Groundwater for Sustainable Development 13 (2021) 100567

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Groundwater for Sustainable Development

journal homepage: http://www.elsevier.com/locate/gsd

Research paper

Fluoride removal from water by using micron zirconia/zeolite molecular

sieve: Characterization and mechanism
Yunan Gao a, b, *, Maofeng Li a, Yafang Ru a, Jinxiang Fu a
a
School of Municipal and Environmental Engineering, Shenyang Jianzhu University, Shenyang, 110168, China
b
Institute for Frontier Materials, Deakin University Geelong, Waurn Ponds, Victoria, 3216, Australia

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

Keywords: High fluoride contaminated in ground water and surface water has been prompting researchers to look for a high-
Micro zirconia efficiency, low-cost, environmental-friendly method. A novel micron zirconia/zeolite molecular sieve (ZrO2-Ze)
Zeolite molecular sieves composite was synthesized and its characterization and adsorption mechanism for fluoride was studied. Scanning
Fluoride
electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) and Fourier
Groundwater
Transform Infrared Spectroscopy (FT-IR) were used to analyze the structure and morphology of the ZrO2-Ze
adsorbents. Experimental conditions such as adsorbent dose (0.5–7.0 g/150 mL), contact time (2–12h), pH value
(3–12) and temperature (5–40 ◦ C) were optimized. The ZrO2-Ze adsorbents with fluoride removal rate of 94.89%
were processed under conditions of dose 2 g/150 mL, contact time 8 h, pH value 6 and temperature 25 ◦ C. Batch
adsorption experiments showed that fluoride adsorption followed the pseudo-second-order kinetics. Freundlich
isotherm model can better describe the behavior of ZrO2-Ze adsorption of fluoride. Thermodynamic parameters
(ΔH◦ , ΔS◦ and ΔG◦ ) were calculated to indicate an exothermic and randomness reaction process. The results in
adsorption and regeneration tests showed the evidence that ZrO2-Ze composite was a promising adsorbent for
fluoride removal.

1. Introduction treatment processes such as coagulation-sedimentation-filtration-

Fluoride ion is a non-biodegradable and persistent pollutant. Fluo­
ride pollution in water can occur due to both natural and human activity
reasons (Alcaine et al., 2020; Kimambo et al., 2019). Since fluoride is
present in several minerals, it can leach from water flow, then
contaminate ground water. On the other hand, fluoride compounds are
usually used for industrial applications such as aluminum extraction,
electronics, glass and ceramics production, semiconductor, fertilizer and
etching processes (Murambasvina and Mahamadi, 2020; Meenakshi and
Maheshwari, 2006; Shen et al., 2003; Kusrini et al., 2015). Fluoride can
leach into air and contaminate the surface water by rainwater. Ac­
cording to the World Health Organization (WHO), the maximum
acceptable concentration of fluoride ions in drinking water is less than
1.5 mg/L (WHO, 1984). The limit fluoride concentration of China
Drinking Water Standard is less than 1 mg/L (Yao et al., 2009). An excess
of fluoride ions (more than 2 ppm) in drinking water can cause various
health problems, such as dental fluorosis, softening of bones and
neurological damage (Hou et al., 2010; Poinern et al., 2011).
In China, most water purification plants use the conventional
disinfection (Zheng et al., 2014). However, these methods are not effi­
cient in the removal of fluoride especially with high concentration.
Many researches perform on defluorination to remove the excess of
fluoride effectively from drinking water (Li et al., 2013), including
adsorption (Yadav et al., 2018), ion exchange (Robshaw et al., 2019),
precipitation (Chen et al., 2017), membrane (Bouhadjar et al., 2019)
and electrodialysis (Belkada et al., 2018). Among these methods,
adsorption was the most commonly used method for fluoride removal
from drinking water due to its selectivity, low cost and high availability
(Teutli-Sequeira et al., 2013). Different adsorbents for fluoride removal
have also been developed, such as alumina and aluminum impregnated
based adsorbents (Goswami and Purkait, 2012), carbon-based adsor­
bents (Kathikeyan and Elango, 2008), calcium-based adsorbents (Basu
et al., 2013), nanoparticles(He et al., 2014), naturals materials (Meseret
et al., 2017), agricultural and biomass-based adsorbents (Maity et al.,
2018; Manna et al., 2018). However, most of the adsorbents worked
efficiently at acidic pH, which was a drawback for actual application
(Yadav et al., 2018). Some of the aluminum impregnated based adsor­
bents can be dangerous to human being health during the defluoridation

