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Insight into the defluoridation efficiency of lateritic soil

Article  in  Environmental Progress & Sustainable Energy · November 2018

DOI: 10.1002/ep.13107

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Insight into the Defluoridation Efficiency of
Lateritic Soil
N. A. Oladoja ,a G. A. Bello,a S. V. Obisesan,b B. Helmreich,a J. A. Ogunniyi,a O. A. Daramola,a
H. A. Bello,a E. T. Anthony,a and T. D. Saliua
a
Hydrochemistry Research Laboratory, Department of Chemical Sciences, Adekunle Ajasin University, Akungba Akoko, Nigeria;
bioladoja@yahoo.com; nurudeen.oladoja@aaua.edu.ng (for correspondence)
b
Technical University of Munich, Chair of Urban Water Systems Engineering, Garching, Germany
Published online 00 Month 2018 in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/ep.13107
The need to explicate the mechanisms that underlies the
defluoridation of potable water using lateritic soil necessitated
this study. Raw laterite sample was thermally !
treated at vary-
!
ing temperatures that ranged between 100 C and 1000 C to
determine the effects of thermal treatment on the surficial fea-
tures and the defluoridation efficiency. The influence of
hydrochemistry (i.e., pH, ionic strength, and anionic interfer-
ence) on the defluoridation efficiency of the lateritic soil was
studied. The determination of the effects of thermal treatment
on the performance efficiency of the laterites sample showed
that the presence of surface hydroxyl group enhanced the
defluoridation efficiency. The kinetic analysis of the process
showed that the pseudo-second-order kinetic equation gave
the best description of the process. The evaluation of the influ-
ence of ionic strength on the defluoridation efficiency showed
that the interaction between the LT0 and the aqua phase F−
occurred via inner sphere complex formation. The assessment
of the impact of the initial F− solution pH value on the process
showed that the possible mode of interaction between the LT0
and the aqua phase F− include electrostatic attraction, ligand
exchange, and H- bonding. The evaluation of anionic (NO3−,
Cl− PO43−, CO32−, and SO42−) interference on the process
showed that the mode of interaction between the LT0 and the
F− occurred via specific adsorption. Laterite can be effectively
used in aqua defluoridation, except where the presence of spe-
cific interfering ionic species are abundant. © 2018 American
Institute of Chemical Engineers Environ Prog, 2018
Keywords: defluoridation, hydrochemistry, inner-sphere
complexation, laterite, ligand exchange, specific adsorption
INTRODUCTION
In order to prevent the epidemics of the blights
(e.g., mottling of teeth, skeletal fluorosis, and crippling fluo-
rosis) that is synonymous with the consumption of water,
whose fluoride (F−) concentration is above the recommended
WHO standard (i.e. >1.5 mg/L), different treatment strategies
are being developed and perfected. Premised on the facile
process requirements of adsorption based water treatment
systems, it is considered an auspicious option for aqua
defluoridation because it could easily be adapted as an
appropriate technology. Despite the merits of this process,
© 2018 American Institute of Chemical Engineers
Environmental Progress & Sustainable Energy DOI 10.1002/ep
the high adsorbent cost often limits the applications, thereby
ousting it from the precinct of appropriate technologies. In
order to keep this water treatment process within the realm
of appropriate technologies, efforts are continually made to
develop low-cost adsorbent for optimal, efficient, sustainable,
and safe use.
In order to rein in adsorption-based water treatment pro-
cess into the fold of appropriate technology for aqua defluori-
dation, the use of green geogenic and biogenic materials are
considered veritable option because of the low cost, abun-
dance, and pervasiveness. The array of green materials adsor-
bents or reactive materials that have been studied in aqua
defluoridation include natural inorganic materials like soils [1],
clays [2], minerals, and building materials and biosorbents like
collagen fibers [3], gelatin [4], chitin and chitosan [5], and
metallic iron [6,7].
A rusty red soil, known as laterite, widely distributed in
tropical, subtropical, and Mediterranean climatic zones, is also
amongst the green geogenic materials investigated [8–10]. Lat-
erite is the common name for iron oxide rich tropical soils that
is formed during weathering of rocks, under strong oxidizing
and leaching conditions. The process of rock weathering leads
to the removal of silica, alkalis, and alkaline earths metals [11].
The mineralogical assemblage of laterites varies greatly and it
is highly dependent on the stage of laterization. Albeit, lateritic
soils may be silica poor but they often contain clay minerals,
goethite, hematite, gibbsite, and sometimes bauxite, which is
formed at the final stage of laterization [11].
Thus far, researchers have predicated the choice of laterite
as adsorbent for aqua defluoridation on the abundance, perva-
siveness, low cost, and the prevalence of metal oxides in it
[8–10]. On the premise of the Pearson’s concept of acid–base
interactions, it is hereby posited that the abundant metal
oxides in laterites provided enabling reactive sites for interac-
tions between aqua phase F− and the lateritic soil. Consequent
upon the high electronegativity and the small ionic size of F−,
it is categorized as hard base, thus the affinity toward multiva-
lent metal ions is high [12]. Pearson [13] posited that interac-
tions between electron pair donors and acceptors occur when
similitude exists in the electronic character of both the acidic
and basic reactive species. Using the acid–base interaction
preference expounded by Pearson, the abundant Fe3+ and Al3+
are hard acid while F− is a hard base. Thus, the interactions
between these reactive species are expected. An overview of
materials that have been studied as adsorbent for aqua
1
defluoridation showed that iron and aluminum rich materials
have been at the core [7,14]. This made the presence of both
metal oxides in lateritic soils advantageous. Aside the role of the
individual metal oxides in aqua defluoridation the synergistic
effects of the two metal oxides that is present in the lateritic soil
might also be strategic in enhancing the defluoridation effi-
ciency [6,7,14].
Hitherto, the defluoridation efficiency of raw and thermally
treated laterites have been studied in batch and fixed bed
operations and the defluoridation potentials have been
reported [6–8]. Considering the promise shown by lateritic soil
in aqua defluoridation, the need to elucidate the role of hydro-
chemistry on the efficiency of defluoridation of this green
