Journal of Environmental Chemical Engineering 5 (2017) 5608–5616

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Journal of Environmental Chemical Engineering

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Fluoride adsorption from aqueous solution using activated carbon obtained T

from KOH-treated jamun (Syzygium cumini) seed
⁎
Ramya Araga, Shantanu Soni, Chandra S. Sharma
Creative & Advanced Research Based On Nanomaterials (CARBON) Laboratory, Department of Chemical Engineering, Indian Institute of Technology, Hyderabad, Kandi-
502285, Telangana, India

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

Keywords: In this study, for the first time, jamun seed derived activated carbon was used as an adsorbent for removal of
Jamun seed fluoride from water. Activated carbon was prepared by KOH activation of jamun seed and subsequent pyrolysis
KOH activation at 900 °C. The fluoride sorption experiments were carried out under batch mode to optimize the various in-
Activated carbon fluencing parameters such as contact time (0–3 h), dosage of adsorbent (20–500 mg), initial fluoride con-
Fluoride ion
centration (2–20 mg L−1), temperature (298–308–318 K), and pH (2.5–10). The contact time and pH for max-
Adsorption
imum fluoride uptake were observed at 120 min and 2.5 respectively. Maximum adsorption capacity (3.65 mg g-
1) of fluoride on activated carbon was found for 10 mg L−1 of initial fluoride concentration using 0.4 g L−1
adsorbent dosage. The equilibrium data were found to follow Dubinin-Radushkevich isotherm among the three
applied isotherm models (Freundlich, Temkin, and Dubinin-Radushkevich) and pseudo-second-order kinetic
mechanism with the rate constant of 0.036 g mg−1 min−1. Thermodynamic analysis revealed that the adsorp-
tion process was exothermic in nature. Performance of the prepared adsorbent was compared with other re-
ported biomass derived activated carbons and it was observed that the proposed adsorbent is efficient in terms of
its adsorption capacity. In addition to synthetic samples, field water samples collected from fluoride affected
villages were also tested for adsorption experiments.

1. Introduction membrane processes include high operational and maintenance cost,

Consumption of contaminated water will have hazardous influences
on human health. Among the various aquatic pollutants, fluoride is one
of the most abundant elements present in environment and it con-
taminates the groundwater by both natural and artificial causes [1].
Fluoride concentration in drinking water is a real health concern be-
cause ingestion of excessive fluoride (permissible value of fluoride in
drinking water suggested by World Health Organization (WHO) is
1.5 mg L−1) causes thyroid disorder, Alzheimer’s syndrome, osteo-
sclerosis (brittle bones) and dental/skeletal fluorosis [2]. The excess
concentrations of fluoride in groundwater have been recognized in
many developed and developing nations including USA, Asia, and
Africa. In India, fluoride was firstly detected in 1937 at Nellore district
of Andhra Pradesh and later it has been found that 17 states of India are
affected with high fluoride content, especially Telangana, Rajasthan,
Madhya Pradesh, Uttar Pradesh and Gujarat [3].
Many methods have been developed to reduce the fluoride content
from water, namely adsorption, coagulation and precipitation, ion ex-
change and membrane process [3,4]. However, ion exchange and
toxic sludge generation, and complicated procedure to treat the
fluoridated water. Coagulation and precipitation is the traditional
method being used for the removal of fluoride from water and Nal-
gonda technique is widely used to treat the fluoride contaminated water
in many countries but the resulting high residual aluminum con-
centration (2–7 mg L−1) is the major disadvantage of this technique.
Among all these techniques, adsorption is widely studied and adopted
because of its low cost, easy maintenance, simple operation and the
efficient performance [4,5].
Other than the conventional adsorbents that are being used for
defluoridation purpose such as activated alumina and alumina modified
adsorbents, various unconventional biomass waste materials have been
tested and reported for the fluoride removal in recent years e.g., acti-
vated coconut fiber dust [6], sugarcane bagasse [7], activated carbons
derived from coconut shell [8], coconut fiber [9], rice straw [10], tea
ash [11], banana peel and coffee husk [12], bael shell [13], and Con-
ocarpus erectus [14] because of their low cost, easy availability and
efficient fluoride removal. Different functional groups present on the
surface of biomass-based adsorbents such as hydroxyl, carboxyl,