* Corresponding author. School of Municipal and Environmental Engineering, Shenyang Jianzhu University, Shenyang, 110168, China.
E-mail addresses: gaoyunan01@163.com, yunan.gao@deakin.edu.au (Y. Gao).

https://doi.org/10.1016/j.gsd.2021.100567
Received 27 November 2019; Received in revised form 29 October 2020; Accepted 22 February 2021
Available online 26 February 2021
2352-801X/© 2021 Published by Elsevier B.V.
Y. Gao et al.
water treatment process, because the aluminum leached into the water
and may cause neurodegenerative diseases (Yadav et al., 2018; Ahamad
et al., 2018). Nanomaterials has been widely investigated for fluoride
removal, due to the high costs of the nanomaterials, it is difficult to
produce a sufficient quantity and limits its application for industrial use
(Yadav et al., 2018; Wallace et al., 2019). Therefore, it is imperative to
develop high-efficiency, low-cost, environmental-friendly new adsor­
bents for fluoride removal from drinking water system.
Zirconia (ZrO2) powder have been widely used in material field. It is
characterized by significant feature such as high thermal and chemical
stability, with the feature of both acid and base active centre as well as
oxidizing and reducing sites on the surface, and considered as a potential
fluoride adsorbent due to its high electrical affinity for fluoride (Dou
et al., 2012; Fattahi et al., 2020). Micron zirconia has a small particle
size and contains a large amount of active Zr–OH and Zr–O, which can
react with fluoride by ion exchange. Due to its lower cost than
nano-zirconia, the use of micron zirconia can be more cost efficient and
easier to put into production. However, the micron zirconia powder has
no fixed shape when it is being used alone and easy to be lost during the
adsorption process. Liu et al. (2018) embedded ZrO2 in the metal skel­
eton for phosphate removal; Sun et al. (2017) used ZrO2 in combination
with magnetic Fe3O4 to remove arsenite by photocatalytic oxidation.
Therefore, it is important to find a supporter to optimize the micron ZrO2
powder during the process of removal fluoride. Zeolite molecular sieve
is a synthetic aluminosilicate with a tetrahedral structure. Due to its
regular internal pores, large specific surface area and stable structure, it
has more efficient adsorption performance than natural zeolite, and
therefore often used as a carrier for adsorption separation (Duan et al.,
2017).
In this study, a low-cost and environmental-friendly adsorbent was
synthesized by micron zirconia modified zeolite molecular sieve for
fluoride contaminated groundwater treatment. To investigate the
characterization of ZrO2-Ze before and after fluoride removal, several
techniques was invited in this study, such as X-ray diffraction (XRD),
scanning electron microscopy (SEM), energy dispersive X-ray spectros­
copy (EDS) and Fourier Transform Infrared Spectroscopy (FTIR). To
check the performance of ZrO2-Ze at different dose, adsorption time, pH
value and temperature, batch experiments have been done to obtain the
adsorption rate and adsorption capacity. The adsorption mechanism was
studied from kinetics, adsorption isotherms and adsorption thermody­
namics. Additionally, optimal regenerant was studied as well for future
application.
2. Experimental procedure
2.1. Chemicals materials
The raw materials included micron zirconia and zeolite molecular
sieve. Micron zirconia(ZrO2, molecular weight 123.22, purity quotient
of 99.97%, average particle size 50 μm) was collected from Shanghai
Hushi Co., Ltd. (Shanghai, China). Zeolite molecular sieve (NaA type,
BET surface area 7.770 m2/g, pore volume 0.113 cm3/g, average pore
diameter 4.403 nm) was purchased from Shanghai New Molecular Sieve
Co.,Ltd. China. The fluoride polluted water samples were prepared by
sodium fluoride (NaF, >98.0%, Sinopharm Chemical Reagent Co., Ltd.
China). The F− stock solution (200 mg/L) was prepared with deionized
water using sodium fluoride. F− bearing solutions (5 mg/L) were pre­