material is apropos. In the present study, the effects of hydro-
chemistry on the performance of lateritic soil in potable water
defluoridation is an issue of concern because the affinity of an
adsorbent for an adsorbate is a function of the adsorbate sur-
face chemistry and the hydrochemistry of both the adsorbate
and the adsorbent. An overview of the defluoridation efficien-
cies of green materials that have been studied as low-cost
adsorbent showed that they often exhibit low defluoridation
efficiencies (<1 mg/g), but due to their abundance and afford-
ability, they are recommended for use, especially in the under-
resourced regions of the world. The low performance effi-
ciency of raw laterite in the removal of another problematic
oxoanion (i.e., arsenic) from aqua system have also been
reported [15,16]. At present, our thesis hinged on the fact that
understanding the role of hydrochemistry on the defluorida-
tion efficiency of a lateritic soil would provide an insight into:
(1) the possible approaches for enhancing the defluoridation
efficiency; (2) the possible aqua milieu for optimal adsorbent
performance; and (3) elucidation of the underlying
mechanism(s) of adsorbate-adsorbent interactions.
In order to explicate the role of hydrochemistry on the
defluoridation efficiency of a tropical lateritic soil, the laterite
sample was thermally treated at varying temperature. The
effects of thermal treatment on the surficial features and the
defluoridation efficiency of the lateritic soil was determined.
The influence of pH, ionic strength and anionic interference
on the defluoridation efficiency was studied and the results
obtained were employed to elucidate the possible underlying
mechanism of aqua defluoridation using lateritic soil.
MATERIALS AND METHODS
Material Preparation and Screening
Lateritic soil was obtained from the University town and
sieved before it was thermally treated in the furnace at differ-
ent !temperatures (0! C, 100! C, 250! C, 500! C, 750! C, and
1000 C) for 2 h. The products were labeled LT0, LT100, LT250,
LT500, LT750, and LT1000; the subscript indicates the tempera-
tures at which each material was thermally treated.
The optimum temperature required for the treatment of the
laterite sample was determined in a batch defluoridation pro-
cess, namely, 50 mL of F− solution, derived from sodium fluo-
ride (NaF) salt (Merck KGaA, Germany), of fixed
concentration (32.1 mg/L) was mixed with 0.1 g of each later-
ite sample. The reactants were thoroughly mixed at 200 rpm
for 2 h before samples were withdrawn and filtered using
0.45 μm polypropylene membrane. The filtrate was analyzed
for residual F− concentration, using a F− selective electrode,
connected to an ion meter. In each case, the defluoridation
efficiency of the adsorbate was estimated via the mass balance
equation.
Material Characterization
The effects of the thermal treatment on the surficial archi-
tecture and the mineralogy of the laterite were evaluated using
X-ray diffraction (XRD) (Seifert XRD 3003 TT) and X-ray fluo-
rescence (XRF) (Philips Model-PW2400), respectively. The
2 Environmental Progress & Sustainable Energy DOI 10.1002/ep
surface microstructure and elemental composition were deter-
mined using scanning electron microscopy (SEM) equipped
with energy dispersive X-ray (EDX) (XL 30 FEG ESEM); the
surficial functional groups were identified with Fourier Trans-
form Infra-red spectrophotometer (FTIR) (Perkin Elmer Spec-
trum 100 with ATR unit). The value of the point zero charge
(pHPZC) was determined through the method described by
Oladoja and Aliu [17].
Batch Defluoridation Process
The time–concentration profiles of the process of defluori-
dation were obtained to derive the kinetic parameters, namely,
1.0 g of the lateritic soil was weighed into 500 mL F− solution
of varying concentrations that ranged between 2.28 and
28.90 mg/L. Samples were withdrawn at regular time intervals
between 0 and 120 min and the reaction was terminated via
filtration, using 0.45 μm polypropylene membrane, and the
residual F− concentration was determined in each case. The
equilibrium isotherm parameters were obtained by the addi-
tion of 0.l g of the LT into 50 mL of F− solution of varying con-
centrations that ranged between 2.33 and 31.6 mg/L. The
mixture was stirred until the equilibrium time, sample was
withdrawn, and filtered before the residual F− concentration
was determined.
Evaluating the Role of Hydrochemistry on the Process
of Defluoridation
The role of hydrochemistry on the defluoridation efficiency
of the lateritic soil was evaluated through the simulation of the
process variables that are semblance of the GW system,
namely, initial solution pH value that ranged between pH 5.0
and 9.0; anionic interference by the addition of different con-
centrations (i.e., 10, 50, and 100 mg/L) of the following anions:
NO3−, Cl−, PO43−, CO32−, and SO42−, derived from the potas-
sium salts, to even out the cationic effects, and ionic strength
was tested in NaCl solutions (%), namely, 0, 0.05, 0.1, 0.2, 0.5,
and 1, equivalent to ionic strengths (mol/L) of 0, 0.0085, 0.017,
0.0342, 0.085, and 0.17.
RESULTS AND DISCUSSION
Laterite Sample Characterization and Screening
The surface architectures of the raw and thermally treated
laterite samples are presented in Figure 1. The thermal treat-
ment transformed the rough surface of the raw laterite sample
to a smooth surface. The results of the elemental composition
(wt %) of the LT0, determined using XRF and presented in
Table 1 showed that silica (SiO2 = 74.81%), aluminum oxide
(Al2O3 = 10.94%), and iron oxide (Fe2O3 = 4.94%) were the
major elements and the other elements identified were present
in minor and trace quantities. The presence of minerals
(i.e., quartz, hematite, aluminum oxide, and nacrite), whose
elemental compositions were defined in the XRF analysis,
were confirmed by the XRD analysis presented in Figure 2 and
Supporting Information Table S1 as the major mineralogical
constituents of the LT0. The XRD patterns of the raw laterite
sample presented in Figure 2 showed the mineralogical assem-
blage. The three major minerals identified in the raw laterite
samples include nacrite (a kaolin mineral), hematite (Fe2O3),
alumina (Al2O3), and quartz (SiO2) (Table 1). The presence of
these array of minerals have also been reported [8] in laterite
samples collected from Bankura District, West Bengal, India.
The XRD patterns (Figure 2) of the thermally treated laterite
samples showed that all the prominent diagnostic peaks
appeared at the same 2-theta positions with the raw laterite
sample but the intensity of the peaks differ from one sample
to another. The variations in the peak intensities of the sam-
ples were ascribed to the thermal treatment procedure, which
differentiated one sample from another.
 LT0 LT100

