Alexandria Engineering Journal (2015) 54, 1273–1284

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Alexandria University

Alexandria Engineering Journal

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ORIGINAL ARTICLE

Removal of fluoride by aluminum impregnated

coconut fiber from synthetic fluoride solution
and natural water
Naba Kumar Mondal *, Ria Bhaumik, Jayanta Kumar Datta

Department of Environmental Science, The University of Burdwan, Burdwan, India

Received 16 June 2015; revised 30 July 2015; accepted 20 August 2015

Available online 14 September 2015

KEYWORDS Abstract Aluminum impregnated coconut fiber ash (AICFA) was used for removal of fluoride
Coconut fiber; from synthetic fluoride solution. The AICFA showed high specific area and strong affinity toward
Fluoride; fluoride. Synthesized AICFA was characterized by pHZPC, FTIR, SEM and XRD studies. Adsorp-
Adsorption; tion kinetics indicated that the adsorption equilibrium was reached within 60 min and the adsorp-
Desorption; tion process followed the pseudo-second-order kinetic model better. The Langmuir isotherm model
Co-ions; could fit the experimental data well. Thermodynamic parameters such as Gibbs free energy (DG
),
Thermodynamic parameters enthalpy (DH
) and entropy (DS
) change of sorption were also evaluated which indicated that the
adsorption process was spontaneous, feasible and exothermic in nature. Furthermore, the coexist-
ing anions had significant effect on fluoride adsorption. Moreover, desorption study with AICFA
showed that nearly 98% of fluoride could be leached out at pH 12. Further, the reusable properties
of the material supported the possibility of its use commercially.
Ó 2015 Faculty of Engineering, Alexandria University. Production and hosting by Elsevier B.V. This is an
open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction by geological sources [4,5]. Fluoride at micro-molar level is

considered as an effective anabolic agent because it promotes
Toxicity of hazardous ions, such as fluoride, is of interest for cell proliferations, whereas in millimolar concentration, it
public health [1,2]. It is the strongest electronegative elements can bind to the functional amino acid groups located around
and in gaseous form is a very powerful oxidizing agent [3]. the active center of an enzyme to cause an inhibitory effect
The natural abundance of fluoride ranges from 0.065% to which leads to decrease enzyme activity [6,7]. According to
0.09% by weight in the earth’s crust and it exists naturally World Health organization (WHO), the acceptable limit of flu-
as fluoride ions (F) which is extremely reactive [3]. The main oride in drinking water is 1.5 mg L1 [8]. In some areas of
source of fluoride for humans is drinking water contaminated India a typical fluoride concentration in underground water
is found to be in the range of 1.5–6.5 mg L1 [9].
* Corresponding author. Cell: +91 9434545694; fax: +91 (342) A number of drinking water defluoridation techniques have
2634200.
been developed. Among them reverse osmosis (RO), is one of
E-mail address: nkmenvbu@gmail.com (N.K. Mondal). the well-known techniques applied for removal of fluoride [10].
Peer review under responsibility of Faculty of Engineering, Alexandria However, RO has serious drawback for its high operational
University. and maintenance costs. Application of solar distillation for
http://dx.doi.org/10.1016/j.aej.2015.08.006
1110-0168 Ó 2015 Faculty of Engineering, Alexandria University. Production and hosting by Elsevier B.V.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
1274 N.K. Mondal et al.

