Journal of Environmental Chemical Engineering 6 (2018) 1364–1377

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Journal of Environmental Chemical Engineering

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Studies on performance characteristics of calcium and magnesium amended T

alumina for defluoridation of drinking water
⁎
Prakash Kumar Singh, Virendra Kumar Saharan, Suja George
Malaviya National Institute of Technology, Jaipur, Rajasthan 302017, India

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

Keywords: Two variants of amended activated alumina named CMAA 650 and CMAA 850 were prepared using activated
Adsorption alumina (AA) granules. AA was successfully coated with calcium and magnesium in the form of calcium mag-
Calcination nesium aluminum oxide (Ca0.965Mg2Al16O27), calcium aluminum oxide (Ca9(Al6O18)) and magnesium aluminum
Amended alumina oxide (MgAl2O4). CMAA 850 had a highly crystalline porous leaf like structure and higher adsorption capacity
Magnesium
than CMAA 650, with surface distribution of Ca & Mg at 30.96 and 3.29 wt% respectively. AA, CMAA 650 and
Fluoride
Calcium
CMAA 850 followed Langmuir and Temkin adsorption isotherms with maximum defluoridation capacity of 2.48,
2.61, and 2.74 mg/g respectively for treating a 10 mg/L of fluoride solution at neutral pH. CMAA 650 had a
homogenous surface and CMAA 850 had a heterogeneous surface while both followed second order rate kinetics
implying chemisorption. Fluoride adsorption equilibrium was attained in 120 min–180 min for all three ad-
sorbents. Regeneration of CMAA 650 and CMAA 850 was carried out effectively by ultrasonication for 2 min
using 1.5 M sodium hydroxide and after the second adsorption cycle, adsorption capacity dropped by 12.41%
and 12.15% respectively. The adsorption capacity of CMAA 850 was unaffected in presence of other co-existing
ions except that it got reduced by 21.4% in the presence of nitrate ions. No residual aluminum was detected in
treated water samples of both CMAA 650 and CMAA 850. However, CMAA 850 was found to be more favorable
with a higher capacity over a wider pH range of 4–9 for defluoridation of water.

1. Introduction To alleviate the problem of fluorosis many drinking water treatment

Fluorine is the most electronegative element on earth and is always
found in reduced form as fluoride or in various combined forms such as
soloist (MgF2), fluorspar (CaF2), cryolite (Na3AlF6) & fluoroapatite
[3Ca3(PO4)2CaF2] [1]. The presence of fluoride in ground water is a
persistent problem worldwide, particularly in mid African, Asian and
South-Asian regions [2]. The electronegative nature of fluorine makes it
highly reactive with electropositive ions like calcium, magnesium,
aluminum etc. Fluoride ions replace hydroxide ions from hydro-
xyapatite (HAP) − calcium containing principal constituent of bone
and teeth, resulting in a compound named fluoroapatite [3], which
forms a protective layer over them. However, continuous body intake of
fluoride through prolonged consumption of water having fluoride
concentrations above 1.0 mg/L cause dental fluorosis, a chronic disease
generally indicated by discoloration and mottling of teeth and skeletal
fluorosis a form of skeletal or non-skeletal deformity [4]. In India,
fluoride concentrations as high as 48 mg/L has been reported in
drinking water resources and 17 Indian states including Rajasthan are
known to be endemic for fluorosis [5].
techniques like membrane filtration, chemical precipitation, ion ex-
change and adsorption have been used [6–8]. Although these various
methods have been studied for treating fluoride in drinking water to
lower its concentration to an acceptable level, adsorption process is the
most widely adopted technique worldwide for water defluoridation
because of its low cost, high selectivity and greater process feasibility.
An ample number of materials have been tested as adsorbents for
fluoride removal from ground water with most of them being aluminum
based metal oxides and hydroxides because of its highest affinity for
fluoride [9]. Activated Alumina is the most widely used adsorbent for
defluoridation but the main disadvantage of activated alumina is its
amphoteric nature and narrow favorable pH range available i.e. pH 5.5
to 6.5 for fluoride removal. Therefore, pre-treatment of feed water is
required for neutral or basic feed [10]. Presence of aluminum in dis-
solved and colloidal forms has been reported in water treated with
aluminum-based adsorbents such as alumina and alum. Moreover, the
regeneration process of exhausted AA uses corrosive acids and bases,
which lead to release of aluminum fluoride complexes and solid alu-
mina waste that are toxic in nature [10,11]. These aluminum complexes

⁎
Corresponding author.
E-mail address: sgeorge.chem@mnit.ac.in (S. George).