pared by diluting F− stock solution with deionized water. SPADNS agent
for fluoride analysis was purchased from HACH, USA. Hydrochloric acid
(HCl), sodium hydroxide (NaOH), sodium chloride (NaCl), sodium car­
bonate (Na2CO3), sodium bicarbonate (NaHCO3) were supplied by
Sinopharm Chemical Reagent Co., Ltd. China. All chemicals were of
analytical reagent grade.
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Groundwater for Sustainable Development 13 (2021) 100567
2.2. Preparation of ZrO2-Ze
The zeolite molecular sieve was sieved into a particle size fraction of
less than 80 μm 5 g 4A zeolite molecular sieve (4A zeolite) was added
into 100 mL HCl（hydrochloric acid）with 6% (v/v), stirred for 30 min;
4 g micron zirconia was added into the zeolite-hydrochloric acid mixed
solution, and stirred in a magnetic stirrer for 10 h, in a room temperature
condition then washed by distilled water, centrifugal separation (4000
rpm, 3 min), dried in the oven at 80 ◦ C for 12 h until constant weight.
2.3. Characterization
The phase and structure of the ZrO2-Ze powder were examined by X-
ray diffractometer (XRD) patterns (Xpent, PANalytical, Netherlands).
The morphology was characterized by scanning electron microscopy
(SEM, S4800 HITACHI, Japan) and elemental mapping imaging was
carried out with the energy dispersive X-ray spectroscopy (EDS, X-act
Oxford, England). FTIR spectra were obtained from FT-IR spectropho­
tometer (Tensor 27, Burker, German) with the scanning range from
4000 to 400 cm− 1. The Brunauer–Emmett–Teller (BET) surface area
analysis was performed by using a Micromeritics ASAP2010 instrument
to determine the specific surface area.
2.4. Adsorption experiment
Adsorption experiments were performed by batch study. Fluoride
concentration of water samples were simulated from fluoride contami­
nated groundwater (average fluoride concentration:5 mg/L) of Liaoning
province, China. The fluoride concentration was determined by using an
ultraviolet–visible spectrophotometer (D3900, HACH, USA). Adsorption
experiments were all performed three times.
Effect of the adsorbent dose (0.5, 1.0, 1.5, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0
g) and contact time (2, 4, 6, 8, 10, 12 h) of ZrO2-Ze adsorbent on fluoride
removal were also studied in 150 mL of solution(5 mgF− /L) at 25 ◦ C
temperature, pH value of 7.
Effect of pH value on fluoride removal by ZrO2-Ze were performed
with 150 mL of 5 mg/L solution of fluoride ions and 2 g of each adsor­
bent. The initial pH value was 3, 4, 5, 6, 7, 9, 11, 12 of each sample
respectively, adjusted by 0.1 M HCl or 0.1 M NaOH. The pH of each
sample was measured when the reaction reached equilibrium after 8 h.
Effect of temperature on fluoride removal was studied by adding 2 g
of ZrO2-Ze adsorbent in 150 mL of 5 mg/L fluoride ion solution at
temperature range from 5◦ C to 40 ◦ C. Each sample was measured after
reaching equilibrium with rotating speed of 150 rpm, pH value of 6.
The adsorption capacity (mg/g) and fluoride removal rate (%) were
calculated as described in Eq. (1) and Eq. (2) below.
qe = (C0 − Ce )V/m (1)
R = (C0 − Ce )/C0 × 100% (2)
where qe is the adsorption capacity (mg/g). Co is the initial concentra­
tion of the adsorbent (mg/L). Ce is the equilibrium concentration (mg/
L). m is the mass of the adsorbent (g). V is the volume of the solution (L).
R is the fluoride removal rate of ZrO2-Ze adsorbents (%).
2.5. Adsorption kinetics experiment
Adsorption kinetic tests were conducted to determine the rate of the
fluoride adsorption and the time to reach equilibrium for adsorption. It
was investigated at fluoride concentration of 5 mg/L. Water samples
were added with 2.0 g/150 mL ZrO2-Ze adsorbent stirred at the speed of
150 rpm, temperature of 25 ◦ C, pH value of 6. Water samples were
shaken for different time intervals (30, 60, 120, 180, 240, 300, 360, 420,
480, 540, 600, 660 and 720 min) and then each fluoride concentration
was analyzed.
Y. Gao et al. Groundwater for Sustainable Development 13 (2021) 100567