LT250 LT500

LT750 LT1000

Figure 1. The surficial physiognomies of the raw and thermally treated laterite samples.

Table 1. Results of the XRF analysis of raw lateritic soil.

Metal oxide Al2O3 SiO2 Fe2O3 P2O5 SO3 MgO K2O CaO Na2O M2O5 TiO2 LOI Total
%composition 10.94 74.81 4.94 0.04 0.00 0.13 0.71 0.38 0.0 0.12 0.96 5.93 98.96

The FTIR spectra (Figure 3) of the raw and thermally trea-
ted laterite samples showed the presence of the different func-
tional groups on the surface of the materials at similar peak
positions but the transmittance values of each peak positions
increased with increasing thermal temperature. Using the LT0
spectra as a reference point, the peaks that appeared at 3687
and 3622 were ascribed to the OHstr of inner surface hydroxyl
groups and OH stretching of inner hydroxyl groups, respec-
tively [18]. Peak at 1635 cm−1 was ascribed to the OHdef of
water while peak at 907 cm−1 was assigned to Si OHstr. The
Si O and Si O (perpendicular) peaks were observed at
787 and 750 cm−1, respectively. Two peaks that are synony-
mous with hematite were identified at 526 and 458 cm−1 [19].
It has been reported that the characteristic vibration bands of
aluminum oxide appear between 1000 and 500 cm−1 [20,21].
Considering the fact that all these minerals have their charac-
teristic FTIR peaks within this same region, the overlay of the
peaks of silica, hematite, and alumina is bound to occur which
would make it tasking to detect the alumina peaks in LT0. An
overview of the FTIR spectra of the raw and thermally treated
laterite sample showed a considerable increase in the transmit-
tance values with increasing thermal treatment temperature
(Figure 3). The greater transmittance values indicated a lower
IR absorption and a lower concentration for the specific func-
tional group [22]. For instance, the substantial reduction in the
intensity of the hydroxyl group with increasing thermal tem-
perature was attributed to the loss of surface and structural
water, which caused the dehydroxylation of the material

Environmental Progress & Sustainable Energy DOI 10.1002/ep 3

 the LT0, determined via the solid addition method, was at pH
value of 4.3. A pHPZC value of 3.98 has been reported [8] for
laterite samples collected from Bankura District, West Bengal,
India.
Owing to the reports [23,24] that heat treatment of
(hydrous) metal oxides and metal rich materials influences the
surface properties and possibly impact on the adsorbate–
adsorbent mode of interactions, the defluoridation efficiencies
of raw and heat treated laterite (i.e., LT0–LT10000) were evalu-
ated in a batch defluoridation process. The results presented in
SI Figure 1 revealed that the raw laterite (LT0) had the highest
defluoridation efficiency and thermal treatment impacted nega-
tively on the defluoridation efficiency. The defluoridation effi-
ciency of the LT0 was 2.6 mg/g while the defluoridation
efficiency of the thermally treated samples ranged between 1.7
and 1.4 mg/g. The reduction in the defluoridation efficiency of
the thermally treated laterite samples was ascribed to the trans-
formation of the metal constituents of the laterite sample into
more crystalline phase and loss of surface hydroxyl groups
which is not favorable for fluoride adsorption [25]. Similar
observation was reported [26] when the role of heat treatment
on the defluoridation efficiency of aluminum oxide infused
diatomaceous earth was investigated.