https://doi.org/10.1016/j.jece.2018.01.053
Received 25 September 2017; Received in revised form 1 December 2017; Accepted 25 January 2018
Available online 16 March 2018
2213-3437/ © 2018 Elsevier Ltd. All rights reserved.
P.K. Singh et al.
when exposed to the environment and on consumption by living beings
through various drinking water sources may lead to various disorders
such as amyotrophic lateral sclerosis, alzheimer’s and autism spectrum
disorders [12]. In recent studies, mixed metal oxides are the major
attraction for fluoride treatment process aiming to enhance adsorption
capacity of alumina. Studies have been reported using various metals
such as cerium, lanthanum etc., to form complexes with activated
alumina for increasing its fluoride adsorption capacity [13,14], how-
ever, these adsorbents may have the disadvantage of releasing the
metals into the treated water which is very harmful. In addition, the
cost of transition metals in mixed metal oxide is one of the main con-
straints regarding their usage for bulk fluoride treatment.
The objective of this study was to modify alumina granules princi-
pally for use in drinking water defluoridation and to ensure there is no
possibility of leaching of aluminum complexes into treated water which
are potential neurotoxins. The primary focus therefore was to prepare a
better adsorbent for defluoridation and the minerals calcium and
magnesium have been considered for amending on the alumina surfaces
because of its bioavailability and as its permissible limits in drinking
water are higher (200 mg/L and 70 mg/L respectively). Inadequate
dietary calcium supply and prolonged consumption of high fluoride
concentrations especially through drinking water resources are the
principal causes of dental and skeletal fluorosis, which is a degenerative
bone disease causing deformities in children, adolescents and disorders
in pregnant and lactating mothers, because of their higher need of
calcium in these groups [15,16]. Studies have been reported on the
reversal of fluorosis with the help of diet rich in calcium products such
as dairy products, calcium tablets etc. [17] and also reported in case of
children in age group of 6–12 [18]. The drawback in administration of
these calcium supplements is its non-availability in rural areas due to
lack of knowledge as well as absence of proper supply channels. Mag-
nesium deficiency is also related with chronic fatigue syndrome, par-
kinson diseases, migraine, epilepsy, hypertension, asthma, osteoporosis,
dental caries etc., even while the calcium content is adequate or high
[19]. Drinking water may contribute significantly to the daily calcium
and magnesium intake for people with mineral deficient diets. Mag-
nesium rich diet is recommended for prevention of heart diseases, os-
teoporosis and hypertension, and recent studies recommends at least
10 mg/L magnesium in drinking water [20]. Calcium and Magnesium
have a good affinity for fluoride ions [21,22] and also the cost of cal-
cium and magnesium salts is comparatively much cheaper than metal
salts such as Zr, La, Se etc. earlier studied for defluoridation process.
However, it is observed that the use of calcium and magnesium for
defluoridation purpose is limited due to its occurrence in the form of its
oxides in powdered form, making it undesirable for continuous de-
fluoridation operations. Therefore, in order to combine the advantage
of affinity of calcium and magnesium towards fluoride and to eliminate
the toxicity of aluminum due to surface leaching of activated alumina
during defluoridation, a novel adsorbent-calcium and magnesium
amended activated alumina CMAA 650 and CMAA 850 was synthesized
and studied for finding its suitability in defluoridation process. In this
study activated alumina granules were amended with magnesium and
calcium on its surface and further studies were conducted to determine
its capacity for fluoride removal application and its regenerability.
2. Materials and methods
2.1. Materials
For the preparation of calcium and magnesium amended alumina,
activated alumina granules (FB101 grade) were purchased from M/s
Bharghava Industries Limited, Surat, India. Activated alumina, calcium
chloride (AR) (CaCl2·2H2O), magnesium chloride (AR) (MgCl2·6H2O),
sodium hydroxide (AR) (NaOH) and double distilled water were used
for preparation of the two adsorbents CMAA 650 and CMAA 850. The
chemicals utilized in the study were of analytical reagent (AR) grade
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Journal of Environmental Chemical Engineering 6 (2018) 1364–1377
and were obtained from M/s Merck India Ltd.
2.2. Synthesis of CMAA 650 and CMAA 850 for defluoridation studies
Activated alumina granules were added to 4 M magnesium chloride
solution maintained at 9.5 pH using 1 M NaOH at room temperature
(30 °C) and aged for 60 min. Further, the granules were dried at 110 °C
for 4 h and subsequently calcined at 650 °C for 3 h. The magnesium
coated alumina granules were further treated with 4 M calcium chloride
solution at 12 pH maintained using 1 M NaOH solution and further
dried for 4 h and calcined for 3 h. The adsorbent was further washed
with double distilled water until the runoff water was clear and dried at
110 °C. The dried adsorbent was activated with 100 mL/g of 0.1 M HCl
solution at 30 °C for 180 min. It was filtered using whatman 42 filter
paper and subsequently washed with double distilled water and dried at
110 °C. Dried adsorbent named CMAA 650 was stored in airtight bottles
for further studies. All steps mentioned above for the preparation of
CMAA 650 were followed for preparation of CMAA 850, in which the
dried granules were calcined at 850 °C for 3 h. In order to evaluate the
coating on the surface of activated alumina granules, characterization
techniques such as XRD, SEM, BET, XPS, FTIR and EDX were carried out
and a comparison was drawn between coated and un-coated activated
alumina granules. Further defluoridation capacity of CMAA 650, CMAA
850 and activated alumina (AA) were evaluated through batch studies.
2.3. Characterization of the adsorbent
The crystallographic structure of CMAA 650 and CMAA 850, phase
analysis and effects of calcination temperature on the adsorbents were
analyzed by X-ray diffraction analysis (X’Pert Powder Panalytical, CuKa
radiations). Two-theta angle used for analysis ranged from 10° to 70°
with a scan step time of 0.500 per sec. Micrographic view of the outer
surface of uncoated activated alumina granules, CMAA 650 and CMAA
850 was determined by scanning electron microscope (Nova Nano SEM
450). In order to determine the physio-chemical composition of the
adsorbent in terms of elemental composition with atomic number,
EDAX (Energy dispersive X-ray spectroscopy) (Xflash 6TI30 Bruker)
was also performed. Energy Dispersive X-ray Spectroscopy (EDS or
EDX) is an X-ray micro analytical technique for qualitative and quan-
titative information on the chemical composition of materials. FTIR
studies were carried out for evaluating reaction mechanism by evalu-
ating the bonding in range of 400–4000 cm−1 and the spectra were
recorded on a Perkin Elmer UTR two spectrophotometer. XPS spectra of
AA, CMAA 850 and CMAAF 850 samples were acquired using ESCA+
omicron nanotechnology oxford instruments. Monochromatic Al Kα X-
rays were generated at 300 W with base pressure of 5* 10−10 Torr and
used for spectrum measurement. The energy resolution of the spectra
was set at pass energy of 50 eV. The surface area of adsorbents was
determined by nitrogen adsorption at 77 K using a Quantachrome
NovaWin automated system.
2.4. Reagent, standard solution and instrumentation
Stock solutions and respective standards were prepared in deionized
water in plastic bottles for defluoridation studies. A 1000 ppm fluoride
stock solution was prepared by dissolving 2.21 g of anhydrous sodium
fluoride in 1000 mL deionized water in a volumetric flask and diluted to
required concentrations. Fluoride ion concentration was measured
using fluoride ion selective electrode after adding TISAB II in the ratio
1:1 (10 mL each) to samples for decomplexation of fluoride ions. TISAB
II (Total ionic strength adjustment buffer) solution was prepared by
addition of 58 g sodium chloride, 57.5 mL glacial acetic acid and 4 g
CDTA (cyclohexylene dinitrilo tetra acetic acid) in 500 mL double dis-
tilled water, solution pH was maintained at 5.5 with the addition of 5 M
NaOH and the final volume was made up to 1L. The fluoride ion con-
centrations, total dissolved solids, electrical conductivity and pH of the
P.K. Singh et al. Journal of Environmental Chemical Engineering 6 (2018) 1364–1377

samples were measured using an ion meter (Model: ORION VERSA

STAR 91) and the fluoride selective electrode (ORION 9609BNWP) was
calibrated prior to each experiment using standard fluoride solutions.
Shaking incubator (Model: REMI CIS 24 PLUS) was used for agitation of
adsorbent batches and solutions. Hot air oven (Make: Diahan) was used
for drying and a muffle furnace (Make: Optics) with a maximum tem-
perature of 1100 °C was used for calcination during the entire study.
The residual aluminum in treated water samples were measured
using an ion chromatography system (Dionex ICS-5000+ DC using
cationic column Dionex Ion Pac™ CS 5A). The mobile phase used for
detection of aluminum comprised of 0.75 M HCl which was passed
through the column at 1.36 mL/min. A post column reagent (PCR) was
used for aluminum detection which was freshly prepared every time
before analysis using ammonia, acetic acid and tiron in ultra-pure
water. The samples were passed through the column and mixed with
PCR reagent in nitrogenous environment before introducing it to
Dionex VMD (Deuterium-UV detector) with a flow rate of 2.01 mL/min.
The aluminum detection was carried out at 310 nm. Each analysis was
performed within time period of 8 min and recorded using software.
Aluminum peaks in the chromatogram were identified and quantified
based on its retention time tR (4.5 min). Aluminum chloride solutions in
ultra-pure water having concentrations 50, 100, 150, 200 and 300 μg/L
were used for generating calibration curve. The samples were filtered
using 0.2 μm Nylon 6,6 membrane and analyzed for the residual alu-
minum concentrations.

