5 to 10 mg L-1 led to an increase in the equilibrium TC uptake (qbed) from

45.64 to 71.28 mg g-1, and an increase in the total TC adsorbed in the column system (from 2.28 to

of
3.56 mg), respectively. However, it also shows that the removal efficiency decreased from 46.93 to

35.89 % with an increasing influent concentration from 5 to 10 mg L-1, respectively.

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3.4. Adsorption mechanism
-p
re
The mechanism of TC sorption onto TB was investigated by comparing the TB characterization

results before and after adsorption. Fig. 7 (a) illustrates the XRD patterns of TB before and after TC
lP

adsorption. The most significant differences appeared in the montmorillonite peaks at 2θ = 5.5° and

20° after adsorption. The first strong peak (001) at 2θ = 5.5° was expanded and shifted. While the
na

montmorillonite peak at 2θ = 20° showed a decrease in the intensity. It was probable that TC bonded

strongly with the hydroxyl groups. These results were similar to previous reports of TC adsorption
ur

on montmorillonite (Kulshrestha et al., 2004) and soil clay (Pils et al., 2007). Meanwhile, the original
Jo

thickness of each 2:1 layer in montmorillonite was about 0.96 nm (Zhao et al., 2012) and the size of

the TC molecule (length 1.29 nm, thickness 0.75 nm and height 0.62 nm) (Gambinossi et al., 2004).

The d-spacing expansion after adsorption suggested that TC intercalated as a monolayer between two

of 2:1 montmorillonite layer together with a monolayer of water molecules (Fig. 7 (e)).

23
Fig. 7 (b) shows the FTIR spectra of TB before and after the adsorption. The FTIR bands of the

backbone structure of TB before and after TC adsorption showed no apparent changes. This behavior

indicates that the adsorption of TC did not affect the clay structure. Originally, clay was free from

vibration bands between 3000 and 1300 cm-1, excluding the water bending vibration at around 1630

cm-1, thereby providing an appropriate window for the observation of TC adsorption bands (Chang

et al., 2009). Moreover, the band at 1635 cm-1 is principally due to the direct water coordination to

the exchangeable cations of the clay (Theng, 1974). Consequently, disappearing or shifting of this

band after interaction with tetracycline was a good indication of the replacement of this interlayer

of
cation by TC. For TC, the most characteristic peaks for the potential interacting functional groups

exist in the region between 1700 – 1200 cm-1. It is clear from the spectra of adsorbent (before and

ro
after TC adsorption) (Fig. 7 (b)) that the band at 1635 cm-1 disappeared for TB and appeared as three
-p
new bands at 1626, 1500, 1461 cm-1 after the adsorption of TC. This can be attributed to the

interaction of clay with the amide and amino carbonyl groups in the TC structure. Similar behavior
re
for TC has been reported by other authors (Kulshrestha et al., 2004). The shift in the band at 3619

cm-1 to lower frequency can be attributed to the interaction between TC and TB.
lP

Fig. 7 (c,d) shows the SEM micrographs obtained for TB before and after TC adsorption,
na

respectively. Before adsorption, the porous and irregular structure was observed for TB. However,

after TC adsorption, the roughness in the adsorbent surface was lost. This could be attributed to the
ur

filling of adsorbent’s pores with TC and hydration.

Overall, TC adsorption by TB can be via (i) ion exchange by the intercalation of TC into the interlayer
Jo

space (Fig. 7 (e①)) of TB (which was confirmed by the interlayer expanding after adsorption based

on the XRD analysis (Fig. 7 (a))), (ii) electrostatic interaction between cationic species of TC and

negative surface binding sites (Fig. 7 (e②)) (which was confirmed by the pHzpc measurements and

TC speciation (Fig. 1 (b) and Fig. 2 (c))) and (iii) surface complexation on the TB edge sites (Fig. 7

(e③)) (which was confirmed by SEM analysis (Fig. 7 (c,d))).

24
3.5. Comparison with other adsorbents

Table 6 shows a comparison between the obtained maximum adsorption capacities (qmax) for the

adsorption of tetracycline by BC and TB with other adsorbents from the literature. The presented data

in Table 6 reflect the very high adsorption capacities of TB adsorbent compared to other adsorbents.