Batch Defluoridation Process

Time–Concentration Profiles of the Defluoridation Process
In order to quantify the rate of aqua defluoridation, using
LT0 as the adsorbent, the time concentration profiles of the
defluoridation process was determined at varying initial F−
concentrations that ranged between 2.28 and 28.9 mg/L. The
results presented in Supporting Information Figure S2 revealed
that the defluoridation efficiency of the LT0 is depended on
the initial F− concentration. The amount of F− removed
Figure 2. The mineralogical assemblage of the raw and increased with increasing initial F− concentrations. Irrespective
thermally treated laterite samples. of the initial F− concentration, the equilibrium time of adsorp-
tion was attained within 30 min. This equilibrium time of
adsorption was considered fast and thus an economically
favorable operational parameter for aqua defluoridation using
laterite as an adsorbent.
LT0 LT100 LT250 LT500 LT750 LT1000 The process kinetic parameters were derived from the fit-
1.1 ting of the time-concentration profiles to the pseudo-first-order
(Equation 1) and pseudo-second-order (Equation 2) kinetic
1 equations are presented in Table 2. The pseudo-first-order
equation described liquid–solid phase adsorption systems and
1635

the adsorption rate based on the adsorption capacity [27],

Transmittance (%)

0.9
681
750
787
3687

while the pseudo-second-order kinetic equation [28] described

3622

458

0.8 chemisorption, as well as ion exchange reactions:

526

0.7 log½qe −qt # ¼ log½qe # − ½k1 =2:303#t ð1Þ

t=qt ¼ 1=k2 qe + 1=qe t ð2Þ
907

0.6
995

where, qe and qt are the adsorption capacity at equilibrium

0.5
3800 3300 2800 2300 1800
Wavenumber (Cm-1)
Figure 3. The FTIR spectra pattern of the raw and thermally
treated laterite samples. [Color figure can be viewed at
wileyonlinelibrary.com]
surface with increasing temperature. The reduction in the mag-
nitude of the IR absorption by the other surface functional
groups was also ascribed to the change in the concentration of
the surface functional groups as a result of the possible ther-
mal transformation of the surface bound organic and inorganic
moieties to species that showed lesser absorption for the IR
radiation. The value of the point zero charge (i.e., pHPZC) of
1300 800 300 and at time t, respectively (mg/g), k1 is the rate constant of
pseudo first-order adsorption and k2 is the overall rate con-
stants of pseudo-second-order sorption [g/(mg/min)].
The kinetic parameters highlighted in Table 2 showed that
the defluoridation process was better described by the pseudo-
second-order kinetic equation than the pseudo-first-order equa-
tion. The values of qe2 mg/g and k2 g/(mg min) increased with
increasing initial F− concentrations. Relative to the other iron
and aluminum rich adsorbents that have been reported for aqua
defluoridation, the values of the pseudo-second-order rate
parameters that ranged between 1.28 × 10−1 and 5.81 × 10−1
obtained in the present study was comparable with the value of
1.2 × 10−1 g/mg min reported for corrosion product adsorbent
[29] but higher than the values reported for granular ferric
hydroxide [30] (1.7 × 10−2 g/mg min) and Fe3O4@Al(OH)3 mag-
netic nanoparticles [31] (3.142 × 10−2 g/mg min).

4 Environmental Progress & Sustainable Energy DOI 10.1002/ep

Table 2. Kinetic parameters for F− sorption in synthetic feed water system.

Pseudo 1st order Pseudo 2nd order parameters

Initial Conc. qe1 K1 qe2 K2
(mg/L) (mg/g) (g/mg min) × 10−2 r2 (mg/g) (g/mg min) r2 k2qe2 t0.5 Rw
2.28 0.4263 6.1 0.8924 0.53 0.128 0.9874 0.0678 14.75 0.109
5.27 0.2757 3.11 0.5659 0.83 0.457 0.9984 0.3793 2.64 0.021
10.60 0.4546 2.5 0.7885 1.59 0.567 0.9989 0.9015 1.11 0.009
19.60 1.197 6.3 0.9831 1.94 0.504 0.9993 0.9778 1.02 0.008
28.90 0.7972 15.6 0.9405 2.09 0.581 0.9994 1.2143 0.82 0.007

qe pHf evaluate the kinetic performance of the process (Equation 4)

4 14
by rearranging Equation 3 to give Equation 4, namely:
3.5 12 dq t
3
¼ k2 ðqe − qt Þ ð3Þ
10 dt

Final solution pH
! "
2.5 dq t=qe qt 2
qe (mg/g)

8
¼ k2 qe 1− ð4Þ
2 dt qe
6
1.5
4 The rearrangement of Equation 3 to give Equation 4
1
revealed that the time changes in dimensionless solid-phase
0.5 2 concentration, d(qt/qe)/dt of F− is directly proportional to the
0 0
square of the residual amount of F− in the aqueous phase,
5.04 5.95 7.06 7.89 9 1 − (qt/qe). Consequently, the proportionality constant k2qe
Initial solution pH was defined as the second-order rate index. Thus, Equation 2
Figure 4. The influence of initial solution pH on the can be rewritten as:
defluoridation efficiency of LT0. [Color figure can be viewed at # $
wileyonlinelibrary.com] 1 1 1
− t¼ ð5Þ
qt qe k2 qe2

and
3.5
qt
ðqe −qt Þ
3 t¼ ð6Þ
k 2 qe
2.5
At the half-life of the adsorption process (i.e., t = t0.5), we
have qt = 0.5qe and
2
qe (mg/g)