2.5. Batch adsorption studies
All batch fluoride adsorption experiments were conducted in
250 mL wide mouth plastic bottles with 100 mL of fluoride samples at
room temperature (30 ± 2 °C). The fluoride removal efficiency and
capacity of the adsorbent was determined after continuous mixing in an
orbital shaker. The effect of adsorbent dose, initial fluoride concentra-
tion, contact time and pH on fluoride removal capacity was investigated
by changing one of the parameters while keeping other parameters
constant. For finding pHpzc of adsorbents, 20 mg of adsorbent was
added into 20 mL of 0.01 M sodium chloride solution in centrifuge
tubes and pH adjustments in the range of 2 to 11 was carried out with
the addition of 0.01 M HCl and 0.01 M NaOH solution. The tubes were
then kept in an orbital shaker at 30 ± 2 °C for 24 h and the final pH of
the solutions was recorded. pHpzc was determined from plot of ΔpH
(initial and final pH difference) versus initial pH. Adsorption kinetics
were studied using various models such as pseudo first order, pseudo
second order, Elovich model and intra particle diffusion model which
were tested on the kinetics data. Equilibrium studies were carried out
using Langmuir, Freundlich, Temkin and Dubinin-Radushkevich iso-
therms. For studying the effect of temperature on adsorption process,
experiments were performed at 20, 30, 40 and 50 °C and thermo-
dynamic parameters were determined. All the experiments were per-
formed in triplicate and the mean values were reported. The adsorption
efficiency (Eq. (1)) and the defluoridation capacity (Eq. (2)) (mg F−
adsorbed/g of adsorbent) at a given contact time for the selected ad-
sorbents were determined using the following equations.
(Co − Ct )
Percentage adsorption = × 100
CO (1)
(CO − Ct )
Capacity(mg/g) =
m (2)
Where, Co and Ct are the fluoride concentration initially and at a given
time t in mg/L, respectively and m dose of adsorbent in g/L.
Fig. 1. Comparative XRD of (a) AA(α is aluminum oxide) (b) CMAA 650 and (c) CMAA
850 (ϕ is magnesium aluminum oxide, * represents calcium aluminum oxide and β is
calcium magnesium aluminum oxide).
3. Results and discussion
3.1. Characterization
CMAA 650 and CMAA 850 was characterized to study the nature of
the surface coating of calcium and magnesium over the activated alu-
mina granules for its crystallinity and surface morphology.
3.1.1. X-Ray diffraction
The comparative evaluation of the X-ray diffraction patterns of
uncoated activated alumina granules (AA) with coated CMAA 650 and
CMAA 850 was drawn on the basis of peak minimum significance 2.00
and highest score and the results are shown in Fig. 1. It was observed
from Fig. 1(a) that all the peaks correspond to aluminum oxide (Al2O3)
only (JCPDS card No. 00-001-1304) which clearly depict the purity of
AA and its amorphous nature. Fig. 1(b) and (c) depicts presence of
peaks of calcium magnesium aluminum oxide (Ca0.965 Mg2Al16O27) (01-
086-0383) calcium aluminum oxide (Ca9(Al6O18)) (01-070-0839) and
magnesium aluminum oxide (MgAl2O4) (00-047-0254) in CMAA 650
and CMAA 850 respectively. The presence of calcium magnesium alu-
minum complexes and lack of prominent aluminum oxide peaks in
CMAA 650 and CMAA 850 may be attributed to the fact that the
amalgamation of calcium and magnesium was more effective on the
surface of AA granules with formation of complexes of oxides of cal-
cium, magnesium and aluminum as observed in the XRD. Higher cal-
cination temperature during adsorbent preparation improves the crys-
talline characteristics of the material as well as the adsorption capacity
of adsorbent [23]. The effect of calcination temperature on CMAA 650
and CMAA 850 is shown in Fig. 1(b) and (c). More prominent peaks of
calcium magnesium aluminum oxide was observed for CMAA 850 than
CMAA 650 which indicate its high crystallographic nature and which is
also beneficial for its high adsorption capacity. The average crystallite
size of complex formed in case of CMAA 650 and CMAA 850 was cal-
culated through Debye Scherrer equation (Eq. (3)) [24] and reported in
Table 1,

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P.K. Singh et al.
Table 1
Average crystallite size and BET surface area of the adsorbents.
Adsorbents Average crystallite size (nm) BET Surface area m2/g
AA 17.43 312.5
CMAA 650 56.02 30.91
CMAA 850 55.76 12.75
Kλ
D=
β2θ COSθmax
where D represents average crystallite size in nm, K is equal to 0.9, λ is
X-ray wavelength (0.154 nm), β2θ is FWHM (full width at half maxima)
and θ is diffraction angle. The peaks of calcium magnesium aluminum
oxide, Calcium aluminum oxide and Magnesium aluminum oxide in
case of CMAA 650 was about 55.81, 26.61 and 57.23 nm respectively.
Whereas in the case of CMAA 850 crystallite size for calcium magne-
sium aluminum oxide, Calcium aluminum oxide and Magnesium alu-
minum oxide was about 57.45, 55.04 and 54.81 nm respectively.
3.1.2. XPS
The XPS spectra of AA, CMAA850 and spent adsorbent CMAAF850
was obtained which is presented in Fig. 2a–c. In the XPS spectra of
CMAA 850, the photoelectron lines at a binding energy of about 65,75,
285, 347 and 532 eV were recognized to be Mg2p, Al2p, C1s, Ca2p and
O1 s respectively. The XPS spectra of spent adsorbent CMAAF 850
shown in Fig. 2(c) shows new peak at binding energy 685 eV confirming
the incorporation of fluoride ion into the metal oxide surface. The
spectra confirm the formation of mixed aluminum, calcium and mag-
nesium oxides on the surface of AA as observed in Fig. 2b in comparison
with 2a and that fluoride had complexed with the Ca, Mg and Al metal
oxides after fluoride adsorption as observed in Fig. 2c.
3.1.3. SEM and EDAX analysis
The surface characteristics of CMAA 650 and CMAA 850 analyzed
using SEM and in comparison, to that of activated alumina is presented
in Fig. 3. The spectra of activated alumina granules indicate surface
Fig. 2. XPS spectra of (a) AA, (b) CMAA 850 and (c) CMAAF 850.
Journal of Environmental Chemical Engineering 6 (2018) 1364–1377
homogeneity as observed in Fig. 3(a). However, on increasing the
temperature to 650 °C, thin rod like shapes appeared in case of CMAA
650 Fig. 3(b) and further increase in temperature to 850 °C, leaf like
structure was observed in case of CMAA 850 Fig. 3(c) on the adsorbent
surface. This can be attributed to the fact that the surface has been
modified due to the presence of calcium and magnesium compounds at
higher temperatures.
The EDAX analysis of the adsorbent surface provides the elemental
composition of the adsorbents depicted in Fig. 3(d)–(f) for activated
alumina, CMAA 650 and CMAA 850 respectively. Fig. 3(d) that corre-
(3)
sponds to activated alumina showed only presence of Al & O implying
100% purity. Presence of peaks of Ca and Mg in the spectra of CMAA
650 and CMAA 850 depicts that coating of Ca and Mg on the surface of
AA was successful. Peaks of Cl in case of CMAA 650 and CMAA 850 was
also observed since calcium chloride and magnesium chloride was used
in the preparation of adsorbent. The weight distribution of Ca and Mg
over alumina surface was 30.96% and 3.29% respectively in case of
CMAA 850, which was fairly higher than 28.68% and 2.65% respec-
tively obtained for CMAA 650 as depicted in Fig. 3(f) and (e) respec-
tively.
3.1.4. Surface area
The BET analysis of activated alumina and the modified adsorbents
were carried out and the data is presented in Table 1. The samples were
degassed at 523 K for 3 h prior to analyses and the surface areas were
calculated using the Brunauer–Emmett–Teller (BET) model. It was ob-
served that the surface area of the CMAA 650 and CMAA 850 were
around 30.91 m2/g and 12.75 m2/g respectively, while surface area of
activated alumina was higher at 312.5 m2/g. The decrease in surface
area for the modified adsorbents can be attributed to increase in cal-
cination temperature from 650 to 850 °C. Overall, the changes in ad-
sorbent specific surface area with the calcination temperature may be
attributed to the changes in phase structure, particle size and surface
morphology, [25] as well as due to the amendment of calcium and
magnesium on the surface.
3.2. Batch defluoridation studies
The effect of various process parameters such as dosage, pH, initial
fluoride concentration, and temperature were studied to identify the
optimum parameters for maximum fluoride removal capacity as well as
for identifying the adsorption mechanism, equilibrium and rate kinetics
for the fluoride adsorption reactions.
3.2.1. Effect of adsorbent dose
To study the effect of adsorbent dosage on the removal efficiency of
fluoride, experiments were conducted by varying adsorbent dose in the
range of 0.5 g/100 mL to 2.5 g/100 mL at constant initial fluoride
concentration of 10 mg/L, 6.5 pH, and 30 ± 2.0 °C with agitation
(200 rpm) in an orbital shaker. An increase in adsorption capacity oc-
curred with increase in the amount of adsorbent, up to an optimum,
which is due to the increase in active adsorption sites available for
adsorption per unit weight of fluoride treated. There is an increase in
the adsorption capacity of CMAA650 and CMAA850 compared to ac-
tivated alumina. This is because the calcium and magnesium ions had
complexed with the aluminum oxide, as observed in the XRD plots as
given in Fig. 1, and the XPS image of Fig. 2. The Ca & Mg ions com-
plexed on the alumina surface which also being positively charged in
the aqueous medium interact with the fluoride ions and therefore en-
hance the adsorption capacity of modified nano alumina. It was ob-
served that 93–95% fluoride adsorption occurred with adsorbent do-
sage of 1.0 g/100 mL, and further increase in adsorbent dosage did not
result in any increase in percentage removal of fluoride as shown in
Fig. 4(a). Therefore, 1.0 g/100 mL adsorbent dosage of CMAA 650,
CMAA 850 and activated alumina (AA) was used for further batch
studies. An optimum adsorbent dose of 1.0 g/100 mL was sufficient to
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P.K. Singh et al. Journal of Environmental Chemical Engineering 6 (2018) 1364–1377