defluoridation demonstrated approximately 97% fluoride deposited on CFA. In this process, the addition of sodium
removal [11]. But the method does not produce large volume hydroxide is very vital and it was controlled by proper check-
of potable water, which is its serious drawback. On the other ing of pH of the mixture. Once the pH of the reaction media
hand, nanofiltration shows remarkable suitability for defluori- reaches the desired value of 5–7, sodium hydroxide addition
dation of water. However, the use of inorganic component was stopped. Finally the resulting adsorbent contains the mix-
such as CaCO3 as filter and membrane produces a smell in ture of sodium sulfate and aluminum hydroxide coated CFA.
the water. In addition, this method requires a huge mainte- Thereafter, the whole slurry was filtered and subsequently
nance cost [12]. Application of precipitation and coagulation dried at 400 K to get the desired adsorbent. However, for fur-
method for defluoridation of water has also been investigated ther use the CFA was thoroughly washed with double distilled
[13,14]. However, the shortcomings of most of these methods water in order to complete removal of sodium sulfate and
are high operational and maintenance costs, secondary pollu- dried in oven at 370 K.
tion (generation of toxic sludge, etc.) and complicated proce-
dure involved in the treatment [15]. 2.2.2. Adsorbent characterization
In comparison with the abovementioned techniques for
defluoridation of water, adsorption is a simple, low cost and The scanning electron microscopy (SEM) images of the adsor-
easily applicable method [16,17]. Literature has reported vari- bent sample are helpful to understand its surface structure. In
ous adsorbents for defluoridation such as egg cell dust, sugar- this study images were recorded by using SEM analyzer
cane rice husk ash, tea ash, leaf biomass, algal biomass, (HITACHI, S-530, Scanning Electron Microscope and ELKO
sugarcane baggies charcoal, bio-char, etc [18–20,16,21,22]. Engineering) at an accelerating voltage of 20.0 kV. Automated
The interest in fluoride removal by biomass based adsor- Mercury Porosimeters (Quantachrome, model Pore Master 60
bents is growing due to their low cost and availability. It is well GT) were used to determine the pore size distribution since this
reported that functional groups such as hydroxyl, carbonyl, method is suitable for determining larger pores such as meso-
amine, amide, carboxyl, sulfhydryl, imidazole, phosphonate, pores or micropores. The FTIR study was done to record the
and phosphodiester present on the biosorbent surface con- potential functional groups involved in the adsorption process
tributed to biosorption [23–25]. Nowadays, it is a great chal- by using FTIR (BRUKER, Tensor 27). The crystalline struc-
lenge in the area of public health to remove fluoride from ture of the adsorbent was characterized using Ni-filtered Cu
drinking water by using low-cost adsorbents at local levels, Ka radiation from a highly stabilized and automated Philips
especially in fluoride affected areas. Moreover, field sample X-ray generator (XRD, PW 1830) operated at 35 kV and
was collected from fluoride affected area of Birbhum district, 25 mA at a scanning speed of 2° min1 from 10° to 70°. The
West Bengal, where plenty of coconut trees are available. With XRD data were matched with standard JCPDS data.
this in perspective, present work was undertaken to explore the
potentiality of aluminum impregnated coconut fiber ash for 2.3. Adsorption experiment
removal of fluoride from synthetic fluoride solution.
An artificial fluoride solution was prepared by dissolving
2. Materials and methods 2.21 g sodium fluoride solid granules in 1 L of deionized water
and subsequently diluted to the required concentrations for the
2.1. Collection of adsorbents adsorption experiments. The adjustment for pH was done
using HCl or NaOH. All the experiments were carried out in
The coconut fiber was collected from fruit shops of local mar- 250 mL conical flask, with 100 mL F solutions at different
ket (24°350 000 N latitude and 87°50 2500 E longitude). After collec- experimental temperature. These flasks, along with test solu-
tion it was cut into small pieces and dried in sunlight. After tion and adsorbent, were shaken by the magnetic starrier, to
drying it was burned in muffle furnace at 423 K for one and study various parameter. The percentage of fluoride removal
half hours. The ash was washed with distilled water, dried in (% F) and the amount of F adsorbed per unit weight of adsor-
sunlight and then dried in oven at 353 K for overnight. It bent at time t (qt, mg g1) and at equilibrium (qe, mg g1) were
was sieved through mesh size of 150 mm and kept in plastic calculated using the following equation, respectively:
air tied container for further use. This material considered as
coconut fiber ash (CFA). All chemical reagents were of analyt- C0  Ce
%F ¼  100 ð1Þ
ical grade. Deionized water was used throughout the C0
experiments.

2.2. Preparation of aluminum coated CFA ðC0  Ct Þv

qt ¼ ð2Þ
m
2.2.1. Method of coating of aluminum hydroxide on CFA
ðC0  Ce Þv
According to Ganvir and Das [26] aluminum impregnation has qe ¼ ð3Þ
been done by using stirred tank reactor with stirring, vacuum/ m
pressure filter and oven/drier (Fig. 1). Initially, 100 g CFA was where v (L) is the volume of fluoride solution, and C0 (mg L1)
taken in stirred reactor tank and 500 mL of 0.6 M aluminum is the initial concentration of F. Ct (mg L1) is the concentra-
sulfate solution was added and stirred the mixture. The reactor tion of F at a given time t, Ce (mg L1) is the concentration of
was stirred at 180–200 rpm with 1.0 M sodium hydroxide solu- F at equilibrium and m(g) is the dry weight of the adsorbents.
tion. In this condition, sodium hydroxide reacts with alu- The relative parameters for the isotherm and kinetic equations
minum sulfate to produce aluminum hydroxide which gets were obtained using v2 relationship between the calculated and
Removal of fluoride by coconut fiber 1275

Figure 1 Process flow sheet of aluminum hydroxide coating on coconut fiber ash (CFA). (Figure adopted and modified from Ganvir and
Das [26]).