1.5
1
0.5
0
0 0.0085 0.017 0.0342
Ionic strength (mol/L)
Figure 5. The influence of ionic strength on the
defluoridation efficiency of LT0. [Color figure can be viewed at
wileyonlinelibrary.com]
The higher linear coefficient values of the pseudo-second-
order plots indicated that the underlying mechanism of the
defluoridation process occurred either via chemisorption or
ion exchange. It has been reported [32] that if the sorbate
uptake is chemically rate controlled, the pseudo-second-order
constants will be independent of particle diameter and flow
rate and will depend on concentration of the adsorbate in
solution. Different studies [29,33–35] have also reported the fit-
tings of the defluoridation process to the pseudo-second-order
kinetic equation.
The rate index parameter was obtained via the use of the
pseudo-second-order rate index parameter, k2qe min−1 [36] to
1
t0:5 ¼ ð7Þ
k2 qe
The values for pseudo-second-order rate index parameter,
k2qe, (Table 2) increased from a value of 0.0678 to a value of
1.2143 with increasing initial aqua phase F− concentrations,
while the half-life of the adsorption process reduced from a
0.085 0.17 value of 14.75 to a value of 0.82 with increasing initial aqua
phase F− concentrations. This is an indication that the half-life
of the defluoridation process strongly depends on the initial
aqua phase F− concentration and the process occurred at a
faster rate at higher initial F− concentration than at lower aqua
phase F− concentrations.
In order to elucidate the profiles of the kinetic curves of the
defluoridation process using LT0, an approaching equilibrium
factor (Rw) (Equation 8) that is based on the pseudo-second-
order kinetic equation [36] was employed:
1
Rw ¼ ð8Þ
1 + k2 qe tref
Rw −1
k2 qe tref ¼ ð9Þ
Rw
where, tref is the longest operation time (min) (based on the
data obtained from the determination of the time-concentration
profiles) in the defluoridation system. When 1 > Rw > 0.1, the
sorption curve is considered to be approaching equilibrium; in

Environmental Progress & Sustainable Energy DOI 10.1002/ep 5

the case of 0.1 > Rw > 0.01, it is considered to be well approach- Temkin : qe ¼ B1 lnkT + B1 lnce ð12Þ
ing pseudo equilibrium; and when Rw < 0.01 it is drastically
approaching equilibrium [36]. where, qe and Ce are as earlier defined, B1 = RT b , T(K) is the
In the present study, the rate of approaching equilibrium is absolute temperature, R is the universal gas constant (8.314 J/
highly dependent on the initial aqua phase F− concentration. mol), KT is the equilibrium binding constant (l/mg), and BI is
The values of the Rw (Table 2) reduced from a value of 0.109 to related to the heat of adsorption (Table 3).
a value of 0.007 with increasing initial aqua phase F− concentra- On the premise of the values of the coefficient of determina-
tions. At the lowest initial aqua phase F− concentration tion (r2 = 0.9281), the Langmuir isotherm equation gave the best
(2.28 mg/L), the rate of attainment of defluoridation equilibrium description of the process, relative to the other isotherm equa-
was lower than at the highest initial aqua phase F− concentra- tions tested. The value of the monolayer adsorption capacity
tion of 28.9 mg/L and this was corroborated with the steepness obtained for LT0 was 2.8 mg/g. In comparison with some other
of the time–concentration profiles (Figure 5), which was sharper adsorbents and reactive materials (Table 4) that have been used
at higher F−concentration than at lower F− concentration. [37–50] for aqua defluoridation, the monolayer adsorption
capacity (qm mg/g) was relatively low, despite the presence of
different metal oxide that is expected to show appreciable affin-
Equilibrium Isotherm Analysis of the Defluoridation ity for F−. The relatively low adsorption capacity of the LT0 was
Process ascribed to the presence of appreciable amount of quartz in the
The process equilibrium isotherm parameters were adsorbent. Chemically, quartz is made up of SiO2, which is the
obtained from the fitting of the equilibrium isotherm data to same chemical species that is found in diatomaceous earth. In
Equation 10: our previous study, diatomaceous earth, the chemical analogue
of quartz showed very poor affinity for aqua F− species [26].
ce 1 1
Langmuir : ¼ ce + ð10Þ
qe qm ka qm
The Role of Hydrochemistry on Defluoridation
where, qe is the quantity of F− uptake per gram of LT0 (mg/g); Efficiency
Ce is the aqueous phase F−concentration; Ka is the adsorption Effects of Solution pH Value on Defluoridation Efficiency
equilibrium constant; qm (mg/g) is the monolayer adsorption The pH of the water matrix impacted on the F− removal
capacity. ability of the LT0 (Figure 4). The defluoridation efficiency
reduced with increasing value of the pH of the water matrix.
1 The highest defluoridation efficiency of 3.4 mg/g was obtained
Freundlich : logqe ¼ logkf + logce ð11Þ at the lowest initial solution pH value of 5.04, while the lowest
n
defluoridation efficiency of 1.79 mg/g was obtained at the
where, qe and Ce are as hitherto defined, kf and n1 are Freun- highest initial solution pH value of 9.0. The attainment of opti-
dlich constants, related to adsorption capacity and adsorption mum defluoridation efficiency at the pH value range of 3 and
intensity, respectively. 6.5 has also been reported for an iron rich material [30].
The influence of the addition of the LT0 into the F− solution
on the operating pH value was studied via the determination of
Table 3. Equilibrium isotherm parameters of the the final equilibrium pH value (i.e., pHf) of the reacting mixture.
defluoridation process. The values of the pHf obtained were within the initial solution
pH values (Figure 4), which showed that the addition of the
Langmuir Freundlich Temkin adsorbent had minimal influence on the operating pH value.
isotherm isotherm isotherm The surficial features of an adsorbent are important param-
qm = 2.8 1/n = 0.4695 B1 = 0.11 eters that determine the extent and mode of adsorbent–
Ka = 0.47 Kf = 0.933 KT = 0.051 adsorbate interactions and one of such features is the pH value
r2 = 0.9281 r2 = 0.683 r2 = 0.8768 at the point of zero charge (i.e., pHPZC). At pH values above
the pHPZC the surface of adsorbents is negatively charged,

Table 4. Comparison of Langmuir monolayer sorption capacity (qe mg/g) of GNS with different adsorbents in aqua
defluoridation.