Fig. 3. SEM images of (a) AA, (b) CMAA 650 & (c) CMAA 850 at 1000 X and EDAX image of (d) AA, (e)CMAA 650 and (f)CMAA 850.

bring the residual fluoride concentration in the solution to the per- Kd =

Cs
missible limit of less than 1 mg/L as per drinking water standards. Cw (4)
The distribution coefficient Kd which shows the binding ability of
Where, Cs is the concentration of fluoride in the solid particles (mg/g)
the surface for an element was calculated using the following equation.
and Cw is the concentration of fluoride in treated water (mg/L). The log
Kd values at a given pH do not change with adsorbent concentration, if

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P.K. Singh et al.
Fig. 4. (a) Effect of adsorbent dose (b) Effect of adsorbent dose on distribution coefficient.
(Process conditions: 6.5 pH, temperature 30 ± 2.0 °C, adsorbent dose 1.0 g/100 mL,
process time 180 min, fluoride ion concentration 10 mg/L).
the surface is homogeneous in nature [26]. The dependence of dis-
tribution coefficient Kd with dosage is presented in Fig. 4(b). For CMAA
650 and AA, it was observed that distribution coefficient values remain
almost constant with change in adsorbent dose at constant conditions of
fluoride concentration, pH and temperature indicating surface homo-
geneity. Whereas the distribution coefficient values increased with in-
crease in adsorbent dose for CMAA 850 which implied that the surface
of CMAA 850 is heterogeneous. The SEM image of CMAA 850 in
Fig. 3(c) also confirmed the surface heterogeneity with leaf like grooved
structures on the adsorbent surface compared to the relatively smooth
surfaces of CMAA650 and AA.
Increase in log Kd values indicate more of fluoride ions complexing
to the surface and this accounts for the higher adsorption capacity of
CMAA850 than that of CMAA650. It is significant to highlight that
surface area of AA and CMAA 650 is 312.5 m2/g and 30.51 m2/g re-
spectively, which are higher than CMAA 850 but higher concentration
of calcium complex on the surface of CMAA 850 resulted in higher
adsorption capacity than CMAA 650 and activated alumina. The cal-
cium (30.96% in CMAA850 and 28.68% in CMAA650) magnesium ions
(3.29%in CMAA850 and 2.65%in CMAA650) complexed with the alu-
minum oxide, and being positively charged in the aqueous medium
complexed with negatively charged fluoride ions and therefore caused
an increase in the adsorption capacity compared to activated alumina.
This high capacity of modified alumina was observed at all pH values of
5 to 9 and this can also be accounted due to the higher reactivity of Ca
and Mg ions towards the counter fluoride ions compared to aluminum
ions (The reactivity series is given as
K > Na > Li > Ca > Mg > Al > C > Zn > Fe).
3.2.2. Effect of equilibrium time on adsorption capacity
Adsorption being an equilibrium driven process, the time required
to approach equilibrium is important for effective defluoridation and
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Journal of Environmental Chemical Engineering 6 (2018) 1364–1377
Fig. 5. Equilibrium time for AA, CMAA 650 and CMAA 850. (Process conditions: 6.5 pH,
temperature 30 ± 2.0 °C, adsorbent dose 1.0 g/100 mL, fluoride ion concentration
10 mg/L).
proper design of adsorption equipment. The defluoridation potential of
the adsorbents AA, CMAA 650 and CMAA 850 was determined for
dosage of 1.0 g/100 mL by varying contact time (5 min to 240 min) with
initial fluoride concentration of 10 mg/L at 30 ± 2 °C, 6.5 pH with
agitation at 200 rpm. As depicted in Fig. 5, a faster removal rate of
fluoride ions from the solution occurred in the initial 30 to 40 min in-
dicating rapid adsorption rates during the initial phase and thereafter it
became slower. Adsorption equilibrium was attained in 100 min for all
the adsorbents. It can be attributed to the fact that initially all the ad-
sorbent sites were vacant and high solute concentration gradients fa-
vored high mass transfer on to the surface of the adsorbent. As equili-
brium was approached around 120 min, the fluoride uptake by
adsorbent remained unchanged due to exhaustion of adsorption sites
and low concentration gradients between adsorbent surface con-
centration and bulk medium. In case of CMAA 850, 90% of fluoride was
removed from the fluoride solution within 30 min in comparison to that
by CMAA 650 and AA in which 78% and 72% of fluoride was removed
respectively for the same contact time. This increase in adsorption rate
of CMAA 850 in comparison to CMAA 650 and AA can be attributed to
the high crystalline nature and the porous leaf like morphology of
CMAA 850. Equilibrium was reached within a time interval of 120 min
to 150 min for all the three adsorbents
3.2.3. Effect of pH
The effect of raw water pH on the defluoridation capacity was
studied by varying the solution pH range from 3 to 9. The pH of the
solution was adjusted to desired level using 0.1 M sodium hydroxide or
0.1 M hydrochloric acid. A solution of initial fluoride concentrations of
10 mg/L, with adsorbent dosages of 1.0 g/100 mL and contact time of
180 min and constant temperature of 30 °C was maintained. Activated
alumina had a narrower working pH range between 3 and 6. At low pH
values, high concentration of H+ ions interact with F− ions forming HF
complexes and hinder fluoride interaction with metal ions or adsorption
on the adsorbent surface. Whereas at higher pH values, the reduction in
adsorption efficiency is due to the abundance of OH− ions with higher
affinity for the metal surfaces that cause hindrance to diffusion and
adsorption of fluoride ions onto the adsorbent. It was observed that
both the adsorbents CMAA 650 and CMAA 850 had higher fluoride
removal capacity over a wider working pH range as against of AA. For
CMAA 650, the best working pH range was 5 to 7. For CMAA 850 it was
observed that there was no effect on adsorption capacity below 9 pH, as
it remained constant in the pH range 4 to 9. In the case of modified
adsorbents, it was observed that pH did not have any significant effect
on the defluoridation capacity and percentage removal was much
greater than that of AA This high capacity of modified alumina at all pH
can be accounted due to the higher reactivity of Ca and Mg ions towards
P.K. Singh et al.
Fig. 6. (a) Effect of pH (b) Point of zero charge (Process conditions: temperature
30 ± 2.0 °C, adsorbent dose 1.0 g/100 mL, process time 180 min, fluoride ion con-
centration 10 mg/L).
the counter fluoride ions compared to aluminum ions and also accounts
why pH changes does not cause any significant effect on the adsorption
capacities in case of the modified adsorbent.
In aqueous medium, point of zero charge of the adsorbent always
plays a vital role in the adsorption phenomenon. The pHpzc for AA,
CMAA 650 and CMAA 850 was observed to be at pH values of 6.0, 8.0
and 9.0 respectively as shown in Fig. 6(b). The higher pHpzc value of
9 pH for CMAA 850 supports the results observed in Fig. 6(a), that there
is no significant change in the adsorption capacity of CMAA 850 for pH
less than 9.0. Maintaining the solution pH below pHpzc value in the
respective adsorbent-adsorbate consortium will cause the surface of the
adsorbent to possess an overall positive charge, which will facilitate
favorably the fluoride adsorption process. However, increase in solution
pH beyond pHpzc will result in an overall net negative charge on the
adsorbent surface resulting in repulsion between fluoride ions in solu-
tion and adsorbent surface and reducing the defluoridation capacity.
The decrease in adsorption capacity beyond pH 9.0 for CMAA 850 and
8 pH for CMAA 650 can be attributed to their respective point of zero
charges. In case of AA, the adsorption capacity was maximum only in
acidic pH range i.e. up to 6.0 pH and beyond 6.0 pH, its capacity re-
duced.
3.2.4. Effect of initial fluoride concentration
The effect of initial fluoride concentration on adsorption capacity
was studied by maintaining other parameters such as dose 10 g/L,
temperature 30 °C, shaking speed 200 rpm, contact time 180 min, and
pH 6.5 ± 0.1 constant. Adsorption capacity for CMAA 850 increased
with increase in initial fluoride concentration as shown in Fig. 7 and it
reached its saturation point i.e. capacity of 2.5 mg/g at concentration of
30 mg/L. In spite of any further increase in fluoride concentration
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Journal of Environmental Chemical Engineering 6 (2018) 1364–1377
Fig. 7. Effect of initial fluoride concentration (Process conditions: 6.5 pH, temperature
30 ± 2.0 °C, adsorbent dose 1.0 g/100 mL, process time 180 min).
beyond 30 mg/L the capacity remained unchanged and the same trend
was observed for other adsorbents.
3.3. Adsorption kinetics
Adsorption kinetics is the most important parameter that decides
the adsorption equipment capacity and needs to be studied to under-
stand fluoride uptake mechanism. The adsorption rate and fluoride
uptake kinetics on adsorbents were mainly determined on the basis of
reaction based model (pseudo first-order, pseudo second-order and
Elovich equations) and diffusion based model i.e. intra particle diffu-
sion model.
3.3.1. Reaction rate based models
Adsorption being a surface phenomenon, the adsorbate molecule
may also adsorb on inner area of porous adsorbent via film diffusion or
intra particle diffusion process. The reaction rates were studied by fit-
ting various rate models into the experimental data and the model
equations are given in Table 2. The pseudo-first order model was used
to study the reversible reaction by fitting the plot of ln(Qe-Qt) vs t,
which should give a straight line with a slope of k1 and intercept lnQe.
The values determined for Qe, Qt and k1 determined for AA, CMAA 650
and CMAA 850 are given in Table 2. The pseudo-second order model
assumes chemisorption as the rate limiting step and is represented by a
plot of t/Qt vs t which gives a straight line with a slope of 1/Qe and
intercept 1/k2Qe2 and corresponding values of k2 and Qe are given in
Table 2. The Elovich kinetic model was also tested which is applicable
for kinetics of chemisorption at solid-liquid interface [27]. The Elovich
model is a linear rate equation which determines the sorption constant
α (mgg−1h−1), the desorption constant β (gmg−1) of the fluoride ions
and Qt (mgg−1) the amount of fluoride ions adsorbed at time t and the
values of α, β, and Qt determined by fitting the model is presented in
Table 2.
3.3.2. Diffusion based model
If intra particle diffusion is the rate controlling step, Weber and
Moris proposed the theory of intra particle diffusion [28] which is re-
presented by the plot of Qt vs t0.5 which gives the value of ki (mg/gh0.5)
intra particle diffusion rate constant and the plots pass through origin.
The data is also presented in Table 2 from the model fit and it was
observed that there was poor fit of the rate kinetics data for the intra
particle diffusion model.
The applicability of the models to the rate kinetic data was eval-
uated based on their corresponding linear regression coefficient R2
values as presented in Table 2. For finding the best kinetic model, va-
lues of the regression coefficient R2 and squared sums of errors (SSE)
values were used for representing fluoride adsorption mechanism. The
SSE values of the models were calculated using the equation given
P.K. Singh et al. Journal of Environmental Chemical Engineering 6 (2018) 1364–1377