 
experimental data employing non-linear analysis. The calcu- 1
e ¼ RT ln 1 þ ð8Þ
lated expression for chi-square, v2 may be written as follows: Ce
X ðqe;exp  qe;cal Þ2
v2 ¼ ð4Þ 1
qe;cal E ¼ pffiffiffiffiffiffi ð9Þ
2b
where qe,exp is experimental equilibrium capacity data and qe,cal The magnitude of E is useful for estimating the type of
is the equilibrium capacity from a model. If data from the sorption reaction. The calculated free energy values suggested
model are similar to experimental data, v2 will be small and the participation of physical forces during sorption [29,30].
if they differ, v2 will be large.
2.5. Adsorption kinetic studies
2.4. Adsorption isotherm analysis
2.5.1. Kinetic rate parameters
The experimental data obtained at equilibrium isotherm of flu-
oride adsorption by AICFA were fitted to the frequently used
k1 t
models, Langmuir and Freundlich absorption isotherm [27]. logðqe  qt Þ ¼ log qe  ð10Þ
2:303
1 1 1
¼ þ ð5Þ t 1 t
qe q0 bCe q0 ¼ þ ð11Þ
qt k2 t2 qe
1
log qe ¼ log Kf þ log Ce ð6Þ qt ¼ Kd t1=2 ð12Þ
n
where qe is the amount of solute adsorbed per unit weight of C 1=2
Df ¼ 0:23  r0 d t ð13Þ
material (mg/g), q0 is the maximum adsorption capacity (mg/g), C
b is the Langmuir constant, Kf is the minimum sorption where qt and qe are the amount of the adsorbed fluoride (mg/g)
capacity (mg/g), n is the adsorption intensity of the Freundlich at time t and at equilibrium time, respectively and Kl and K2
isotherm, and Ce is the equilibrium concentration of fluoride are first order and second order rate constants for adsorption.
(mg/L). The isotherm parameters are shown in Table 1. The Kd is the intraparticle diffusion rate constant (mg g1 min0.5).
applicability of the isotherm equation was compared by evalu- The results are shown in Table 2. The correlation coefficient
ating the correlation co-efficient (R2). It is revealed from the value for the pseudo-second order adsorption model
results that Langmuir isotherm model is the fittest fluoride (R2 = 0.9993) is much higher than that obtained for the
adsorption process on AICFA. The Freundlich isotherm pseudo first order kinetics (R2 = 0.8049). On the other hand
reveals adsorption capacity of 3.14 mg/g for AICFA, which Df is the diffusion coefficient expressed in cm2/s, r0 is the radius
is much higher than for granular red mud, at 0.85 mg/g [28].
of the sorbent expressed in cm, t1=2 is the half-life period in sec,
D–R isotherm is more general than the Langmuir because it
does not assume a homogeneous surface or constant sorption d is the film thickness expressed in cm and CC is equilibrium
potential. D–R model is expressed by Eqs. (15) and (16), where loading of the sorbent.
b is the activity coefficient related to mean sorption energy
(mol2 kJ2); e is the Polanyi potential, R is the ideal gas con- 2.6. Distribution coefficient
stant, T is the absolute temperature and E (kJ mol1) is defined
as the free energy change required to transfer 1 mol of ions A distribution coefficient, KD, reflects the binding ability of the
from solution to the solid surfaces, which equals to the follow- surface for an element and is dependent on pH of the solution
ing equation: and type of surface of the adsorbent. The distribution coeffi-
cient values for fluoride adsorbed on CFD at pH 6.0 were cal-
ln qe ¼ ln qm  be2 ð7Þ culated [31] using the following equation:
1276 N.K. Mondal et al.

Cs
KD ¼ ðm3 =kgÞ ð14Þ

0.314
0.621
0.411
0.451
Cw

v2
where Cs is the concentration of fluoride on the solid particles

0.893
0.867
0.899
0.831
(mg/kg) and Cw is the equilibrium concentration in solution

R2
(mg/m3).

E (kJ mol)
3. Results and discussion

0.927
0.918
0.946
0.826
3.1. Characterization of AICFA

The surface morphology of the AICFA examined by SEM

b (mol2 kJ2)

(Figs. 2a and 2b) clearly revealing a smooth layer surface

structure shows high adsorption capacity. The SEM structure
0.581
0.593
0.611
0.732
of AICFA before and after adsorption of fluoride showed lit-
tle variation in surface structure. This change of surface
chemistry is due to the introduction of foreign ions (Al)
qm (mg g1)

[32]. Figs. 2a and 2b compare the surface features of adsor-

bents before and after fluoride adsorption at a magnification
3.412
5.621
5.718
5.331
D–R

of 2000. On the other hand, X-ray powder diffraction was

studied to analyze the existence of aluminum in AICFA
(Fig. 2c). From Fig. 2c, the presence of aluminum in AICFA
8.191
64.302

(2h, 39.65) is clear. XRD analysis directly provides evidence

61.66
44.27

that aluminum was impregnated in coconut fiber. The surface

v2

areas of unimpregnated coconut fiber and AICFA were

recorded as 20.4 and 26.3 m2/g, respectively. Results clearly
0.440
0.155
0.914
0.068
R2

revealed that AICFA showed little higher surface area than

unimpregnated coconut fiber. This is perhaps due to the uni-
form coating of alum on the surface of the coconut fiber, and
0.797
1.235
0.306
0.767

hence the increase in the pore volume [33]. However, exactly

n

opposite result can be expected. This is because on impregna-

tion, surface area of impregnated adsorbent usually decreases
0.301
5.984
0.004
0.036
KF

due to the diffusion of impregnated particles into the pores of

the adsorbent [34]. The FTIR spectra of AICFA before and
after fluoride adsorption are shown in Figs. 3a and 3b. The
qm (mg g1)
Freundlich

FTIR spectral analysis of AICFA shows distinct peaks at

3436, 2363 and 2345 cm1. The broad and strong bend at
3.192

6.104
6.004
4.95

3436 cm1 indicates the presence of AOH stretching. The

Isotherms constant for adsorption of fluoride onto AICFA.