This can be attributed mainly to the presence of different types of functional groups on TB and its

high surface area and unique porous properties. Therefore, thermal activation of bentonite is one of

of
the best clay modification techniques which can enhance its adsorption capacities for tetracycline.

Some of the adsorbent materials shown in Table 6 display a higher uptake of tetracycline as compared

ro
to the results obtained in this work. This could be due to the difference in structure and specific surface

area of adsorbents and the effective interactions between tetracycline and the adsorbent.
-p
re
4. Conclusions
lP

The natural bentonite clay collected from Al-Hammam area, Egypt was studied in terms of its

adsorption capability to remove tetracycline antibiotics from aqueous solution. Simple pre-treatment
na

and thermal activation technique were successfully applied to modify bentonite to achieve higher

adsorption efficiency for TC. The characterization of BC and TB showed that the structure of the raw
ur

clay was successfully modified without destructing the structural integrity of bentonite adsorbent.

The BET analysis revealed that the specific surface area and pore volume increased more than 2 times
Jo

after thermal activation. The elemental composition confirmed the polycationic nature of bentonite

with the dominance of SiO2 and Al2O3. The sorption ability of bentonite toward TC was significantly

elevated after activation. This sorption improvement is mostly due to the loss of water and hydroxyl

in bentonite structural, which could uncover the binding sites with negative potential and enhance its

activity. The equilibrium data fitted better with the PSO model which governs the rate kinetics of the

25
adsorption process. The Freundlich isotherm model was found to be more appropriate for describing

the adsorption behavior amongst other studied models. Increasing the ionic strength had a detrimental

effect on the adsorption efficiency of the adsorbent. Regeneration studies showed that TB can be

reused for 5 cycles using 0.1 M NaOH as eluent. Analysis of the column data revealed that increased

influent flow rate and influent concentration inversely affected the column efficiency, whereas the

increased amount of adsorbent loading reciprocated the removal efficiency of the column. Overall,

the results of this study demonstrate that TB is a promising adsorbent for TC removal. This also

suggests that the modified bentonite can be assessed as an adsorbent for other emergent pollutants in

of
large scale, which can lead to future environmental benefits.

ro
Declarations of interest -p
None
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Acknowledgements

First author (A.M.) is grateful to the cultural affairs and missions sector, the Ministry of Higher
na

Education, Egypt, for the financial support toward this study. Also, the first author is grateful to Gijs

Peters, Hogeschool van Arnhem en Nijmegen, Netherlands for his assistance in some lab
ur

experiments.
Jo

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 https://doi.org/10.1016/J.MSEC.2013.09.005

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ro
-p
re
lP
na
ur
Jo

36
 f
oo
(a) pKa2=7.7 pKa1=3.3 (c)

pr
e-
Pr
(b)
pKa3=9.7 (d)
l
na
pKa1=3.3 pKa3=9.7 Chemical Tetracycline (TC)

pKa2=7.7 Molecular formula C22H24N2O8

+ ± − − 444.44 g mol-1
ur

Molecular weight
TC TC TC T
λ max 357
Jo

Solubility (at 25 C) 231 mg L-1

Therapeutic group Antibiotic
0 2 4 6 8 10 12
pH

37
Fig. 1. (a) Chemical structure of TC depicting ionizable groups and their dissociation constant (pKa) values, (b) pH dependent TC speciation, (c)
3D structure of TC and (d) Chemical formula and properties of TC.

f
oo
pr
e-
l Pr
na
ur
Jo

38
 Jo
ur
na
l Pr

39
e-
pr
oo
f
 70
Volume Adsorbed (cm /g STP)
60
(c)
(cm3/g STP)

50
3

40

30 TB
N2 adsorption
20 N2 desorption

10
Volume Adsorbed

of
0
500.0 0.2 0.4 0.6 0.8 1.0
Volume Adsorbed (cm /g STP)

Relative pressure (P/P0)

ro
40
3

30

20
BC
-p
N2 adsorption
re
N2 desorption
10
lP

0
0.0 0.2 0.4 0.6 0.8 1.0
Relative pressure (P/P0)
Relative pressure (P/P 0)
na
ur
Jo

40
 4 (d)

2
Δ pH

of
0
2 4 6 8 10

ro
-1
pH BC
-p TB
-2
re
Fig. 2. Characterization results of the natural bentonite before and after treatment (a) XRD Pattern,
lP

(b) FTIR spectra, (c) N2 adsorption–desorption isotherm, (d) pHzpc measurements.

na
ur
Jo

41
 f
oo
pr
e-
l Pr
na
ur
Jo

Fig. 3. EDX spectra results of (a) BC and (b) TB, the micrographs of the samples with different magnifications of (c) BC and (d) TB.