The data was modeled using Lagergren pseudo-first-order kinetic regeneration, fluoride removal rate, adsorption capacity and regenera­
model (Eq. (3)), pseudo-second-order kinetic model (Eq. (4)). A pseudo- tion rate (Eq. (10)) of ZrO2-Ze adsorbents were measured. The average
first order model can be represented as (Lagergren, 1898): initial fluoride concentration was 5.0 mg/L.
qer
log(qe − qt ) = log qe −
k1 t
(3) Rr = × 100% (10)
2.303 qen

Where qt and qe are fluoride adsorption amounts at time t (min) and at
time of equilibrium respectively, (mg/g); k1 (min− 1) is the constant of
the quasi-first-order kinetic model. The quasi-second-order kinetic
model is based on the assumption that the adsorption rate is controlled
by the chemical adsorption mechanism. The formula is as follows (Kong
et al., 2014):
t 1 t
= + (4)
qt k2 q2c qe
Where k2 is the second-order adsorption rate constant (g/(mg⋅min)).
2.6. Adsorption isotherm experiment
Adsorption isotherm studies were performed at fluoride concentra­
tions of 2, 4, 6, 8, 10, 12 mg/L in contact with 150 mL of a 2 g ZrO2-Ze
adsorbent respectively during 8 h at 150 rpm and 25 ◦ C temperature.
The adsorption process is commonly explained by the Langmuir (Eq.
(5)) and the Freundlich (Eq. (6)) equations (Langmuir, 1918; Freund­
lich, 1907), listed below:
Ce Ce 1 before and after fluoride adsorption obtained by EDS analysis. It was
= + (5)
qe qm qm KL
qe = KF Ce1/n (6)
Where qe is the adsorption capacity (mg/g) and qm(mg/g) indicates the
maximum adsorption capacity. KL (L/mg) is Langmuir isotherm coeffi­
cient.1/n is the Freundlich constants representing adsorption capacity,
and KF(mg/g) is the Freundlich constants representing adsorption
intensity.
Where Rr is the regeneration rate（%）. qer is the equilibrium adsorp­
tion capacity of regeneration ZrO2-Ze（mg/g）. qen is the equilibrium
adsorption capacity of new ZrO2-Ze（mg/g）.
3. Results and discussion
3.1. SEM and EDS analysis
Fig. 1a-d illustrated the surface morphology of ZrO2-Ze adsorbent
before and after fluoride adsorption at 5000 and 10000 magnification,
respectively. The images (Fig. 1a and b) showed that ZrO2-Ze before
fluoride adsorption presented cube-like rhombohedral shapes with
smooth surface. The porous structure of ZrO2-Ze was loosening (Zhang
et al., 2014). According to the detection result of BET, the specific sur­
face area of ZrO2-Ze was 24.606 m2 g− 1, the average pore diameter was
4.208 nm, and the pore volume was 0.006 cm3 g− 1. After adsorption
(Fig. 1c and d), the surface of ZrO2-Ze was wrapped in densely packed
small particles. No other changes were observed in the morphology of
the ZrO2-Ze.
Fig.2 and Table 1 showed the composition of ZrO2-Ze adsorbent
observed that O (51.64%), Si (14.84%), Al (9.79%) and Zr (10.39%)
were the main compensation element in ZrO2-Ze adsorbent. It also
verified the presence of C, Na, Ca. After adsorption with fluoride, F
(1.18%) element increased on ZrO2-Ze, which indicated ZrO2-Ze reacted
with fluoride. Content of O element was lowered after adsorption, which
showed parts of Zr–OH, Zr–O exchanged with fluoride ions (Yu et al.,
2018).
3.2. XRD analysis

2.7. Thermodynamic experiment
Thermodynamic parameters of adsorption, standard free energy
change(ΔG0), standard enthalpy change(ΔH0) and standard entropy
change(ΔS0) were calculated by the following equations (Eq.(7)–(9))
(MilonjiĆ, 2007). The tests were conducted in the same way as kinetics
except with different temperature at 278, 283, 288, 293, 298, 303, 308
and 313K, respectively.
ΔG0 = − RT ln K = ΔH 0 − TΔS0 (7)
(C0 − Ce ) qe
K= = (8)
Ce × m Ce
ΔS0 ΔH 0
ln K = − (9)
R RT
Where R is a universal gas constant 8.314 J/(mol⋅K). T is absolute
temperature(K). K is the apparent equilibrium constant. qe is adsorption
capacity (mg/g).
2.8. Regeneration
2.0 g of ZrO2-Ze adsorbents saturated with fluoride was placed in
100 mL of 1 mol/L NaOH, 1 mol/L Na2CO3, 1 mol/L NaHCO3, 1 mol/L
NaCl solution, respectively, with temperature of 25 ◦ C, rotation speed of
130 rpm and oscillation time of 12 h. Then, the adsorbents regenerated
by different chemical regenerants were rinsed with deionized water, and
dried at temperature of 60 ◦ C for 5 h until weight became stable. After
Fig.3 showed the X-ray diffraction (XRD) patterns of ZrO2-Ze
adsorbent before and after fluoride adsorption. According to the char­
acteristic peak of ZMS, 2θ values at 17.36◦ , 34.22◦ and 57.10◦ had good
agreement with the NaX zeolite crystal structure data file (JCPDS No.
38–0241) in the instrument library (Cai et al., 2015). And the new
diffraction peaks at the diffraction angles 2θ of 23.96◦ , 28.19◦ , 31.36◦ ,
35.19◦ , 38.54◦ , 40.68◦ , 44.70◦ , 45.47◦ , 49.18◦ , 50.07◦ , 54.07◦ , 55.29◦
and 57.94◦ were the characteristic peaks of hydrated zirconia (JCPDS
65–1022) (Dou et al., 2011), which indicated that the zirconia was
supported on the zeolite molecular sieve surface. Comparing patterns
between ZrO2-Ze adsorbent before and after fluoride adsorption, the
characteristic peaks of the ZrO2-Ze framework remain basically un­
changed. For the composite after adsorption, the additional peaks at
40.78◦ , 57.23◦ , 44.88◦ and 49.31◦ , 55.42◦ represented NaZrF5 and ZrF4
respectively, due to the interaction of fluoride ions with zirconium
(JCPDS-pdf 19–1197,15-0346) (Dunne et al., 2009).
3.3. FTIR analysis
FTIR spectra from the scanning range 4000 cm− 1 to 400 cm− 1 of
ZrO2-Ze adsorbent before and after fluoride adsorption were shown in
Fig.4. In the spectrum of ZrO2-Ze (line a), the band at 3385 cm− 1 was
attributed to the tensile vibration of the X–OH group (Zr–OH, Si/Al–OH)
on the surface of the zeolite molecular sieve skeleton (Samatya et al.,
2007). The strong band at 975 cm− 1 was caused by -YO4 group (Y means
Si/Al). These two bands indicated the tetrahedral basic skeleton of
zeolite molecular sieve (Yu et al., 2019). The peak observed at 490.58
cm− 1 was due to the stretching vibration of Zr–O group. A significant