ACH2 stretching vibration could be ascribed to the band that

appeared at 2363 cm1. The strong peak at 2345 cm1 indi-
0.275
0.503
0.714
1.182

cates the presence of AC„C group while adsorption at

v2

1404 cm1 is due to ANAH vibration. Thus, FTIR spectral

0.942
0.975
0.954
0.972
R2

Table 2 Kinetics constant for adsorption of fluoride onto

KL (L mg1)

AICFA.
0.183
12.273
12.636
11.000

Kinetic model Parameters Temperature (K)

313 333 357 373
Pseudo-first order qe,exp (mg/g) 3.13 2.21 1.67 0.612
qm (mg g1)

K1  102 (min1) 1.039 0.409 0.768 0.456

Langmuir

R2 0.809 0.818 0.847 0.787

v2
1.128

5.827
5.619

0.431 0.633 0.539 0.446

5.60

Pseudo-second qe,exp (mg/g) 1.13 2.76 0.931 0.411

order K2 (g/mg min) 0.416 3.889 1.790 3.545
Temperature (K)

R2 0.999 0.983 0.980 0.915

v2 0.313 0.631 0.611 0.431
Intra-particle kid  (mg/g min0.5) 88.703 5.627 4.853 3.421
Table 1

diffusion R2 0.688 0.948 0.928 0.929

v2
313
333
353
373

0.331 0.635 0.411 0.661

Removal of fluoride by coconut fiber 1277

18.0
17
16
15
14
13
%T 669.97
12
11
10
1404.46 1102.72
9 1634.73 1580.01
3436.99
2363.19
8 2345.59
7.0
4400.0 4000 3000 2000 1500 1000 400.0
cm-1

Figure 2a Aluminum impregnated coconut fiber ash (before Figure 3a AICFA before adsorption of fluoride.
fluoride stress) (magnification 500).

28.0
27
26
25
24
23
22
%T 21 2373.94
2346.30
20
2921.85
19 1110.66
1420.34 1053.62
18
17
16 1583.09
15
13.9 3443.11
4400.0 4000 3000 2000 1500 1000 400.0
cm-1

Figure 3b AICFA after adsorption of fluoride.

Figure 2b Aluminum impregnated coconut fiber ash (after
fluoride stress) (magnification 500).
was reported earlier by Mondal et al. [18]. Moreover, transmis-
sion bands at 1420 and 1583 cm1 are more dominant in case
of fluoride sorbed on AICFA. This observation suggests possi-
700
ble interaction between fluoride and AICFA. A similar obser-
600 vation was reported by Vences-Alvarez et al. [35] in their work
on fluoride sorption by hybrid adsorbent-lanthanum carbon.
Intensity (a. u.)

500
39.65 Al(111)
38.472 (JCPDS 04-0787)
400 3.2. Effect of pH
300
Fig. 4 indicates that maximum fluoride adsorption occurs at
200
pH 5 which is below the pHzpc of AICFA. Fluoride removal
100 was not satisfactory at pH below 5. This can be attributed to
the distribution of F and HF which are controlled by pH
10 20 30 40 50 60 70
of the aqueous solution [36]. However calculation (Eq. (15))
2 theta (degree)
showed that fluoride ion is the dominated species when pH
of the solution exceeds the pKa (3.16) value of HF [37].
Figure 2c XRD of coconut fiber under aluminum loaded
condition. 1
Pions ¼ ð15Þ
½1 þ 10ðpKa pHÞ 
analysis demonstrates that the functional groups such as alco- Results also revealed that F removal significantly reduced
holic groups and unsaturation dominate the surface of when pH of the solution increased to 8 or higher (Fig. 4). This
AICFA. After fluoride adsorption the intensity of hydroxyl might be attributed to the pHzpc of AICFA (Fig. 5). The sur-
carbonate and halide bowls of the adsorbent is reduced com- face charge of the pHzpc is usually assessed by the zero point
pared to that of the adsorbent before adsorption of fluoride. charge (pHzpc = 7.2), and at pH < pHzpc, the surface charge
Strong adsorption band of 3436 cm1 (AOH stretching) was is positive, at pH = pHzpc, the surface charge is neutral, and
shifted to 3443 cm1 after fluoride adsorption. These results at pH > pHzpc, the surface charge is negative [38]. At a pH,
suggest that fluoride interacts with the AOH and ANH groups above pHzpc more of the surface sites are negatively charged
present on AICFA surface. Similar shifting of adsorption band and subsequently electrostatic repulsion occurs between
1278 N.K. Mondal et al.