Langmuir monolayer Maximum conc.

Adsorbent type capacity (qm mg/g) (C0 mg/L) References
Calcium chloride modified natural zeolite 1.8 100 [32]
Quick lime 16.7 – [33]
Calcium-supported carbon 19.1 50 [34]
Metallurgical grade alumina 12.6 – [35]
Activated alumina 2.4 14 [36]
Alumina cement granules 10.2 20 [37]
Manganese-oxide-coated alumina 2.9 30 [38]
Activated alumina 1.1 30 [39]
Amorphous alumina 3.6 – [40]
Mesoporous alumina 8.3 – [41]
Granular supported nano MgO 19.5 28.6 [42]
Aluminum infused DE 13.1 38 [21]
Calcium aluminate-DE composite 18.6 38.4 [43]
Granular LDH composite 14.1 28.3 [44]
Gastropod shell 19.8 30.94 [45]
LT0 2.8 31.6 Present study

6 Environmental Progress & Sustainable Energy DOI 10.1002/ep

therefore the negatively charged adsorbate are repelled from
the adsorbent surface. At pH values below the pHPZC, the
adsorbent surface is positively charged and electrostatic mode
of interaction is developed between the adsorbent and the
adsorbate. In the present study, the defluoridation efficiency of
the LT0 was appraised above the pHPZC value of the LT0
(i.e., pH = 4.3) thus there is no basis for an opinion on the
influence of the pHPZC on the defluoridation efficiency of LT0.
Considering the fact that the LT0 is a conglomeration of
metal oxides vis-à-vis the hydrochemistry of metal oxide sur-
faces, the underlying mechanism of the defluoridation process
could be deciphered. On the premise that the LT0 is a metal
oxide rich material, the mechanism of F− adsorption on the
LT0 could be equated with the underlying principle of adsorp-
tion of anions on metal oxide rich mineral adsorbents
(e.g., alumina, gibbsite, serpentine, and clay minerals). The
reactive sites for aqua phase anionic species on these materials
are aquo groups ( M OH2+) and hydroxo groups ( M OH).
The surficial chemistry of an oxide in an aqueous milieu is
largely influenced by deprotonation or a hydroxyl association
reaction as shown below:
M− OH + H2 O ¼ − M−OH2 + + OH − ð13Þ
−M− OH + H2 O ¼ − M− O − + H3 O + ð14Þ
Equations 13 and 14 showed that the specific surficial chemistry
that predominates on the metal oxide surface is a function of the
aqua phase pH value. Within the acidic pH value range, Equa-
tion 13 is favored while within the basic pH values, Equation 14
predominates [51]. In order for the F− to get adsorbed onto the LT0
surface, a source of protons is required to protonate the LT0 sur-
face to create a potential between the LT0 surface and the aqua
phase F− as shown in Equation 13. Thus, the F− gets adsorbed on
the LT0 surface through electrostatic attraction within the acidic pH
value range. Within this same acidic pH value range, the ligand
exchange mechanism has also been proposed, as shown in Equa-
tions 15 and 16, as the possible underlying mode of adsorption of
anions on metal oxide surfaces [14] thus:
−M− OH + HX ¼ – MOH2 + − − − −X − ð15Þ
−MOH2+ − − − − − X − + A − ¼ − M− A + X − + H2 O ð16Þ
where, A− is the anion adsorbate.
Within a neutral milieu, it has also been postulated that
anions can be adsorbed by a ligand exchange mechanism
[51] thus:
−M− OH + A − ¼ −M −A + OH− ð17Þ
Taking into cognizance the equilibrium pH value of the
defluoridation system and the fact that the defluoridation effi-
ciency values obtained depended on the initial solution pH
value, the higher defluoridation efficiency values obtained at
lower pH value were ascribed to the fact that the surface of
the LT0 was favorable to electrostatic mode of attraction, at this
pH value range than at higher pH value range, where a
decline in the defluoridation efficiency was observed. Addi-
tionally, the protonation of the LT0 surface that occur within
the acidic pH value range enhanced the magnitude of H-atom
on the LT0 surface and thus promote H-bonding between the
surface H-atoms and aqua phase F−, resulting in increased F−
adsorption [52]. Within the acidic pH value range, the possibil-
ity of occurrence of F− adsorption via ligand exchange mecha-
nism is also favored because of the development of a stronger
attractive force between F− and the LT0 surface and the pres-
ence of more hydroxylated sites for exchange with F− than at
higher pH value [53,54]. In the alkaline region, the observed
lower defluoridation efficiency of the LT0 was attributed to the
Environmental Progress & Sustainable Energy DOI 10.1002/ep
postulate [14] that at pH value >8, the defluoridation efficiency
reduced not only because the adsorbent surface becomes neg-
atively charged but also because of the accretion of the con-
centrations of hydroxyl, bicarbonate and silicates ions that are
capable of competing with aqua phase F− for adsorption or
reactive sites on the LT0 surface.
Effects of Ionic Strength on Defluoridation Efficiency
The ionic composition of GW varies from one GW system
to another, thus, there are variations in the ionic strength
values of GW from different geochemical systems. The effects
ionic strength of GW on the defluoridation efficiency of the
LT0 was tested in synthetic feed water with different ionic
strength values that ranged between 0 and 0.17 M. The values
of the defluoridation efficiencies, obtained from F− solution of
different ionic strength values, showed that increasing the ionic
strength of the aqua system enhanced the defluoridation effi-
ciency (Figure 5). A steady increase in the values of the
defluoridation efficiency from a value of 2.49 mg/g, in the orig-
inal adsorbate solution, denoted as zero ionic strength, to a
value of 3.33 mg/g, when the ionic strength was increased to
0.17 M, was noted.
Ionic species in aqua system are capable of complex forma-
tion via the outer-sphere or inner-sphere mode of complexa-
tion. The outer-sphere complexation occurs via electrostatic
attraction while the inner-sphere complexation occurs via cova-
lent bond formation. The anions that are adsorbed through
outer-sphere association are intensely responsive to variation in
the value of ionic strength, thus, the magnitude of adsorption is
reduced via competition with weakly adsorbing anions. This is
because electrolytes also form outer-sphere complexes through
electrostatic mode of interaction [55]. In contrast, anions that are
adsorbed through inner-sphere complexation either show mini-
mal responsiveness to the alteration in the ionic strength or
respond to enhanced ionic strength value with greater adsorp-
tion efficiency [56]. At present, if the fluoride uptake by the LT0
occurred via the outer-sphere surface complex formation, the
defluoridation efficiency of the LT0 is bound to reduce with
increasing value of the ionic strength. In the present study,
(Figure 5), the defluoridation efficiency of the LT0 increased
with increasing ionic strength, which is an indication that the
process of defluoridation using LT0 occurred via inner sphere
complexation with the metallic active sites.
Effects of Anionic Interference on Defluoridation Efficiency
GW is replete with array of ionic species that are capable of
influencing the chemistry and the defluoridation efficiency of
the LT0. Therefore, the defluoridation efficiency of the LT0 was
evaluated in synthetic feed water system that contains different
concentrations of anionic species that are usually found in the
GW system, namely, NO3−, Cl− PO43−, CO32−, and SO42−. The
different anionic specie showed varying influence on the
defluoridation efficiency of the LT0 (Figure 6). While the pres-
ence of Cl− enhanced the defluoridation efficiency, the pres-
ence of PO43−, SO42−, and NO3− showed no discernible
pattern, but the presence of CO32− negatively impacted on the
defluoridation efficiency of the LT0 (Figure 6). The negative
impacts of the presence of carbonate on the defluoridation
efficiency of corrosion products of iron [35] and granular ferric
hydroxide [30] have also been reported.
Adsorption of anions in soil occurs via specific and non-
specific mode of interactions. Anions (e.g., Cl−, NO3−, and
ClO4−) that are retained using columbic forces and mainly
depends on the pHpzc of the adsorbent are called non-
specifically adsorbed anions while anions (e.g., HPO42−,
H2PO4−, H2AsO4−, and F−) that are retained via anion
exchange, ligand exchange, or anion penetration are dubbed
specifically adsorbed anions. Since F− is one of the anions that
specifically adsorbed anions onto soil surface, it could be
inferred that the adsorption of F− on the LT0 occurred via
7
 specific adsorption and any anionic interferent that impacted materials but a reduction in the peak intensities of the FLT0
negatively on the defluoridation efficiency also occurred via was recorded. The substantial reduction in the peak intensities
this specific mode of adsorption onto the LT0.