⁎
Corresponding author.
E-mail address: cssharma@iith.ac.in (C.S. Sharma).

http://dx.doi.org/10.1016/j.jece.2017.10.023
Received 16 June 2017; Received in revised form 2 October 2017; Accepted 12 October 2017
Available online 18 October 2017
2213-3437/ © 2017 Elsevier Ltd. All rights reserved.
R. Araga et al.
carbonyl, amide and amine may involve in the physiochemical inter-
actions of fluoride ions [3].
The major objective of this study is to evaluate the fluoride removal
efficiency of a novel and low-cost adsorbent which is jamun seed de-
rived activated carbon from aqueous solution by carrying out the batch
adsorption experiments. Among various chemical reagents (KOH,
H3PO4, ZnCl2 etc.), KOH was found as efficient activating agent because
of its well-defined micropore size distribution and high surface area of
resultant carbon material [15]. The jamun seed powder was im-
pregnated with KOH solution to increase the surface area, consequently
adsorption capacity. Various influencing parameters of defluoridation
process viz., contact time, adsorbent dosage, initial fluoride con-
centration, temperature, and pH were optimized and further desorption
studies were also carried out to check the reusability of adsorbent. The
suitability of prepared adsorbent was tested by field water samples
collected from the nearby fluoride affected villages.
2. Materials and methods
2.1. Materials
Jamun seed powder was purchased from Patanjali Ayurved Limited,
India. Potassium hydroxide (KOH) was purchased from Merck, India.
Sodium fluoride (NaF, 99%) and Sodium hydroxide pellets (NaOH,
98%) were purchased from Alfa Aesar. Hydrochloric acid (HCl, 37%)
was purchased from Sigma-Aldrich, India. All the materials were used
as received without any further purification. Deionized distilled water
(resistivity of 18.2 MΩ-cm, Millipore) was used for all of the experi-
ments.
2.2. Preparation of adsorbent
Jamun seed powder was mixed with the aqueous solution of KOH,
with the precursor to KOH ratio of 1:0.1 by weight, and stirred at room
temperature for 2 days as reported elsewhere [15]. Later the treated
sample was dried at 110 °C for 12 h to remove the water content. As-
obtained dried sample was pyrolyzed in a tubular high-temperature
furnace (Nabertherm GMBH) under high purity nitrogen (N2) (99.99%)
atmosphere. N2 flow rate was maintained at 1.25 l min−1 after initial
purging. The pyrolysis process consisted of following steps: (a) from
room temperature to 350 °C with the heating ramp of 2 °C min−1 (b) a
dwell at 350 °C for 30 min (c) from 350 °C to 900 °C with the heating
ramp of 5 °C min−1 (d) dwell at 900 °C for 1 h and finally (e) cooling
from 900 °C to room temperature. After cooling, the sample was taken
out from the furnace tube and washed several times with hydrochloric
acid solution (0.1 M) and distilled water to remove the residual KOH.
The activated carbon sample was then dried at 110 °C overnight and
crushed into a fine powder prior to adsorption studies, which was la-
beled as activated jamun seed (AJS). Another set of sample which is not
treated with KOH but pyrolyzed is also prepared (labeled as pyrolyzed
jamun seed, PJS) for comparison of adsorption capacities.
2.3. Characterization
The morphology of as-prepared jamun seed derived inactivated and
activated carbon was examined using field emission scanning electron
microscopy (FESEM) (Zeiss). The structural characterizations of carbon
samples were investigated by using powder X-ray diffractometer (XRD)
(PANalytical) with Cu Kα radiation (0.154 nm) and Raman spectro-
meter (Senterra, Bruker) with an excitation wavelength of 532 nm. The
presence of functional groups in the prepared samples was investigated
by Fourier transform infrared spectroscopy (FTIR) (Tensor 37, Bruker).
The Brunauer-Emmett-Teller (BET) surface area was calculated by the
adsorption/desorption isotherms of N2 conducted at 77 K using BET
surface analyzer (Quantachrome autosorb). The isoelectric point of
KOH treated and pyrolyzed jamun seed was measured by zeta potential
