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The need to explicate the mechanisms that underlies the the high adsorbent cost often limits the applications, thereby
defluoridation of potable water using lateritic soil necessitated ousting it from the precinct of appropriate technologies. In
this study. Raw laterite sample was thermally !
treated at vary-
!
order to keep this water treatment process within the realm
ing temperatures that ranged between 100 C and 1000 C to of appropriate technologies, efforts are continually made to
determine the effects of thermal treatment on the surficial fea- develop low-cost adsorbent for optimal, efficient, sustainable,
tures and the defluoridation efficiency. The influence of and safe use.
hydrochemistry (i.e., pH, ionic strength, and anionic interfer- In order to rein in adsorption-based water treatment pro-
ence) on the defluoridation efficiency of the lateritic soil was cess into the fold of appropriate technology for aqua defluori-
studied. The determination of the effects of thermal treatment dation, the use of green geogenic and biogenic materials are
on the performance efficiency of the laterites sample showed considered veritable option because of the low cost, abun-
that the presence of surface hydroxyl group enhanced the dance, and pervasiveness. The array of green materials adsor-
defluoridation efficiency. The kinetic analysis of the process bents or reactive materials that have been studied in aqua
showed that the pseudo-second-order kinetic equation gave defluoridation include natural inorganic materials like soils [1],
the best description of the process. The evaluation of the influ- clays [2], minerals, and building materials and biosorbents like
ence of ionic strength on the defluoridation efficiency showed collagen fibers [3], gelatin [4], chitin and chitosan [5], and
that the interaction between the LT0 and the aqua phase F− metallic iron [6,7].
occurred via inner sphere complex formation. The assessment A rusty red soil, known as laterite, widely distributed in
of the impact of the initial F− solution pH value on the process tropical, subtropical, and Mediterranean climatic zones, is also
showed that the possible mode of interaction between the LT0 amongst the green geogenic materials investigated [8–10]. Lat-
and the aqua phase F− include electrostatic attraction, ligand erite is the common name for iron oxide rich tropical soils that
exchange, and H- bonding. The evaluation of anionic (NO3−, is formed during weathering of rocks, under strong oxidizing
Cl− PO43−, CO32−, and SO42−) interference on the process and leaching conditions. The process of rock weathering leads
showed that the mode of interaction between the LT0 and the to the removal of silica, alkalis, and alkaline earths metals [11].
F− occurred via specific adsorption. Laterite can be effectively The mineralogical assemblage of laterites varies greatly and it
used in aqua defluoridation, except where the presence of spe- is highly dependent on the stage of laterization. Albeit, lateritic
cific interfering ionic species are abundant. © 2018 American soils may be silica poor but they often contain clay minerals,
Institute of Chemical Engineers Environ Prog, 2018
goethite, hematite, gibbsite, and sometimes bauxite, which is
Keywords: defluoridation, hydrochemistry, inner-sphere
formed at the final stage of laterization [11].
complexation, laterite, ligand exchange, specific adsorption
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
INTRODUCTION [8–10]. On the premise of the Pearson’s concept of acid–base
In order to prevent the epidemics of the blights interactions, it is hereby posited that the abundant metal
(e.g., mottling of teeth, skeletal fluorosis, and crippling fluo- oxides in laterites provided enabling reactive sites for interac-
rosis) that is synonymous with the consumption of water, tions between aqua phase F− and the lateritic soil. Consequent
whose fluoride (F−) concentration is above the recommended upon the high electronegativity and the small ionic size of F−,
WHO standard (i.e. >1.5 mg/L), different treatment strategies it is categorized as hard base, thus the affinity toward multiva-
are being developed and perfected. Premised on the facile lent metal ions is high [12]. Pearson [13] posited that interac-
process requirements of adsorption based water treatment tions between electron pair donors and acceptors occur when
systems, it is considered an auspicious option for aqua similitude exists in the electronic character of both the acidic
defluoridation because it could easily be adapted as an and basic reactive species. Using the acid–base interaction
appropriate technology. Despite the merits of this process, 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
© 2018 American Institute of Chemical Engineers materials that have been studied as adsorbent for aqua
LT250 LT500
LT750 LT1000
Figure 1. The surficial physiognomies of the raw and thermally treated laterite samples.
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- aluminum oxide appear between 1000 and 500 cm−1 [20,21].
ted laterite samples showed the presence of the different func- Considering the fact that all these minerals have their charac-
tional groups on the surface of the materials at similar peak teristic FTIR peaks within this same region, the overlay of the
positions but the transmittance values of each peak positions peaks of silica, hematite, and alumina is bound to occur which
increased with increasing thermal temperature. Using the LT0 would make it tasking to detect the alumina peaks in LT0. An
spectra as a reference point, the peaks that appeared at 3687 overview of the FTIR spectra of the raw and thermally treated
and 3622 were ascribed to the OHstr of inner surface hydroxyl laterite sample showed a considerable increase in the transmit-
groups and OH stretching of inner hydroxyl groups, respec- tance values with increasing thermal treatment temperature
tively [18]. Peak at 1635 cm−1 was ascribed to the OHdef of (Figure 3). The greater transmittance values indicated a lower
water while peak at 907 cm−1 was assigned to Si OHstr. The IR absorption and a lower concentration for the specific func-
Si O and Si O (perpendicular) peaks were observed at tional group [22]. For instance, the substantial reduction in the
787 and 750 cm−1, respectively. Two peaks that are synony- intensity of the hydroxyl group with increasing thermal tem-
mous with hematite were identified at 526 and 458 cm−1 [19]. perature was attributed to the loss of surface and structural
It has been reported that the characteristic vibration bands of water, which caused the dehydroxylation of the material
0.9
681
750
787
3687
458
0.6
995
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
1.5 t0:5 ¼ ð7Þ
k2 qe
1
The values for pseudo-second-order rate index parameter,
0.5
k2qe, (Table 2) increased from a value of 0.0678 to a value of
1.2143 with increasing initial aqua phase F− concentrations,
0
while the half-life of the adsorption process reduced from a
0 0.0085 0.017 0.0342 0.085 0.17 value of 14.75 to a value of 0.82 with increasing initial aqua
Ionic strength (mol/L) phase F− concentrations. This is an indication that the half-life
of the defluoridation process strongly depends on the initial
Figure 5. The influence of ionic strength on the
aqua phase F− concentration and the process occurred at a
defluoridation efficiency of LT0. [Color figure can be viewed at
faster rate at higher initial F− concentration than at lower aqua
wileyonlinelibrary.com]
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-
The higher linear coefficient values of the pseudo-second- order kinetic equation [36] was employed:
order plots indicated that the underlying mechanism of the
defluoridation process occurred either via chemisorption or 1
ion exchange. It has been reported [32] that if the sorbate Rw ¼ ð8Þ
uptake is chemically rate controlled, the pseudo-second-order 1 + k2 qe tref
constants will be independent of particle diameter and flow Rw −1
k2 qe tref ¼ ð9Þ
rate and will depend on concentration of the adsorbate in Rw
solution. Different studies [29,33–35] have also reported the fit-
tings of the defluoridation process to the pseudo-second-order where, tref is the longest operation time (min) (based on the
kinetic equation. data obtained from the determination of the time-concentration
The rate index parameter was obtained via the use of the profiles) in the defluoridation system. When 1 > Rw > 0.1, the
pseudo-second-order rate index parameter, k2qe min−1 [36] to sorption curve is considered to be approaching equilibrium; in
Table 4. Comparison of Langmuir monolayer sorption capacity (qe mg/g) of GNS with different adsorbents in aqua
defluoridation.
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
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.