42
 (a) BC
100
TB

80
TC sorbed (%)

60

40

of
20

ro
0
3 4 5 6 7 8 9
pH -p
re
100
(b) 120

Adsorption capacity (mg g-1)

lP

80 100
TC sorbed (%)

Removal efficiency
na

BC 80
60 TB
Adsorption capacity
BC 60
ur

40 TB
40
Jo

20
20

0 0
0.0 0.2 0.4 0.6 0.8 1.0
Dosage (g L-1)

43
 100
(c) BC
TB
80
TC sorbed (%)

60

40

20

of
ro
0
Control 0.1 M 0.2 M 0.3 M 0.4 M 0.5 M
NaCl Concentration (M)
100
(d)
-p BC
TB
re
75
lP
TC sorbed (%)

na

50
ur

25
Jo

0
1 2 3 4 5
Cycle number
Fig. 4. Effect of (a) pH, (b) adsorbent dosage, (c) ionic strength on TC adsorption onto BC and TB,
(d) regeneration studies of TC adsorption onto BC and TB using 0.1 M NaOH as eluent.

44
 (a) (b)

f
oo
qt (mg g-1)

pr qt (mg g-1)
e-
Pr
Time (min) Time (min)
(c) (d)

l
na

qe (mg g-1)
qe (mg g-1)

ur
Jo

Ce (mg L-1) Ce (mg L-1)

Fig. 5. (a and b) adsorption kinetic modelling of TC (30 mg L−1) by BC and TB, respectively (0.4 g L−1), (c and d) adsorption
isotherms modelling of TC (concentration: 5–200 mg L−1) by BC and TB, respectively (0.4 g L−1).
45
 1.0 (a)
0.8

0.6
Ct/Co

0.4

of
0.2
50 mg

ro
25 mg
0.0
0 100 200 300 400 500
Time (min) -p
(b)
re
1.0
lP

0.8
na

0.6
Ct/Co

ur

0.4
Jo

0.2
1.5 mL min-1
3 mL min-1
0.0
0 100 200 300 400 500
Time (min)

46
 1.0 (c)

0.8

0.6
Ct/Co

0.4

of
ro
0.2
5 mg L-1
-p 10 mg L-1
0.0
0 100 200 300 400 500 600 700
re
Time (min)
lP

Fig. 6. Effect of various parameters on breakthrough curve of TC adsorption in the Fixed-bed

column onto TB (a) adsorbent loading 50 and 25 mg of TB, (b) flow rate 1.5 and 3 mL min-1, (c)
TC concentrations 5 and 10 mg L-1.
na
ur
Jo

47
 Jo
ur
na
l Pr

48
e-
pr
oo
f
Fig. 7. (a) XRD pattern of TB before and after TC adsorption, (b) FTIR spectra of TB before and after TC adsorption, SEM micrograph of TB (c)
before and (d) after TC adsorption, (e) possible adsorption mechanism of TC adsorption onto TB.

f
oo
pr
e-
l Pr
na
ur
Jo

49
Table 1. The chemical composition of natural (BC) and thermal activated bentonite (TB) sample
(% by weight).

Metal oxide Bentonite Clay samples

(Wt%) BC TB
SiO2 54.33 53.91

of
Al2O3 19.83 20.22

TiO2 0.93 0.97

ro
Fe2O3 8.99 12.01

MgO

CaO
2.46

0.66
-p 6.35

0.61
re
K2O 1.50 1.44
lP

Na2O 1.32 0.62

P2O5 0.06 0.03

na

L.O. I 9.93 2.84

Al2O3 / SiO2 0.36 0.37

*L.O.I.= loss on ignition
ur
Jo

50
Table 2. The textural properties of bentonite samples based on N2 adsorption-desorption isotherms.

Samples
Properties
BC TB

BET Surface Area (m2 g-1) 13.19 26.94

Vm (cm3(STP) g-1) 3.03 6.19

of
Total pore volume (cm3 g-1) 74.27 *10-3 95.76 *10-3

ro
Mean pore diameter (nm) 22.53 14.22

Langmuir surface area (m2 g-1) 12.63 -p 27.88

BJH surface area (m2 g-1) 15.25 27.95

re
lP
na
ur
Jo

51
Table 3. Pseudo-first-order, pseudo-second-order and Avrami model parameters of TC adsorption
onto BC and TB.

Pseudo-first-order model
Adsorbent
k1 (min−1) qe(cal) (mg g−1) qe(exp) (mg g−1) RMSE R2