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Journal of Environmental Chemical Engineering 5 (2017) 5608–5616
analyzer (Delsa nano, Beckman Coulter).
2.4. Batch adsorption experiments
All the adsorption experiments were carried out with 50 ml of
known concentration of fluoride solution. After adding a known weight
of adsorbent, the solution contained conical flasks were shaken in a
shaking incubator (RIS-24 Plus, REMI India) at the speed of 150 rpm.
Once the equilibrium is attained, the solution was taken out from the
flask and filtered through the vacuum filtration system (Millipore). The
residual fluoride concentration was determined with ion chromato-
graphy (Basic IC Plus, Metrohm AG).
The amount of fluoride adsorbed by the carbon sample (qe, mg g−1)
and percentage adsorption (%) were calculated using the following
equations respectively.
V (Ci − Ce )
qe =
W (1)
(Ci − Ce )
Percentage adsorption (%) = × 100
Ci (2)
−
Where Ci and Ce are the initial and equilibrium concentrations of F in
solution (mg L−1); V is the volume of solution (L), and W is the weight
of adsorbent (g) respectively.
2.5. Desorption experiments
In order to examine the regeneration ability of AJS, desorption
studies were carried out with the fluoride adsorbed activated carbon.
Initially, fluoride was adsorbed onto activated carbon by using
10 mg L−1 of fluoride solution onto 300 mg of adsorbent. Once the
equilibrium was reached, solution was filtered and the residue (fluoride
adsorbed activated carbon) was further subjected to desorption.
Desorption studies were carried at different pH values (4–10) by the
addition of 0.1 M HCl or 0.1 M NaOH and the suspensions were
maintained for 30 min in orbital shaker at the speed of 100 rpm. Later
the residue was filtered, the filtrate fluoride concentration was mea-
sured and the procedure was repeated at least for five times using the
same activated carbon.
3. Results and discussion
3.1. Characterization of adsorbent
3.1.1. Morphology
The surface morphology of the untreated jamun seed powder, PJS
and AJS were examined by FESEM (as shown in Fig. 1). The particle
size distribution of untreated jamun seed powder (Fig. 1a and b) is
random and the particles were found to be agglomerated during the
KOH treatment and pyrolysis process. Those agglomerated particles
were grinded using a mortar to obtain a fine powder and used for SEM
imaging and later for fluoride adsorption studies. SEM micrographs of
the activated sample (Fig. 1e and f) illustrate that the activated carbon
particles are porous in nature and such type of porosity is not seen in
the inactivated carbon sample (Fig. 1c and d).
3.1.2. Structural characterizations
The powder X-ray diffraction patterns were recorded to study the
crystalline structure of the prepared charcoal samples and are shown in
Fig. 2(a). XRD patterns of both inactivated and activated carbon show
the broad noncrystalline peaks at 2θ of 25° and 43° corresponds to re-
flections of (0 0 2) and (1 0 0) planes. The absence of distinct peaks for
the crystalline forms of carbon is evident for the disordered nature of
samples [16].
Fig. 2(b) shows the deconvoluted Raman spectra of synthesized
inactivated and activated charcoal samples and it displays two broad
R. Araga et al.
peaks centered at about 1350 and 1580 cm−1, which are associated
with characteristic D band (1350 cm−1) and G band (1580 cm−1). The
intensity ratio of D to G (ID/IG) is calculated to be 0.93 for inactivated
carbon and 1.06 for activated carbon, which indicates both the carbons
are disordered carbons [17].
Disordered carbons (hard carbons) are known to have good ad-
sorption properties due to the availability of high surface area and more
Fig. 2. (a) XRD and (b) Raman spectra of PJS and AJS.
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Journal of Environmental Chemical Engineering 5 (2017) 5608–5616
Fig. 1. FESEM images of (a-b) untreated jamun seed
powder, (c-d) PJS and (e-f) AJS.
active sites on the surface because of randomly arranged crystallites