98 0.98
100 removal
qemgg
0.97 4
Removal 90
qe
96 0.96
Removal (%)

Removal (%)
80

qe (mg/g)
0.95

qe (mg/g)
70
94 0.94 2
60
0.93
50
92 0.92
40
0
0.91
2 4 6 8 10 12 0 2 4 6 8 10
pH Initial Con. (mg/L)

Figure 4 Effect of pH on removal of fluoride from water (initial Figure 6 Effect of initial concentration (mg/L) on removal of
conc. = 1 mg/L, adsorbent dosage = 0.05 g/L, contact time = 1 h, fluoride from water (adsorbent dosage = 0.05 g/L, contact
temperature = 313 K). time = 1 h, pH = 6.5, temperature = 313 K).

Therefore, the present experiment suggests that AICFA can

1.5
remove >88% F from water if its concentration is below
3 mg/L. The saturation behavior of adsorbent under such
low level of fluoride is probably due to the fact that ratio of
1.0
surface active sites to total fluoride is high; hence, the fluoride
pH change

ions could interact with the adsorbent surface to occupy the

0.5
active sites on the AICFA surface sufficiently, a significant fac-
tor that favors fluoride removal [40]. A similar study on fluo-
0.0
ride adsorption was reported using KMnO4-modified
activated carbon derived from stem pyrolysis of rice straw [41].
-0.5

3.4. Effect of AICFA

2 4 6 8 10
pH
The removal efficiency of anions by any sorbent is closely
Figure 5 pHZPC of the experimental adsorbent. related to its adsorption sites [42]. The defluoridation efficiency
by AICFA dose is shown in Fig. 7a. Fig. 7a showed that when
adsorbent amount increased from 0.2 to 1 g L1, the fluoride
F and negative charge of the AICFA. At pH 5, the surface of removal increased from 90.1% to 97.1%, respectively. This
the AICFA is positive; hence, electrostatic attraction between higher adsorption is probably due to larger surface available
positively charged AICFA surface and fluoride ions dose to sorption which promoted the sorption of fluoride [43]. On
works well for fluoride removal. Almost similar type of the other hand, Fig. 7b shows that the KD increases with an
interaction was reported by Junlian et al. [39]. They suggested increase in adsorbent dose at constant pH (5.0) that implies
that the adsorption of fluoride through the formation of that the surface of AICFA is not completely homogeneous.
inner-sphere surface complexes with the surface hydroxyl sites. If the surface is completely homogeneous, the KD values at a
BMAOH þ Hþ þ F () BMOHþ
2 ......F

ð16Þ given pH should not change with adsorbent dose.

BMAOH þ Hþ þ F () Mþ . . . . . . :F þ H2 O ð17Þ 3.5. Effect of contact time

BMAOH þ F () Mþ . . . . . . :F þ OH ð18Þ Fig. 8 shows fluoride removal at different contact time using
AICFA as an adsorbent. With increasing contact time, fluoride
BMAOH þ Naþ þ OH removal increased rather rapidly, but then dropped at 60 min
þ F () MAO . . . . . . Naþ . . . ::F þ H2 O ð19Þ and approached a more or less constant value denoting attain-
ment of equilibrium. The sorption of fluoride is very rapid in
less than 60 min. This may be the result of the instantaneous
3.3. Effect of adsorbate concentration sorption reaction in which fluoride sorbed quickly on to the
surface of AICFA. Moreover, the sudden rise in removal of
The effect of different concentration of fluoride solution on the fluoride (from 20 min to 40 min) indicates that the adsorption
adsorption process was studied under optimized conditions of of fluoride probably takes place due to the diffusion taking
shaking time and AICFA dose. Fig. 6 shows the proportional place into the pores on the surface of the adsorbent [44]. After
relationship between the fluoride concentration and the 60 min, fluoride removal rate leveled off significantly, denoting
adsorbed amount of fluoride. However, increase in fluoride attainment of equilibrium and the nonavailability of sorption
concentration above 3 mg/L, reduced fluoride removal (4%), sites. The present results are in very good agreement with those
probably due to saturation of adsorption sites on the surface. of Nasr et al. [43]. As no further significant removal of fluoride
Removal of fluoride by coconut fiber 1279

98 0.98 98.0 0.976

Removal 0.97
qe 0.974
97.5 Removal
96 0.96 qe
0.972
0.95 97.0
Removal (%)

Removal (%)
qe (mg/g)

qe(mg/g)
94 0.970
0.94
96.5
0.93 0.968
92 96.0
0.92 0.966

0.91 95.5 0.964

90
0.90
95.0 0.962
0.01 0.02 0.03 0.04 0.05 0.06 310 320 330 340 350 360 370 380
adsorbent dose (g) Tempereture (K)

Figure 7a Effect of adsorbent dose (g) on removal of fluoride Figure 9 Effect of temperature (K) on removal of fluoride from
from water (initial conc. = 1 mg/L, pH = 5, contact time = 0.5 h, water (initial conc. = 1 mg/L, adsorbent dosage = 0.05 g/L,
temperature = 313 K). pH = 5, contact time = 40 min.).