Characterization of the Fluoride Laden LT0 LT0-F LT0

1.1
The SEM analysis of both the virgin and F− laden LT0
(FLT0) presented in Figure 7 showed that the surficial architec-
1
ture of the FLT0 was rougher than that of the virgin LT0. The
comparison of the FTIR peaks of the virgin LT0 with the FLT0
0.9

Transmi!ance (%)
(Figure 8) showed that all the peaks observed in the virgin LT0
also appeared in the FLT0 and no diagnostic peak that can
0.8
help to elucidate the underlying mechanism of the defluorida-
tion process was noted. The only difference observed was the
0.7
enhanced transmittance values of the peaks observed in the
FLT0 relative to the virgin LT0. The absence of diagnostic peak
0.6
on F− laden adsorbent has been reported in the batch defluori-
dation appraisal of aluminum oxide infused diatomaceous
0.5
earth [26]. This observation was attributed to the fact that fluo- 3900 3400 2900 2400 1900 1400 900 400
ride is a light atom and has little vibration information or Wavenumber (cm-1)
adsorption response, thereby creating difficulty in the use of
Figure 8. Results of the FTIR analysis of LT0 and F-LT0. [Color
FTIR spectroscopy to provide detailed chemical information of
figure can be viewed at wileyonlinelibrary.com]
adsorbed F− on adsorbents [57,58].
The results of the XRD analysis of both the virgin and FLT0
(Figure 9) showed similarities in the peak positions of both

10 mg/L 50 mg/L 100 mg/L FLT0 LT0

3500
3
3000
2.5
Defluoridation efficiency(mg/g)

2500

2
2000
Intensity (a.u.)

1.5
1500

1
1000

0.5
500

0 0
CO3 PO4 Cl NO3 SO4 Raw Sample
10 20 30 40 50 60 70 80
Interfering anions
-500
2-Theta
Figure 6. The influence of interfering anion on the
defluoridation efficiency of LT0. [Color figure can be viewed at Figure 9. Results of the FTIR analysis of LT0 and F-LT0. [Color
wileyonlinelibrary.com] figure can be viewed at wileyonlinelibrary.com]

LT0 F-LT0

Figure 7. Comparison of the surficial architecture of virgin and fluoride laden LT0.