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Y. Gao et al. Groundwater for Sustainable Development 13 (2021) 100567

Fig.1. SEM image of the ZrO2-Ze sample before and after fluoride adsorption. (a) ZrO2-Ze ( × 5000), (b) ZrO2-Ze ( × 10000),(c)fluoride-adsorbed ZrO2-Ze ( × 5000)
and (d)fluoride-adsorbed ZrO2-Ze ( × 10000).

Fig.2. EDS of the ZrO2-Ze sample before and after fluoride adsorption. (a) ZrO2-Ze and (b) ZrO2-Ze after fluoride adsorption.

Table 1
Element percentage of ZrO2-Ze before and after fluoride adsorption.
Samples Element(wt.%) C O Na Al Si Ca Zr F Total amount

ZrO2-Ze Weight percentage 9.65 51.64 3.36 9.79 14.84 0.35 10.39 100.00
Atomic percentage 15.29 61.11 2.78 6.90 10.06 0.13 3.71
Fluoride-adsorbed ZrO2-Ze Weight percentage 12.30 47.99 3.95 9.56 15.32 0.55 9.14 1.18 100.00
Atomic percentage 18.64 56.61 3.12 6.45 10.93 0.28 2.82 1.13

decrease in the intensities of peaks were observed for both groups
(Zr–OH and Zr–O) after F− adsorption, due to the F− exchange with –OH
and –O groups on the surface of adsorbents (Raghav and Kumar,2019),
and the position of the two peaks were shifted to 3436.29 cm− 1 and
577.24 cm− 1. After adsorption with fluoride ion, new bands appeared in
1642.4 cm− 1([HF2]− group), 739.17 cm− 1(Zr–F group), and 505.08
cm− 1([ZrF5]- group), which indicated the presence of F− on the surface
of ZrO2-Ze adsorbent after fluoride adsorption. The peak at 873.21 cm− 1
corresponding to Al–F was observed after absorbed with fluoride which
might be due to the interaction among the fluoride ions and Al–OH
groups present on the zeolite molecular sieve.
3.4. Effect of the adsorbent dose
The effect of ZrO2-Ze adsorbent dose (0.5, 1.0, 1.5, 2.0, 3.0, 4.0, 5.0,
6.0, 7.0g/150 mL) on fluoride removal at the fluoride concentration of 5
mg/L, pH of 7 and temperature of 25 ◦ C was illustrated in Fig.5. It was
shown that the removal rate of fluoride was increased from 85.5% to
92.7% with the increase in the dose of ZrO2-Ze from 0.5g/150 mL to
2.0g/150 mL. When the dose was more than 2g/150 mL, the fluoride
removal rate increased slowly. In contrast to the removal rate, the
amount of adsorption capacity decreased with the dose increasing. This
was due to the concentration of fluoride in the solution was limited, with
increasing amount of the adsorbent, accumulation of adsorbent particles
could reduce the adsorption rate of adsorbents, which illustrated the

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3.5. Effect of the contact time

Fig.6 showed the effect of contact time on the ZrO2-Ze adsorbent

adsorption capacity and fluoride removal rate at dose of 2 g/150 mL,
initial fluoride concentration of 5 mg/L, temperature of 25 ◦ C and pH of
7. It was observed that the fluoride capacities increased faster in the first
8 h. Adsorption of fluoride ions increased with increasing contact time.
However, after 8 h reaction, the adsorption capacity of the adsorbent
was almost unchanged due to low concentration of fluoride remaining in
water. Optimal time was fixed as 8 h.