F onto AICFA decreased. Probably rise of temperature

3.5
affects the solubility of F and it tends to escape from the solid
Distribution Coefficient (K )
D

3.0 phase to the bulk solution phase with increasing temperature.

2.5 Sujana et al. [13] reported that the exothermic nature of
2.0
adsorption of F on alum sludge existed because the rising tem-
perature increased the tendency for F to escape from the adsor-
1.5
bent. Another reason given was an increase in thermal energy
1.0 of adsorbed F at higher temperatures, causing increased des-
0.5 orption. Our results showed good agreement with many other
0.5 1.0 1.5 2.0 2.5 3.0 3.5
earlier studies [41,44,45].
Adsorbent dose (g/l)
3.7. Effect of co-ions on fluoride removal
Figure 7b Plot of KD value as a function of adsorbent dose (g/L)
(pH 5.0). [F]initial dose 0.5–3.5 g/L, pHinitial  5.0, volume of Previous reports have shown that some coexisting anions such
solution 0.1 L; contact time 60 min; shaking speed 450 rpm. as Cl, NO 2  2 3
3 , SO4 , HCO3 , CO3 , and PO4 could interfere in
the fluoride adsorption process [46,47]. Present study evaluates
the fluoride adsorption behavior in the presence of 100 mg L1
0.67
salt solutions of nitrate, chloride, sulfate and phosphate inde-
66 Removal 0.66 pendently, at the initial fluoride concentration of 1.0 mg L1.
qe The interference of these co-ions on F removal is shown in
0.65
Fig. 10. Fig. 10 reveals that fluoride removal is decreased from
Removal (%)

64 0.64 93.08% to 81.34% in the presence of sulfate and to 66.22% in

qe (mg/g)

the presence of phosphates. However, slightly increased

0.63
removal was noticed in the presence of chloride and nitrate
62
0.62 ions. It is quite possible because some anions would enhance
0.61
columbic forces and some would compete with fluoride for
60 the active sites [48]. On the other hand, it is reported that, mul-
0.60 tivalent anions are adsorbed more readily than monovalent
0 10 20 30 40 50 60 70 80 anions [49]. The relative performance of fluoride removal in
Contact time (min) the presence of anions increased in the order PO3 4 < SO4
2
 
< Cl < NO3 . This can be nicely explained with the help of
Figure 8 Effect of contact time (min) on removal of fluoride z/r (charge/radius) values of the anions, which is in the order
from water (initial conc. = 1 mg/L, adsorbent dosage = 0.05 g/L, of PO3 4 (3/3.40) > SO2 4 (2/2.40) > Cl (1/1.81) > NO 3
pH = 5, temperature = 313 K). (1/2.81). Very similar results are also reported by Chen et al.
[2] for removal of fluoride by granular ceramic [2].
was recorded after 60 min, an equilibrium time of 60 min was
chosen and this was used in all subsequent experiments. 3.8. Isotherm study

3.6. Effect of temperature The isotherm constants were calculated from the slope and
intercept of Langmuir, Freundlich and D–R isotherms and
Fig. 9 shows that temperature exerts striking effect on the are presented in Table 1. The equilibrium parameter RL, which
adsorption process. As temperature increased, the uptake of is defined as RL ¼ 1=ð1 þ bCA0 Þ, in the range of 0 < RL < 1
1280 N.K. Mondal et al.

100 interactions [54,55]. Adsorption kinetic study was carried out

with initial fluoride concentration of 1.0 mg L and adsorbent
80 dose of 0.5 g L1 at 313 K. Pseudo-first-order and pseudo-
second-order adsorption model and intra-particle diffusion
Removal (%)