and graphene layers [16,18]. Consequently, jamun seed derived hard
carbon was tested for removal of fluoride.
3.1.3. Functional group characterization
The FIIR spectra of prepared carbon samples were presented in
Fig. 3. No significant changes have been observed in the characteristic
R. Araga et al.
Fig. 3. FTIR spectra of jamun seed derived carbon before and after activation.
absorption peaks of the inactivated and activated carbon samples. Even
though numerous functional groups were present on the surface of
carbon, the peaks centered at 803 cm−1 (]CeH bend), 1028 cm−1 and
1092 cm−1 (CeO stretch), 1260 cm−1 (CeO Stretch), 1630 cm−1
(C]C Stretch) and 3437 cm−1 (OeH stretch) are prominent among
them [19]. Among these functional groups, the fluoride ions can bind
effectively to eOH and eCO functional groups [6].
3.1.4. Surface area characterization
The surface area of product inactivated and activated carbons were
determined by degassing 100 mg of sample mass at 300 °C for 4 h to
remove any adsorbed species before N2 adsorption experiment.
Nitrogen adsorption isotherms were measured at 77 K adsorption
temperature. The surface area calculated from BET plots (shown in Figs.
4a and 4b ) is as follows: 13.67 m2 g−1 for PJS and 747.45 m2 g−1 for
AJS whereas total pore volume is determined as 0.019 cm3 g−1 for PJS
and 0.41 cm3 g−1 for AJS. The BET surface area and pore volume of the
activated carbon are increased prominently and it is evident of the great
influence of porogen addition to the biomass.
3.1.5. Point of zero charge determination
The pH at which surface charge of the adsorbent takes a zero value
is defined as point of zero charge (pHPZC). At pHPZC, the charge of
positive surface sites is equal to charge of negative surface sites. If the
solution pH is higher than pHPZC, the sorbent surface is negatively
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Journal of Environmental Chemical Engineering 5 (2017) 5608–5616
Fig. 5. Effect of pH on zeta potential of jamun seed activated carbon in aqueous sus-
pension.
charged and it could interact with positive species in the solution. If the
solution pH is lower than pHPZC, the sorbent surface is positively
charged and it could interact with negative species in the solution [13].
The zeta potential of activated carbon suspension at different pH
values was determined by zeta potential analyzer. For this purpose, the
pH of carbon suspensions was adjusted to initial values between 2 and
11, by adding either HCl or NaOH. Then zeta potential was measured
and plotted against initial pH, as illustrated in Fig. 5. The pH at which
zero-crossing occurs is taken as pHPZC and the value of pHPZC for the
prepared activated carbon sample is determined as 4.9. To attract the
fluoride ions, the adsorbent surface must be positively charged and
positive carbon surface can be achieved when the pH of the solution is
lower than pHPZC which is 4.9.
3.2. Adsorption experiments
3.2.1. Effect of agitation time
Initially, the adsorption of fluoride on prepared activated carbon
was studied as a function of time in order to find out the equilibrium
time for maximum adsorption. The time profile of fluoride adsorption
onto activated carbon is presented in Fig. 6. As-prepared activated
carbon of 50 mg was used for 50 ml of 10 mg L−1 fluoride solution. The
amount of fluoride adsorption (mg g−1) increased with increase in
agitation time initially, but gradually it became sluggish and ap-
proached to nearly a constant value at the time of 120 min, beyond
which there is no further adsorption. The active sites which are avail-
able in the initial stage of adsorption become limited due to the binding
of fluoride ions. The occupation of remaining vacant active sites by the
Fig. 4. BET surface area analysis of jamun seed derived
carbon (a) before and (b) after activation.
R. Araga et al.
Fig. 6. Effect of agitation time on F− adsorption of jamun seed derived activated carbon.
fluoride ions is difficult because of the formation of repulsive forces
between adsorbate on the solid surface and the liquid surface [6].