3.6. Effect of pH

The pH value was one of the critical factors during the fluoride
removal process. Fig.7 showed the adsorption capacity results in the pH
range of 3–12 with ZrO2-Ze adsorbent dose of 2 g/150 mL, initial fluo­
ride concentration of 5 mg/L, contact time of 8 h at 25 ◦ C temperature.
Fig.3. XRD pattern of ZrO2-Ze before and after fluoride adsorption. (a) ZrO2-
When pH value was 3–4, hydrogen fluoride was predominant ions in the
Ze; (b) ZrO2-Ze after fluoride adsorption.
solution (Velazquez-Peña et al., 2017), fluoride was not available to be
absorbed. Consequently, the adsorption capacity and removal rate of
fluoride were not high. In the acidic environment, H+ combined with
fluoride to form HF, the presence of a large amount of H+ inhibited the
hydrolysis of HF, making the ZrO2-Ze adsorbent unable to exchange
with fluoride (Asgari et al., 2012). When pH value was between 5 and 6,
adsorption pH intervals of the adsorbent were at high-efficiency, and the
adsorption capacity and removal rate reached 0.36 mg/g and 94.89%.
When pH was 7, the adsorption amount and removal rate decreased
slightly, but still maintain at a high level, indicating that it was appli­
cable in practice. In the alkaline environment, the OH− and the fluoride
formed a competitive relationship, the hydroxyl ions may compete with
fluoride ions for the active sites on the ZrO2-Ze adsorbent which resulted
in the decreasing of the removal efficiency at pH values above 7 (Bia
et al., 2012; Zhang et al., 2015; Chaudhary et al., 2016). Therefore,
ZrO2-Ze adsorbent had a good adsorption capacity for fluoride removal
under neutral and acidic conditions.

3.7. Effect of temperature

Fig.4. FTIR spectra of the ZrO2-Ze samples before and after fluoride adsorp­
tion. (a) ZrO2-Ze and (b)fluoride-adsorbed ZrO2-Ze.
The relation between the temperature and adsorption capacity,
fluoride removal efficiency of ZrO2-Ze adsorbent was shown in Fig.8.
The tests were conducted at the condition of ZrO2-Ze adsorbent dose of
2 g/150 mL, contact time of 8h, initial fluoride concentration of 5 mg/L
and pH value of 6. The adsorption capacity of the adsorbent and removal
rate of fluoride increased from 0.32 mg/g to 0.34 mg/g and from
89.46% to 94.83% with increasing temperature from 5 ◦ C to 25 ◦ C. After
that, there was no obvious change from 25 ◦ C to 40 ◦ C. Taking the actual
water temperature and economic cost into consideration, the optimal

Fig. 5. Effect of dose on fluoride removal

decreasing of the adsorption capacity (Teimouri et al., 2016). In terms of

raw material cost, as well as comprehensive adsorption amount and
removal rate, the optimum dose was chosen to be 2 g/150 mL.

Fig. 6. Effect of contact time on fluoride removal

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Y. Gao et al. Groundwater for Sustainable Development 13 (2021) 100567

Table 2
Kinetic parameters.
Adsorbent First-order Second-order
2
qe1/ k1/ R qe2/ k2/[g/ R2
(mg/g) (min− 1) (mg/g) (mg⋅min)]

ZrO2-Ze 0.051 0.005 0.8904 0.364 0.280 0.9999

Fig. 7. Effect of pH value on fluoride removal
t/qt against time produced straight lines(R2 = 0.9999), which was more
correlated than pseudo-first-order model(R2 = 0.8904). The values of qe1
and qe2 obtained by two theoretical model were 0.051 mg/g and 0.364
mg/g, respectively. According to the results of previous effects experi­
ments, the adsorption capacity of the ZrO2-Ze adsorbent was 0.34 mg/g
with ZrO2-Ze adsorbent dose of 2g/150 mL, contact time of 8h, initial
fluoride concentration of 5 mg/L, pH value of 6 and temperature of
25 ◦ C, which was almost consistent with the qe2 result by quasi-
secondary rate model. The results showed that the adsorption process
mainly followed the quasi-secondary rate model, and the whole process
was controlled by chemical adsorption.