BC 0.01 45.82 45.22 1.02 0.996

TB 0.03 70.65 73.62 4.41 0.971

Pseudo-second-order model

k2 (g mg-1min-1) qe(cal) (mg g−1) qe(exp) (mg g−1) RMSE R2

of
BC 2 *10-5 59.76 45.22 0.60 0.999

TB 5 *10-4 79.91 73.62 2.69 0.990

ro
Avrami model

kav nav qe(cal) (mg g−1) qe(exp) (mg g−1) RMSE R2

BC 011 0.11 45.82

-p 45.22 1.09 0.996

TB 0.17 0.17 70.65 73.62 4.72 0.966

re
lP
na
ur
Jo

52
Table 4. Langmuir, Freundlich, Sips and Redlich–Peterson isotherm model parameters for TC
adsorption onto BC and TB.

Langmuir isotherm model

Adsorbent
qm (mg g−1) kL (dm3 mg-1) R2 RMSE SSE

BC 156.70 0.018 0.968 7.51 451.4

TB 388.10 0.015 0.977 15.18 1153

Freundlich isotherm model

KF (mg g−1) (L mg-1)1/n n R2 RMSE SSE

of
BC 10.76 2.079 0.989 4.49 161.4

TB 21.13 1.944 0.997 5.72 163.5

ro
Sips isotherm model

KS (L g−1) βS aS R2 RMSE SSE

BC 11.41 0.45 -0.013

-p 0.987 4.78 159.7

TB 21.13 0.52 1.705 e-10 0.996 5.72 163.5

re
Redlich–Peterson isotherm model

KR (L g−1) aR (mg-1) R2
lP

g RMSE SSE

BC 13400 1245 0.52 0.989 4.80 161.4

TB 131600 6230 0.49 0.995 6.39 163.5

na
ur
Jo

53
 Table 5. The effect of flow rate, adsorbent loading and initial TC concentration on the total adsorbed TC (qtotal), equilibrium uptake (qeq), total
removal efficiency of the column (RE %) and total unadsorbed TC concentration at equilibrium (Ceq).

f
oo
Parameters
Co Q M Veff ttotal qtotal qbed mtotal RE Ceq

pr
Experiments (mg L-1) (mL min-1) (mg) (mL) (min) (mg) (mg g-1) (mg) (%) (mg L-1)

Column 1 10 1.5 50 780 520 3.56 71.28 9.93 35.89 8.16

e-
Column 2 10 3 50 660 260 2.64 52.87 7.66 34.49 7.61

Column 3 10 1.5 25 360 240 1.21 48.42 4.11 29.44 8.06

Pr
Column 4 5 1.5 50 930 620 2.28 45.64 4.86 46.93 2.78

l
na
ur
Jo

54
Table 6. Comparison of maximum adsorption capacities of various adsorbents reported in the
literature for TC adsorption.

Adsorbents Adsorption References

capacity qmax (mg g-1)
Illite 32.0 (Chang et al., 2012)

Stevensite 127.0 (Antón-Herrero et al., 2018)

Montmorillonite 250.0 (Zhao et al., 2012)

Palygorskite 99.0 (Chang et al., 2009)

Nanodiamond 132.0 (Giammarco et al., 2016)

Scenedesmus quadricauda

of
295.3 (Daneshvar et al., 2018)
microalgae
Fe/graphene 442.0 (Alatalo et al., 2019)

ro
Bamboo charcoal 22.7 (Liao et al., 2013)

Zeolite Imidazole Framework-8 303.0 -p (Li et al., 2019)

Bentonite (BC) 156.7 present study

re
Thermal activated bentonite (TB) 388.1 present study
lP
na
ur
Jo

55