Table 2
Reaction and diffusion kinetic model.

Kinetics Linear equation Parameters Value

CMAA 650 CMAA 850 AA

Pseudo first order ln(Qe − Qt) = lnQe − k1.t Qeexp(mg/g) 0.874 0.982 0.923
Qe = amount of fluoride adsorbed at equilibrium Qtcal(mg/g) 0.308 0.148 0.371
Qt = amount of fluoride adsorbed at time t k1(min−1) 0.029 0.008 0.018
k1 = equilibrium rate constant R2 0.917 0.695 0.963
SSE 0.419 0.387 0.37

Pseudo second order t

=
1
+
t Qeexp(mg/g) 0.901 0.929 0.911
Qt k2Q2e Qe
Qe = amount of fluoride adsorbed at equilibrium Qtcal(mg/g) 0.875 0.9225 0.879
Qt = amount of fluoride adsorbed at time t k2(g/mgmin) 0.215 0.855 0.173
k2 = equilibrium rate constant R2 0.999 0.999 0.998
SSE 0.0007 0.003 0.0004

Elovich model Qt = βln(αβ) + βlnt Qt(mg/g) 0.966 0.986 1.014

Qt = amount of fluoride adsorbed at time t α(mg/gh) 8.066 1.33*107 153.9
α = adsorption rate β(g/mg) 0.115 0.0519 0.1154
β = desorption constant R2 0.9229 0.9096 0.9803
SSE 0.011 1.6*10−5 0.0097

Intra particle diffusion Qt = kit0.5 Qt(mg/g) 1.002 1.006 1.008

Qt = amount of fluoride adsorbed at time t ki(mg/gh0.5) 0.0302 0.0141 0.0316
ki = intra particle diffusion rate constant R2 0.7805 0.8295 0.9047
SSE 0.021 0.0005 0.008

below: strength of adsorption or heterogeneity factor. The value of 1/n nor-

mally lies between 0 and 1, and higher value of n indicates favorable
(Qt exp − Qt cal )2
SSE = ∑ adsorption condition [30]. The values of 1/n and Kf obtained from the
Q2t exp (5) Freundlich model fit is presented in Table 3.
Temkin isotherm model is based on the assumption that linear de-
The linear plots of various models, the regression coefficient value
crease in heat of adsorption with increase in coverage is due to ad-
(R2), respective rate constants, calculated fluoride uptake capacity (Qe),
sorbent–adsorbate interactions and adsorption is categorized by a uni-
and SSE values decide the best fit model [28]. Based on these, it was
form distribution of binding energies [31]. The linearized Temkin
observed that low SSE value in case of Elovich model fit indicated that
isotherm equation describes the equilibrium binding constant AT (L/g)
experimental data supported Elovich reaction model, which is an in-
corresponding to the maximum binding energy and constant BT related
dication of chemisorption. The high value of α (mgg−1h−1) for all the
to the heat of adsorption. A linear plot of Qe vs. ln Ce enables the de-
three adsorbents indicate rapid reaction rate and the low value of
termination of the isotherm constants BT and AT from the slope and
desorption constant β (g mg−1) for fluoride ions indicate permanent
intercept of the plot and values of AT and BT determined from the model
coverage of adsorbate on the adsorbent. The kinetic model explains
fit is presented in Table 3. AT (L/g) being the binding energy constant
rapid adsorption of fluoride for all the adsorbents studied. Based on the
had significantly high value for CMAA 650 (4.25), CMAA 850 (25.70)
data given in Table 2, the diffusion based models intra particle diffusion
and AA (10.47) which represent strong bond formation at the time of
model was unable to explain the adsorption behavior of the adsorbents
adsorption.
studied. The high R2 and low SSE values was obtained for the pseudo
The nature of adsorption i.e., physical or chemical can also be
second order model, indicate second order adsorption rate kinetics,
identified by plotting Dubinin–Radushkevich isotherms which is a
which implies chemisorption.
linear plot of ln Qe vs & ε2. Obtaining the slope K and further the mean
free energy Es (kJmol−1) is estimated for adsorption of fluoride per
3.4. Adsorption isotherms mole adsorbate using equation (Eq. (6)) as given below:

Four adsorption isotherm models, including Langmuir, Freundlich, 1

Temkin as well as Dubinin-Radushkevich (D-R) isotherms were tested
on the adsorption equilibrium data to identify the best fit model for
adsorption isotherm and are presented in Table 3. Langmuir isotherm
model is related to monolayer adsorption, and the characteristics of this
isotherm can be expressed in terms of separation factor RL. The iso-
therm is described by a plot of Ce/Qe vs Ce which result in a straight line
with slope 1/Qm and intercept 1/QmKl. A linear plot for the model for
the three adsorbents studied and corresponding values of Qm and Kl
determined from the model fit are presented in Table 3. Separation
factor (RL) for CMAA 650 is 0.238 whereas that of CMAA 850 and ac-
tivated alumina (AA) was found to be 0.075 and 0.18 respectively. The
value of separation factor was greater than zero in case of all the three
adsorbents studied which indicate that adsorption was favorable.
Freundlich isotherm supports multi-layer, non-linear adsorption
process [29], which is represented by a plot of log Qe vs log Ce that
gives a straight line with a slope 1/n and intercept log Kf. The constant
Kf (mg/g) indicates the adsorption capacity and n is the function of the
ES = −
2K (6)
The range of bonding energy i.e. for values of Es < 8 kJ/mol, the
adsorption process is physical in nature, for 8 kJ/mol–16 kJ/mol ion-
exchange mechanisms occur and for values greater than 16 kJ/mol, the
process is controlled by chemical adsorption [29]. The values of Es for
CMAA 650, CMAA 850 and AA was 5000 kJ/mol, 7453.53 kJ/mol and
9128.7 kJ/mol respectively.
The equilibrium data obtained was analyzed for accuracy of fit
using regression correlation coefficient (r) and chi- square analysis
(SSE) for all the isotherm model equations of Langmuir, Freundlich,
Temkin and Dubinin. The chi-square statistic test the sum of the square
of the difference between the experimental data and data obtained by
calculating from the models, with each squared difference divided by
the corresponding data obtained by calculating from the models.
(Qe − Qc)2
χ2 = ∑ Qc (7)

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P.K. Singh et al. Journal of Environmental Chemical Engineering 6 (2018) 1364–1377

Table 3
Model fitting for various adsorption isotherm.

Isotherms Linear equation Parameters Value

CMAA 650 CMAA 850 AA

Langmuir Ce
=
1
C +
1
Where RL =
1 Qe 2.24 2.6 2.27
Qe Qm e Qm Kl 1 + C0 KL
Qm = maximum adsorption capacity Qm (mg/g) 2.61 2.74 2.48
Kl = Langmuir adsorption constant (L/g). Kl(L/g) 0.32 1.28 0.43
Qe = amount of fluoride adsorbed at equilibrium R2 0.986 0.997 0.971
Ce = fluoride conc.in solution at equilibrium χ2 0.173 0.178 0.571

Freundlich logQ e = logK f +

1
logCe 1/n 0.439 0.340 0.314
n
Qe = fluoride adsorbed at equilibrium N 2.27 2.940 3.18
Kf = adsorption capacity Kf (mg/g) 0.719 1.27 0.9219
N = heterogeneity factor R2 0.912 0.940 0.921
Ce = fluoride conc. in solution at equilibrium χ2 0.1586 0.26149 0.0922

Temkin Qe = B T lnAT + B T lnCe Qe = amount of fluoride adsorbed at equilibrium AT (L/g) 4.25 25.70 10.47
AT = equilibrium binding constant BT 1.21 1.06 0.94
BT = Temkin isotherm constant R2 0.971 0.967 0.949
Ce = fluoride concentration in solution at equilibrium χ2 0.0817 0.077304 0.1002

Dubinin-Radushkevich lnQe = lnQd − Kε2 Qd(mg/g) 2.618 2.008 1.89

(
ε = RTln 1 +
1
Ce )
ε = polanyi potential K (mol2 kJ−2) −2*10−8 −9*10−10 −6*10−9
Qd = theoretical adsorption capacity Es (kJmol−1) 5000.00 7453.55 9128.70
Qe = amount of fluoride adsorbed at equilibrium R2 0.933 0.751 0.739
Ce = fluoride concentration in solution at equilibrium χ2 4.3215 5.509863 3.1804

Where Qc is equilibrium capacity obtained from model prediction (mg/

g) and Qe is experimental data of the equilibrium capacity (mg/g).
Based on linear regression coefficient value and chi-square values,
all the adsorbents followed Langmuir adsorption and Temkin adsorp-
tion isotherm, which indicate monolayer adsorption with chemisorp-
tion. This combination of isotherms also explains the rapid adsorption
behavior of the adsorbent observed in the kinetic experiments, as most
of the fluoride was adsorbed in first 30 min of the reaction. In case of
Freundlich adsorption isotherm values of 1/n for all the adsorbents was
between 0 and l and the higher value of ‘n’ illustrated favorable con-
ditions for adsorption. In case of Dubinin–Radushkevich isotherm the Es
(mean free energy Es) value for all the adsorbents was more than 16
kJmol−1 which indicates the process is governed by chemisorption.

3.5. Adsorption thermodynamics

Adsorption experiments were conducted at temperature ranges

varying from 293 to 323 K, in order to determine the effect of tem-
perature on adsorption behavior of fluoride on respective adsorbents,
and the thermodynamic parameters such as change in enthalpy, en-
tropy (Eq. (9)) and Gibbs free energy (Eq. (10)) were calculated using
the following equations [32].
qe
KD =
ce (8)

ΔS ΔH0
ln KD = ⎛ 0 ⎞ − ⎛ ⎞
⎝ R ⎠ ⎝ RT ⎠ (9)

ΔG0 = ΔH0 − TΔS0 (10)

where KD is the distribution coefficient for the adsorption in g/L, ΔGo
(J/mol) change in Gibbs free energy, R (J/molK) universal gas constant,
T (K) absolute temperature, ΔS0 (J/molK) change in entropy and ΔHo
(J/mol) change in enthalpy. The Van’t Hoff plot of log Kd vs 1/T based
on (Eq. (9)) is shown in Fig. 8(b) which give values of thermodynamic
parameters ΔHo/R and ΔSo/R which helps in predicting parameters
such as ΔHo, ΔSo, and ΔGo and respective values are given in Table 4.
Fig. 8(a) presents the extent of fluoride removal while treating
10 mg/L of fluoride solution at 293 K–323 K at pH 7 for 180 min. In case
Fig. 8. (a) Effect of temperature on fluoride removal by adsorbents CMAA 650, CMAA
850 and AA, (b) Van’t Hoff plots (Process conditions: 6.5 pH, adsorbent dose 1.0 g/
100 mL, process time 180 min, fluoride ion concentration 10 mg/L).
of CMAA 650, adsorption of fluoride on the surface of adsorbent slightly
decreased with increase in temperature from 293 K to 323 K. The re-
duction in ΔG0 value for CMAA 650 with increase in temperature in-
dicates that the reaction is becoming less spontaneous. In case of CMAA
850 and AA, a very slight increase in ΔG0 value was observed for CMAA
850 and AA with increase in temperature from 293 K to 323 K. However

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P.K. Singh et al. Journal of Environmental Chemical Engineering 6 (2018) 1364–1377

Table 4
Thermodynamics parameters of adsorbents at various temperatures.