60 model were used to test the kinetic data in order to establish

the mechanism of adsorption. The models are shown in Eqs.
40 (10)–(12), respectively [56,57] and the output of kinetics con-
stants are given in Table 2. The plot of intraparticle diffusion
20
is shown in Fig. 11. The plot reflects three stage maturities,
with an initial linear portion (a) followed by an intermediate
linear portion (b) and a sharp linear portion (c). The initial
0
Blank NaNO3 NaCl Na2SO4 Na3PO4
curve of the plot is due to the diffusion of F through the solu-
Types of salts
tion to the external surface of AICFA or to the boundary
layer. The second linear portion of curve describes the intra-
Figure 10 Effect of interfering ions for fluoride removal on particle diffusion of F on AICFA surface, and the last por-
AICFA (adsorbent dose 0.5 g L1, initial fluoride concentration tion is the adsorption equilibrium stage [58,59]. Moreover, it
1 mg L1, equilibrium contact time 1.0 h, initial pH 5.0 and is observed that the second portion did not pass through the
temperature 313 K). origin, indicating that the adsorption mechanism on AICFA
is probably complex and both the external adsorption and
intra-particle diffusion contribute to the adsorption process
reflects the favorable adsorption process [50]. In the present [60]. This is further supported by calculating the intraparticle
investigation the equilibrium parameter was found to be in
diffusion coefficient (D) using Eq. (13). According to Michel-
the range of 0 < RL < 1 (results are not shown). This indi-
son et al. [61] a D value of the order in 1011 Cm2 S2 is indica-
cated the fact that the sorption process is very favorable and
tive of intraparticle diffusion as rate determining step. In this
the adsorbent has a good potential for fluoride removal [40].
Again, Langmuir and Freundlich adsorption isotherm con- investigation, the value of D (2.81  108 Cm2 S2) was
stants usually do not provide any idea about the mechanisms obtained in the order of 108 Cm2 S2 which is more than
of adsorption [51]. In order to understand the adsorption type, three orders of higher magnitude. It indicates that the intra-
whether physical or chemical, equilibrium data were tested particle diffusion is not only the rate controlling step. It is con-
with Dubinin–Radushkevich isotherm. The value of R2 was cluded that both boundary layer and intraparticle diffusion
higher for both D–R and Langmuir than Freundlich isotherm. may be involved in this F removal process.
Moreover, The values of D–R isotherm constants, b (mol2/J2)
and qm (mg/g) were calculated from the slope and intercept of 3.10. Thermodynamic study
the plot. The values of b are found as 0.581, 0.593, 0.611 and
0.732 mol2 kJ2 at 313, 333, 353 and 373 K, respectively. Sim- The values of DG
, DH
and DS
are shown in Table 3. The
ilarly, the corresponding values of qm are obtained as 3.412, results show that DG
is negative, which indicates that adsorp-
5.621, 5.718 and 5.331 mg/g. The value of b is found to be tion of F on AICFA is a spontaneously process and the neg-
increasing along with increasing temperature while the value ative value of DH for the reaction indicates the exothermic
of qm shows increasing trend from 313 to 353 K, but is nature of the reaction. Therefore, lower temperature promotes
decreased at 373 K. The mean adsorption energy (E) is usually fluoride adsorption. The DS
is positive, which suggests
employed to differentiate the process of adsorption between increased randomness at the solid/solution interface during flu-
chemical and physical. If the value of E is in between 8 and oride adsorption.
16 kJ/mol, the adsorption process is said to be chemical while
the value below 8 kJ/mol indicates physical adsorption [52,53]. 3.11. Fluoride removal from groundwater
The values of E as determined using Eq. (9) for adsorption of
fluoride on AICFA were found as 0.927, 0.918, 0.946 and In order to assess the potential application of AICFA for
0.826 kJ/mol, respectively at the experimental temperatures removal of fluoride from drinking water, tests were conducted
indicated earlier. As all these values are less than 8 kJ/mol,
the fluoride adsorption on AICFA seems to be physisorption
in nature. Physical adsorption usually provides better regener-
ation scope [53].
Overall, using the linearized forms of different adsorption
isotherm models, it is observed that for fluoride adsorption
by AICFA, Langmuir isotherm fits well for other selected tem-
peratures except at 313 K. Freundlich isotherm fits well only at
353 K.

3.9. Kinetic study

The kinetics of any sorption process is a function of different

parameters, such as the structural properties of adsorbent, nat-
ure and concentration of adsorbate and adsorbent–adsorbate Figure 11 Intra-particle diffusion.
Removal of fluoride by coconut fiber 1281

Table 3 Thermodynamic parameters for fluoride adsorption 100

on AICFA.
80
DH
(kJ mol1) DS
(kJ mol1) DG
(kJ mol1)

Desorption (%)
331 K 333 K 353 K 373 K
60
34.90 116.29 9.534 9.720 10.202 10.177
40

with tube well water samples collected from the fluoride con-
taminated village of Nasipur, Birbhum district, West Bengal, 20

India. Various water parameters of the groundwater samples

were analyzed and are shown in Table 4. Defluoridation of 0
1 2 3 4 5 6 7 8 9 10 11 12 13
samples of groundwater was conducted without adjusting pH
of the experimental samples at the rate 0.5 g/L AICFA under pH

identical experimental conditions of the equilibrium batch

Figure 12 Regeneration of adsorbent (AICFA) at different pH.
adsorption study. It was found that the fluoride levels in
groundwater could come down to <0.96 mg/L.