8 Environmental Progress & Sustainable Energy DOI 10.1002/ep

of the FLT0 was ascribed to the presence of surface coverage
by relatively less crystalline fluoride specie.
Mechanistic Insight into the Defluoridation Process
Judging from the instrumental and experimental evidences,
the operating mechanism(s) of F− removal from aqueous sys-
tem using lateritic soil could be considered to be multifaceted.
The multifaceted nature of the underlying mechanism could
be attributed to the complexity in the chemical composition of
the LT0.
The role of heat treatment on the defluoridation efficiency
of the LT0 showed that the surface hydroxyl group played sig-
nificant role. This observation is in tandem with the fact that
the chemistry of metals and metal rich surfaces in anionic
adsorption is controlled by the aquo group (i.e., M OH2+) o
the hydroxo group (i.e., M OH). The fitting of the time–
concentration profile data of the defluoridation process to dif-
ferent kinetic equations revealed that the defluoridation pro-
cess was best described by the pseudo-second-order kinetic
equation. Using the theoretical underpinning of this equation,
which posited that the conformity of adsorption data to this
kinetic equation is an indication that the process was con-
trolled by chemisorption, as well as ion exchange reactions. It
could be inferred that the defluoridation process, using LT0 as
an adsorbent, occurred via chemisorption or ion exchange or
the two mechanisms occurred synchronously.
The surface charge of an adsorbent, expressed as the point of
zero charge pH (pHPZC) value, is an important surface property
that influences the affinity of an adsorbent for an adsorbate. In the
present study, the value of the pHPZC obtained for LT0 was at pH
value of 4.3, while the least operating pH value was 5.1, which
showed that all the experiment was conducted above the pHPZC
value. Consequently, the role of pHPZC value on the defluoridation
efficiency of LT0 could not be validated in the present study.
The influence of the value of ionic strength on the defluori-
dation efficiency of the LT0 showed that inner-sphere complexa-
tion was the underlying mode of interaction between the LT0
and the aqua phase F−. The determination of the influence of
pH value on the defluoridation efficiency of LT0 showed that
the trend in the defluoridation efficiency with fluctuation in the
aqua phase pH value could be ascribed to the underlying prin-
ciples that guide the adsorption of anions by metal oxides sur-
faces. Consequently, electrostatic interaction, ligand exchange
and H-bonding were the possible mode of interactions that
could justify the trends in the defluoridation efficiency of the
LT0 with changes in the aqua phase pH values.
The XRD analysis showed that nacrite, hematite, alumina,
and quartz were the major minerals present in the LT0 and the
presence of these minerals were substantiated with the results
obtained from the XRF analysis, which showed that the major
metallic composition of LT0 was Fe and Al. The active metal
components (i.e., Fe and Al) of the LT0 are amphoteric. Thus,
the displayed surface charge (i.e., either positive or negative) is
highly dependent on the system pH value. Consequently, the
LT0 possess the ability to attract both the positive and negative
chemical species, depending upon the pH of the system. Beside
the electrostatic attraction, specific adsorption via ligand
exchange, or anion penetration is also possible on surfaces rich
in such amphoteric metal oxides. Since the adsorbent of interest
in the present study (i.e., F−) is a specific adsorbing anionic spe-
cie, it could be inferred that the underlying mechanism of
defluoridation process occurred via specific adsorption of F− on
the LT0 surface. Through these specific adsorption process,
anionic species can enter six-fold coordination with Al3+ or Fe3+
ions and replace OH− ions on hydrous oxides surfaces.
−Fe− OH + F − ¼ Fe− F + OH −
−Al− OH + F − ¼ Al −F + OH −
Environmental Progress & Sustainable Energy DOI 10.1002/ep
Thereafter, the surface of the LT0 transformed from
hydroxyl surface to fluoride surface. It should be noted that
ligand exchange is different from non-specific anion adsorp-
tion because while non-specific anion adsorption can occur
only on positively charged surfaces, ligand exchange or spe-
cific adsorption can occur on surfaces with negative, positive,
or neutral charge.
Using the experimental facts obtained from the present
study as a premise, we hereby hypothesized that the underly-
ing mechanism of aqua defluoridation using raw laterite is
highly dependent on the surface hydroxyl functional group
and the process is as complex as the chemical composition of
the laterites. The reaction mechanisms that have been identi-
fied included electrostatic attraction, H-bonding, and ligand
exchange. Using the results obtained from the determination
of the effects of ionic strength, the occurrence of electrostatic
attraction must have occurred minimally. The occurrence of H-
bonding is assumed to also have occurred to a lesser degree
while ligand exchange is assumed to be the major player in
the process. The results obtained from the determination of
the influence of ionic strength and anionic interference
showed that the ligand exchange occurred via the specific
mode of adsorption.
CONCLUSION
• The determination of the effects of thermal treatment on
the defluoridation efficiency of the lateritic soil showed that
the surface hydroxyl group on adsorbent played significant
role in the defluoridation efficiency
• Kinetic analysis showed that pseudo-second- order kinetic
equation gave better description of the defluoridation pro-
cess which indicated that chemisorption and/or ion
exchange played significant role in the defluoridation
process
• Premised on experimental evidences, it was posited that
electrostatic attraction, ligand exchange, and H-bonding
were responsible for the higher magnitude of F− by the LT0
within the acidic pH value of the water matrix
• The effects of anionic interference on the defluoridation
efficiency of the LT0 showed that only specific interfering
species impacted negatively on the defluoridation
efficiency
ACKNOWLEDGMENT
The Authors are grateful to the Alexander von Humboldt
Foundation for the award of Equipment Fellowship Grant to
Oladoja N.A. to undertake this research work.
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