Temperature (K) ΔG0(J/mol)

CMAA 650 CMAA 850 AA

293 −2185.43 −1823.48 −2516.67

303 −1574.57 −3781.08 −3501.71
313 −964.731 −5738.68 −4486.75
323 −454.268 −7500.52 −5471.91
Thermodynamic Parameters
ΔH0(J/mol) −2.01 × 107 5.5 × 107 2.63 × 107
ΔS0(J/molK) −61.02 195.76 98.504

overall no significant effect of temperature on fluoride adsorption

processes was observed in case of the three adsorbents.

3.6. Adsorbent desorption and regeneration

In case of chemisorption, adsorbate having stronger bond with ad-

sorbent will result in poor desorption of the adsorbate in respective
eluent. Therefore, adsorbent regeneration which is one of the prime
factor for process economics, was studied for the modified adsorbents
CMAA 650 and CMAA 850. Prior to regeneration studies, the ad-
sorbents were completely exhausted with continuous treatment of very
highly concentrated fluoride solution (100 mg/L) for four hours. The
exhausted adsorbent was dried in hot air oven at 110 °C for 2 h and
subsequently washed with double distilled water. The residual con-
centration in the washed water was determined for all the adsorbents,
which was found to be negligible. Thereafter regeneration of the ad-
sorbent was studied using various reagents such as 0.1 M sodium hy-
droxide, 0.1 M hydrochloric acid and double distilled water. The satu-
rated adsorbent was subjected to sonication/orbital shaking for 2 min in
regeneration media and subsequently filtered and dried. Regeneration
was observed to be most effective in case of 0.1 M sodium hydroxide in
combination with ultra-sonication in comparison to the other reagents
as shown in Fig. 9(a). Thereafter the desorption and regeneration stu-
dies of the exhausted adsorbent were carried out using different con-
centrations of NaOH (0.1M-4.0 M) solution. In regeneration process,
1.0 g of adsorbent was treated with 100 mL NaOH solution for two
minutes in a sonication bath at 25 °C after which the adsorbent was
washed with double distilled water and dried at 110 °C for 2 h. In
previous studies, regeneration was usually carried out using acid and
alkali wash for more than 90 min [33]. In this study, ultra-sonication
along with alkali wash was utilized for regeneration and was found to
be effective. Fig. 9(b) presents the extent of fluoride desorbed from AA
surface into the solution with NaOH solutions for concentration varying
from 0.1 to 4 M. As observed in Fig. 9(c) in case of CMAA 650 and Fig. 9. (a) Selection of regenerant (b) Fluoride desorbed with increase in NaOH con-
CMAA 850, 1.5 M sodium hydroxide was able to regenerate exhausted centration for AA (c) Fluoride desorbed with increase in NaOH concentration for CMAA
adsorbent and 95- 98% of fluoride was desorbed within 2 min. This is 650 and CMAA 850.
because of the asymmetric cavity collapse and subsequent microjets
created at the adsorbent surface that helped in desorption of the
fluoride. In case of activated alumina (AA) 4.0 M sodium hydroxide ^MOH2+ + F− ↔ ^MF + H2O (12)
solution was required for regeneration of adsorbent. High concentration
Desorption: ^MF + NaOH ↔ ^MOH + NaF (13)
of sodium hydroxide required for regeneration as observed in case of
AA adsorbent indicate strong bonding between adsorbate and ad- M represents metal ions such as Ca, Mg or Al and MOH represent their
sorbent. Further, the capacity of fluoride adsorption by AA, CMAA 650, respective surface hydroxide, whereas MF represents metal fluoride
and CMAA 850 in the second and third adsorption cycles is presented in complex [34].
Fig. 10. The regenerated adsorbent was used for fluoride treatment and To observe the post adsorption structure modifications in case of the
it was observed that after second adsorption cycle the adsorbent ca- virgin and spent adsorbent FTIR, XRD and XPS studies were carried on
pacity reduced by 12.41%, 12.15% and 7.88% for CMAA 650, CMAA the pre-and post fluoride treated CMAA 850 adsorbent. The FTIR data is
850 and AA respectively. as shown in Fig. 11(a). The peaks for the virgin adsorbent CMAA 850,
The mechanism proposed for the reactions representing ion ex- observed at 3242–3853 cm−1 correspond to the stretching vibration
change interaction between hydroxyl and fluoride ions for adsorption modes of OH bands, and peaks between 1464 and 1638 cm−1 corre-
and desorption on the adsorbent surface is as follows: sponds to the HeOeH bending vibrations of water molecules. The peak
around 1160.34 could be due to bending vibration of hydroxyl group of
Adsorption: ^MOH + H+↔^MOH2+ (11)

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P.K. Singh et al. Journal of Environmental Chemical Engineering 6 (2018) 1364–1377

Fig. 10. Reduction in adsorption capacity with number of regeneration cycle for CMAA
650, CMAA 850 and AA. (Process conditions: 6.5 pH, temperature 30 ± 2.0 °C, adsorbent
dose 1.0 g/100 mL, process time 180 min, fluoride ion concentration 10 mg/L).

Fig. 12. XRD spectra of (a) CMAA 850 (ϕ is magnesium aluminum oxide, * represents
calcium aluminum oxide and β is calcium magnesium aluminum oxide) and (b)
CMAAF850 (δ is calcium aluminum fluoride hydroxide, ε is Magnesium fluoride and o
represents calcium fluoride).

(MgF2) and calcium fluoride (CaF2) were present in the spectra of the
spent adsorbent whereas the oxide forms of the mixed metals were
observed in the virgin adsorbent. These observations along with the
isotherm studies indicate ion-exchange mechanism of fluoride adsorp-
tion as given in Eqs. (11) and (12) which follows chemisorption [35]. In
regeneration process, under highly basic conditions, the hydroxyl ion
replaces fluoride ions from the surface. The XPS spectra of AA,
CMAA850 and spent adsorbent CMAAF850 also confirm the formation
of mixed aluminum, calcium and magnesium oxides on the surface of
AA and that fluoride has complexed with the Ca, Mg and Al metal
oxides.

3.7. Effect of other co-existing ions

Ground water usually contains several other co-existing ions such as

sulfate, nitrate, chloride, and phosphate along with fluoride, which may
compete with fluoride ions for the active adsorption sites thereby af-
Fig. 11. Comparative FTIR Spectra of (a) virgin adsorbent CMAA 850 and (b) spent
CMAAF 850. fecting the defluoridation capacity [34]. The effect of co-ions on the
defluoridation capacity with concentration varying in the range of
100–300 mg/L is presented in Fig. 13a–c for AA, CMAA 650 and CMAA
metal oxides (MeOH) [22]. The bands in the range of 800–400 cm−1
850 respectively. In case of activated alumina (AA), fluoride adsorption
instigate from metal–oxygen vibrations [35]. In case of the spent ad-
capacity reduced by 17% when phosphate anion was present in the
sorbent CMAAF 850 as observed in Fig. 11(b), the elongated peak at
solution Fig. 13(a) whereas for CMAA 650 the reduction in adsorption
3469.83 indicates weak interactions with fluoride ions through prob-
capacity was very less in the presence of most of the anions as depicted
able formation of OeHeF hydrogen bonding [36,37]. The reduction in
in Fig. 13(b). A reduction in fluoride adsorption capacity by 4.3% in
the peak intensity along with peak shift from 1160.34 in virgin ad-
presence of phosphate and 21.4% in presence of nitrate was observed
sorbent to 1137.8 cm−1 after fluoride ions adsorption shows that the
for CMAA 850. The level of interference of the competing ions against
OH ions of the metal oxide have been replaced with the fluoride ions.
fluoride ion in aqueous medium from the highest to lowest for the
Appearance of a new adsorption peak at 426.45 cm−1 in the case of
adsorbents AA, CMAA 650 and CMAA 850 are as follows:
spent adsorbent CMAAF 850 corresponds to metal-fluoride complex
[22]. {(PO−4 3) > SO−4 2 > (Cl−1) > (NO−3 1)} for AA
Further XRD analysis of the spent adsorbent was compared with that
of virgin adsorbent and is presented in Fig. 12. Peaks of calcium alu- {(PO−4 3) > SO−4 2 > (NO−3 1) > (Cl−1)} for CMAA 650
minum fluoride hydroxide (CaAl2F4(OH)4), Magnesium fluoride and