3.12. Regeneration
Table 5 Comparison of the defluoridation capacities of
Water purification by adsorption technology is considered eco- different biomass carbon and modified biomass causes.
nomical when the adsorbent is regenerable. Moreover, reuse of Adsorbent pH Adsorption References
adsorbent helps to reduce environmental impacts of disposal capacity
of the used adsorbents. Desorption studies were carried out (mg g1)
with 2 g/L fluoride adsorbed AICFA at varying pH by using Eichhormia crassipes Biomass 5.8 0.52 [62]
0.1 M NaOH. Fig. 12 shows that up to pH 8, there is no fluo- Carbon at 300 °C
ride leaching. However, desorption of fluoride occurs better at Biomass Carbon at 600 °C 1.54 [62]
pH greater than 8 and reaches maximum of 98% at pH 12. The Moringa indica based activated 2.0 0.23 [63]
adsorption capacity of regenerated AICFA reduces from 92% carbon
to 84% in first time and thereafter decreases gradually. It Used tea waste carbon [18]
seems probably that at higher pH, OHA ions accumulated Activated carbon derived from rice 2.0 15.90 [41]
on fluoride loaded AICFA. Therefore, it is necessary to reacti- strand
Pine wood biochar 2.0 7.66 [21]
vate the AICFA under suitable pH medium for further use.
Pine wood biochar 2.0 9.77 [21]
Almost similar regeneration of adsorbent by varying concen-
Ammonium carbonate activated 7.05 22.33 [3]
tration of NaOH solution was reported by Bhaumik and Mon- carbon of Tamarindus indica fruit
dal [42]. However, a further study is needed to assess the shell
potentiality for reuse of AICFA. Zirconium(iv)-impregnated 2.23 [64]
groundnut (Anacardium
3.13. Comparison with other adsorbents occidentale) shell carbon
Cynodon dactylon-based activated 7.0 4.617 [65]
carbon
The adsorption isotherms for the removal of fluoride ions from
Zirconium impregnated cashew nut 7.0 1.83 [66]
aqueous solution obtained in the present study were compared (Anacardium occidental) shell
with those reported earlier in the literature (Table 5). However, carbon
direct comparison of AICFA with other adsorbents is difficult, Sugarcane bagasse carbon [16]
Phyllanthus embolic based 7.0 7.014 [67]
thermally activated carbon
Pecan (carya illinoinensis)nut shell 7.0 1.61–2.51 [68]
Table 4 Physico-chemical characteristics of groundwater carbon modified with egg shells
samples. calcium
Scandinavia spruce wood modified 6.9 7.92 [69]
Parameters Nasipur with aluminum and iron oxides
Conductivity (lS/cm) 102 ± 1.01 carbonized at 500 °C
Hardness (mg/L, CaCO3) 180 ± 2.66 Scandinavia spruce wood modified 6.9 5.67 [69]
Carbonate (mg/L) ND with aluminum and iron oxides
Chloride (mg/L) 10.1 ± 0.03 carbonized at 650 °C
Nitrate (mg/L) 8.7 ± 0.61 Scandinavia spruce wood modified 6.9 5.67 [69]
Sulfate (mg/L) 0.88 ± 1.02 with aluminum and iron oxides
Fluoride (mg/L) 6.01 ± 0.11 carbonized at 900 °C
Sodium (mg/L) 106 ± 1.07 Activated bagasse carbon 6.0 1.15 [15]
Calcium (mg/L) 12.5 ± 1.28 Aluminum impregnated coconut 5.0a 3.192a Current
pH 7.80 fiber ash studied
a
Mean ± SD. Freundlich adsorption capacity.
1282 N.K. Mondal et al.

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[8] WHO (World Health Organization), Guidelines for Drinking
one of the modified forms of coconut fiber, has been reported
Water Quality, World Health Organization, Geneva, 2004.
in the present paper for fluoride removal from aqueous solu- [9] WHO (World Health Organization), Guidelines for Drinking
tions and some of the important conclusions have been drawn. Water Quality, World Health Organization, Geneva, 1993.
Aluminum impregnated coconut fiber ash (AICFA) has signif- [10] P.I. Ndiaye, P. Moulin, L. Dominguez, J.C. Millet, F. Charbit,
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(PO3 2
4 and SO4 ) has negative effect on fluoride adsorption. Investigation on fixed bed column performance of fluoride
The regenerated AICFA shows lower fluoride adsorption per- adsorption by sugarcane charcoal, J. Environ. Biol. 34 (2013)
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Acknowledgments equilibrium, kinetic and thermodynamic study, J. Modern
Chem. Chem Technol. (2012) 1–21.
This work was financially supported by the University of Bur- [19] N.K. Mondal, R. Bhaaumik, T. Baur, B.A. Das, P. Roy, J.K.
dwan, Burdwan, to the Department of Environmental Science. Datta, Studies on defluoridation of water by tea ash: an
Moreover, authors extend their sincere thanks to Dr. Partha unconventional biosorbent, Chem. Sci. Trans. 1 (2012) 239–256.
Mitra, Associate Professor, Department of Physics, The [20] R. Bhaumik, N.K. Mondal, B. Das, P. Roy, K.C. Pal, C. Das,
University of Burdwan for his kind cooperation and necessary A. Banerjee, J.K. Datta, Egg shell powder as an adsorbent for
instrumental help. removal of fluoride from aqueous solution: equilibrium, kinetics
and thermodynamics study, E-J. Chem. 9 (3) (2012) 1457–1480.
[21] S.V. Mohan, S.V. Ramanaiah, B. Rajkumar, P.N. Sarma,
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