3.9. Adsorption isotherms

The adsorption isotherm experiment was conducted by using the

Langmuir and Freundlich isotherms. 2.0g ZrO2-Ze adsorbent was added
to conical flasks containing 150 mL fluoride ions solution with different
initial fluoride concentration respectively, then each was put into a
thermostatic shaker for 8h. Finally, the suspension was passed through a
filter (pore size 0.45 μm), and the fluoride concentration of the filtrate
was analyzed.
It can be seen from Table 3 and Fig.10 that the Freundlich adsorption
isotherm model (R2 = 0.986) can better describe the behavior of ZrO2-Ze
adsorption of fluoride, which indicated the adsorption process was a
multi-layer adsorption. It was generally considered that when n < 0.5,
adsorption was difficult to proceed, and in the isothermal formula, n =
Fig.8. Effect of temperature on fluoride removal
0.515, so the adsorption reaction was easy to continue (Kusrini et al.,
2015).
adsorption temperature was determined to be 25 ◦ C.
Table 3
3.8. Adsorption kinetics
The isotherm adsorption model parameters.
Adsorbent Langmuir Freundlich
Kinetic studies of fluoride removal were conducted with an initial
concentration of 5 mg/L (Fig.9), according to the kinetic data of the qm/(mg/ b/(L/ R 2
Kf/[(mg/g)/ n R2
adsorption fluoride ions in water by ZrO2-Ze adsorbent at room tem­ g) mg) (mg/L)1/n]

perature. Table 2 showed the kinetic parameters. By correlating the ZrO2-Ze 0.340 2.419 0.876 3.236 0.515 0.986
kinetic data with the above two rate models, it was found that the plot of

Fig.9. Pseudo-first-order kinetic(a) and Pseudo-second-order kinetic (b)

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Fig. 10. Adsorption isotherms for fluoride adsorption(a) Langmuir (b) Freundlich

3.10. Adsorption thermodynamic

By studying thermodynamics to determine the nature of the

adsorption process and verify its feasibility, the three basic thermody­
namic parameters, including standard Gibbs free energy change(ΔG0),
standard enthalpy change(ΔH0) and standard entropy change(ΔS0) were
calculated in Table 4. Values of ΔH0 and ΔS0 calculated from the van’t
Hoff plot of lnK vs 1/T. According to the data shown in Table 4, K
increased with temperature changing from 5 ◦ C to 40 ◦ C, which indi­
cated high temperature improved the adsorption capacity of fluoride on
ZrO2-Ze. Negative values of ΔG0 at above 20 ◦ C temperatures for ZrO2-Ze
confirmed that the adsorption of fluoride was spontaneous and ther­
modynamically favourable. The ΔG◦ values were positive below 15 ◦ C
indicating that the adsorption required energy from an external source
to convert reactants into products (Kara et al., 2003). ΔS0 for ZrO2-Ze
adsorbents was 68.35 × 10− 3 KJ/(K⋅mol). The value of ΔS0 indicated
that there was an increase in randomness at the solid-liquid interface
during fluoride adsorption on the ZrO2-Ze adsorbents (Lai et al., 2018). Fig.11. Regeneration studies of ZrO2-Ze by different regenerants
Values of ΔH0 for ZrO2-Ze showed that the adsorption of fluoride was
endothermic, and this proved that the adsorption amount increased as tests (FTIR and XRD) were conducted to investigate the functional
the temperature increasing. groups and bonds present on the surface of adsorbents before and after
use. From XRD and FTIR analysis, it was observed that zirconia was
3.11. Regeneration present mostly in oxidized form of Zr–O and Zr–OH which had signifi­
cant contribution in enhancing the adsorption efficiency by surface re­
The fluoride removal rates of the ZrO2-Ze absorbents after regener­ actions between ZrO2 and F− ions (Wang et al., 2019). As described by
ation by NaOH, Na2CO3, NaHCO3 and NaCl were 79.65%, 42.02%, Mohan et al. (2017), one molecule of ZrO2 can bind with five fluoride
59.36% and 62.88%, respectively (Fig.11). The fluoride adsorption ions which caused increasing uptake capacity of adsorbents (Fig.12). pH
regeneration rate was 79.14% with 1 mol/L NaOH as the regenerant value of the solution was an important effector on protonation or
which was the best among four regenerants. deprotonation of the adsorbent taking place. During hydroxyl proton­
ation, the ZrO2 existed as seven coordinated polyhedral form and F− can
3.12. Reaction mechanism be adsorbed by the protonated hydroxyl group of ZrO2 (Mullick and
Neogi, 2019). As each F− ion attached with the protonated hydroxyl
The possible mechanism of fluoride adsorption onto the ZrO2-Ze group (H2O+), the zirconium fluoride was formed by losing one mole­
surface can be explained from different perspectives. Characterization cule of water, as shown in Fig.12(1)–(5) (Dou et al., 2012). In this way,
one molecule of ZrO2 can combine up to five F− ions with the gradual
Table 4
formation of mono-, di-, tri-, tetra- and pentafluoro zirconium species
The thermodynamic parameters. (Mullick and Neogi, 2018). On the other hand, zeolite molecular sieve
was a kind of synthetic sodium zeolite, with a Si–Al–Si framework
Adsorbent T/ T/ ΔG0 ΔH0 ΔS0 KJ⋅(K.
(K) (◦ C) (KJ⋅mol− 1) (KJ⋅mol− 1) mol)− 1
tetrahedral structure, and large specific surface area. Due to the zeolite
3
molecular sieve had a weak adsorption effect on anions, it can be
278 5 1.0432 19.9 68.35 × 10−
modified by hydrochloric acid during the preparation process, which
283 10 0.6174
288 15 0.1652 made it hydrophobic and non-polar, and easy to adsorb the F− . As shown
ZrO2-Ze 293 20 − 0.3964 in FTIR analysis, Al–F was found after the F− adsorption. It was illus­
298 25 − 0.7926 trated that Al–OH in zeolite molecular sieves can be protonated and had
303 30 − 1.1443 ion exchange reaction with fluoride ions (Mukherjee et al., 2018).
308 35 − 1.1038
313 40 − 1.1821