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P.K. Singh et al.
Fig. 13. Effect of co-existing ions on fluoride adsorption capacity for (a) Activated alu-
mina (AA), (b) CMAA 650 and (c) CMAA 850. (Process conditions: 6.5 pH, temperature
30 ± 2.0 °C, adsorbent dose 1.0 g/100 mL, process time 180 min, fluoride ion con-
centration 10 mg/L).
{(NO−3 1) > PO−4 3 > (SO−4 2) > (Cl−1)} for CMAA 850
It was observed that the phosphate and sulphate ions which are
inner-sphere complex forming ions hindered the fluoride adsorption in
case of AA and CMAA 650 reducing its capacity. In case of CMAA 850,
nitrate ions which are outer-sphere complexing ions interfered reducing
fluoride removal capacity. However, there was no effect on adsorption
behavior in the presence of sulphate and chloride ions for CMAA 850 as
depicted in Fig. 13(c).
3.8. Treated water quality
The quality of treated water using the three adsorbents was studied
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Journal of Environmental Chemical Engineering 6 (2018) 1364–1377
Table 5
Treated water quality parameters with modified and unmodified adsorbents.
Parameters CMAA 650 CMAA 850 AA Permissible limit
pH 7.3 7.5 6.5 6.5–8.5
Conductivity μS/cm 66.2 70.4 44.3 –
TDS mg/L 32.99 34.38 21.4 500
Alkalinity(CaCO3 eqv.,mg/ 30 25 0 600
L)
Total hardness mg/L 120 156 0 500
Residual Fluoride mg/L 0.483 0.387 0.425 0–1.5
Residual Aluminum μg/L Nil Nil 77.76 200
to determine its suitability for drinking water conditions, and to ensure
that all standard drinking water parameters are met as per the re-
quirements. The treated water was obtained by treating 1.0 g of ad-
sorbent in 10 mg/L of fluoride solution at 30 °C at pH 7 for 180 min and
filtered in a whatman 42 filter paper. Table 5 presents all the para-
meters such as pH, conductivity, TDS, alkalinity, total hardness, re-
sidual fluoride and residual aluminum of treated water along with their
permissible limits given by WHO. As observed from Table 5, all the
parameters were under permissible limits which makes the treated
water suitable for drinking purpose.
Table 6 presents a comparison of adsorbents earlier studied based
on calcium, magnesium, alumina or amended forms of alumina for
water treatment in terms of point of zero charge (pzc), working pH
range, fluoride removal capacity and adsorbent dose required to treat a
10 mg/L fluoride solution to permissible limit of 1 mg/L in treated
drinking water. As per the data given in Table 6, adsorbents other than
magnesium-incorporated hydroxyapatite [33], CMAA 650 and CMAA
850 have their working pH range in acidic to neutral and are not sui-
table for basic conditions. Ground water in fluoride rich regions are
mostly alkaline with pH conditions around 8 to 9 pH, and therefore the
adsorbents will have very low performance. Manganese-oxide-coated
alumina [38] may have slightly higher adsorption capacity then CMAA
850, but its permissibility limit in drinking water limit is 0.05 mg/L
[39]. Table 6 clearly indicate the applicability of newly developed
adsorbents CMAA 850 for water defluoridation over a wider pH range
from 4 to 9 pH because of its higher point of zero charge and which is
an added advantage in comparison to other amended adsorbents. In
order to evaluate for the potential application of the adsorbent, based
on its adsorption capacity, the amount of adsorbent required to bring
fluoride concentration from 10 to 1 mg/L in 1 m3 of aqueous solution
[36], for the various adsorbents were calculated using mass balance
(Eq. (14)) and is also presented in Table 6.
VCo = mq e + VCe (14)
where, V is volume in L, Co is initial fluoride concentration in mg/L, Ce
is the equilibrium fluoride concentration in solution in mg/L, m is mass
of adsorbent in g and qe (mg/g) is the amount of fluoride adsorbed at
equilibrium. As observed in Table 6, only 3.28 to 3.44 kg of modified
adsorbent will be required to treat 1000 Litres of fluoride water as
compared to 10.46 kg of activated alumina. This indicate that the cost
of water treatment will be lower using CMAA650 and CMAA850
compared to other adsorbents because of its higher adsorption capacity,
lesser adsorbent requirement and its applicability for treatment over a
wider drinking water pH range.
4. Conclusions
Two variants of calcium and magnesium amended activated alu-
mina granules, named CMAA 650 and CMAA 850 were prepared from
activated alumina granules by the conventional sol gel method followed
by calcination at 650 °C and 850 °C to study its fluoride removal ca-
pacity. The amalgamation of calcium and magnesium on to the acti-
vated alumina surface was successful with the formation of calcium and
P.K. Singh et al.
Table 6
Comparison of few adsorbents based on calcium, magnesium and aluminum for their point of zero charge, fluoride adsorption capacity and working pH range.
Adsorbents pHpzc Adsorption Capacity(mg/g)
Hydroxyapatite 7.5 1.49
Manganese dioxide-coated activated alumina N.M.* 0.17
Magnesium-incorporated hydroxyapatite 7.5 1.4
Manganese-oxide-coated alumina N.M.* 2.85
Activated alumina N.M.* 2.41
Activated alumina N.M.* 0.86
CMAA 650 8.0 2.61
CMAA 850 9.0 2.74
* Not Mentioned.
magnesium complexes with aluminum oxide surface thereby increasing
the reactivity of the adsorbent towards fluoride. CMAA 850 had a
highly crystalline porous leaf like structure and higher adsorption ca-
pacity (2.74 mg/g) than CMAA 650 (2.61 mg/g) and AA (2.48 m/g).
The modified adsorbents prepared also had a higher point of zero
charge in comparison to AA resulting in wider pH range application for
defluoridation. The adsorbents followed pseudo second order kinetics
and isotherm study indicated Langmuir and Temkin adsorption iso-
therm implying chemisorption. Thermodynamic study revealed that
CMAA850 and CMAA650 had higher capacities even at higher tem-
peratures which is an added advantage for its application in warm and
tropical climatic regions. Regeneration of CMAA 650 and CMAA 850
was carried out by ultra-sonication for 2 min using 1.5 M sodium hy-
droxide and after the second adsorption cycle, adsorption capacity
dropped by 12.41% and 12.15% respectively. CMAA 850 showed high
fluoride selectivity in presence of co-existing ions. Aluminum leaching
was observed in case of AA which was absent for the amended ad-
sorbents CMAA 650 and CMAA 850. Therefore, CMAA850 is found to
be applicable for field scale applications having advantages such as
high capacity, no aluminum toxicity in treated water, bioavailability of
the amended product, applicability for wider pH range and health
benefits than activated alumina.
Acknowledgments
The authors are thankful to DST Rajasthan for the financial sup-
ports, Malaviya National Institute of Technology (MNIT) Jaipur, India
and Materials Research Centre, MNIT Jaipur for providing all the
characterization facilities needed for this paper.
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