7
Y. Gao et al.
Fig.12. Reaction mechanism of ZrO2-Ze for fluoride adsorption
4. Conclusion
Drinking fluoride-contaminated groundwater for prolonged time can
cause severe harm to human health. This study focused on preparing a
low-cost, environmentally friendly adsorbent ZrO2-Ze for treating fluo­
ride in groundwater. The adsorbent was mainly characterized by use of
micro zirconia, which was lower-cost compared to nano zirconia.
Additionally, the prepared ZrO2-Ze can act as an adsorbent for the
8
Groundwater for Sustainable Development 13 (2021) 100567
groundwater treatment with good adsorption for fluoride. When initial
fluoride concentration was 5 mg/L, removal rate of fluoride can reach
94.89% by using this ZrO2-Ze adsorbent with dose of 2g/150 mL, con­
tact time of 8h, pH value of 6 and temperature of 25 ◦ C. Based on results
of characterization and adsorption mechanism of XRD and FTIR, Zr–O
and Zr–OH in zirconium have significant contribution in adsorption
efficiency, and Al–OH in zeolite molecular sieves also had ion exchange
reaction with fluoride ions. The regeneration study revealed that the
Y. Gao et al. Groundwater for Sustainable Development 13 (2021) 100567

ZrO2-Ze has good adsorption efficiency of 79.65% after regenerated by He, J., Siah, T.S., Chen, J.P., 2014. Performance of an optimized Zr-based nanoparticle-
embedded PSF blend hollow fiber membrane in treatment of fluoride contaminated
1M NaOH solution，higher than Na2CO3, NaHCO3 and NaCl. Future
water. Water Res. 56, 88–97. https://doi.org/10.1016/j.watres.2014.02.030.
research on this ZrO2-Ze adsorbent will focus on the optimization of Hou, D., Wang, J., Zhao, C., Wang, B., Luan, Z., Sun, X., 2010. Fluoride removal from
regeneration processes and experiments on dynamic processes to pro­ brackish groundwater by direct contact membrane distillation. J. Environ. Sci. 22
vide technical parameters for large-scale production applications. (12), 1860–1867. https://doi.org/10.1016/s1001-0742(09)60332-6.
Kara, M., Yuzer, H., Sabah, E., Celik, M.S., 2003. Adsorption of cobalt from aqueous
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Declaration of competing interest s0043-1354(02)00265-8.
Kathikeyan, M., Elango, K.P., 2008. Removal of fluoride from aqueous solution using
graphite: a kinetic and thermodynamic study. Indian J. Chem. Technol. 15 (6),
The authors declare that they have no known competing financial 525–532. http://nopr.niscair.res.in/handle/123456789/2851.
interests or personal relationships that could have appeared to influence Kimambo, V., Bhattacharya, P., Mtalo, F., Mtamba, J., Ahmad, A., 2019. Fluoride
occurrence in groundwater systems at global scale and status of defluoridation –
the work reported in this paper. state of the art. Groundwater for Sustainable Development 9, 100223. https://doi.
org/10.1016/j.gsd.2019.100223.
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