Further the data obtained were successfully used to evaluate the ad-
sorption kinetics which were discussed in section 3.3.2.
3.2.2. Effect of adsorbent dosage
Fig. 7 shows the amount of fluoride removed as the function of
carbon dosages at 10 mg L−1 of initial fluoride concentration. The
amount of dosage was varied from 20 to 500 mg per 50 ml of fluoride
solution under the optimized condition of agitation time. The result
shows that by increasing the amount of adsorbent, the percentage re-
moval also increases but decreases the adsorption capacity. Percentage
adsorption has attained the equilibrium at the adsorbent dosage of
300 mg (optimum weight of activated carbon) beyond which there is no
substantial removal of fluoride.
Various factors are reported which can cause the effect of adsorbent
dosage. Those includes: (a) with an increase in the adsorbent dosage,
the unsaturation of adsorption sites may lead to drop in adsorption
capacity (b) agglomeration of adsorbent particles at higher doses may
lead to reduce in the surface area and increase the diffusional path
length [10].
3.2.3. Effect of initial fluoride concentration
The effect of initial fluoride solution concentration on adsorption
process was studied under optimum conditions of shaking time and
carbon dose as illustrated in Fig. 8. The adsorption capacity was varied
from 0.1 mg g−1 to 1.25 mg g−1 with an increase of fluoride
Fig. 7. Effect of carbon dosage on% adsorption and adsorption capacity of fluoride ions
onto activated jamun seed derived carbon.
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Journal of Environmental Chemical Engineering 5 (2017) 5608–5616
Fig. 8. Effect of initial fluoride concentration on% adsorption and adsorption capacity of
fluoride ions onto as-prepared jamun seed derived activated charcoal.
concentration from 2.7 mg L−1 to 20.04 mg L−1, whereas the fluoride
removal efficiency is initially high for low F− concentrations because of
the more interaction of F− ions with the adsorption sites. Further, it
reduced at higher concentrations due to the saturation of available
active sites [13].
3.2.4. Effect of solution pH
It can be seen from Fig. 9 that the adsorption is strongly dependent
on pH. Fluoride ion removal increases with a decrease in pH and the
optimum pH was observed at the value of 3. Jamun seed derived ac-
tivated carbon acquires a positive charge at low pH (as discussed in the
section 3.1.5). Thus, high percentage of adsorption in the acidic
medium can be explained by the attractive forces of surface positive
charges towards the F− ions and low percentage adsorption in alkaline
medium is attributed to the repulsion of F− ions by the gradual increase
of negative surface charges. A similar effect of pH on fluoride adsorp-
tion has been reported by other authors as well [10,11]. In case of
pH < 3, no significant improvement was observed in the adsorption
capacity of the prepared adsorbent material. Therefore, all the batch
sorption experiments were carried out at the pH value of 3.
3.2.4.1. Possible adsorption mechanism:. The pH of solution was found
to be one of the most important factors that control the adsorption of
F− ions onto surface of activated carbon. The fluoride adsorption onto
prepared charcoal can be explained by the following two-step ligand
exchange reaction as reported in the literature [10,20,21]:
Fig. 9. Effect of pH on adsorption of fluoride ions onto jamun seed derived activated
carbon.
R. Araga et al. Journal of Environmental Chemical Engineering 5 (2017) 5608–5616

-COH + H+ ↔ COH2+ (3) Table 1

Summary of equilibrium isotherm parameters for the fluoride ion adsorption onto acti-
−
-COH2+ +F ↔ CF + H2O (4) vated jamun seed derived carbon at different temperatures.

Hence, the combined reaction is Temperature (K) Freundlich constant

−
-COH + H +
+F ↔ CF + H2O (5) Kf (mg g−1) N R2

Where −COH represents the surface hydroxyl group of activated 298 0.035 0.477 0.928
carbon. Another mechanism is proposed by Y. Wang et al. [22] as fol- 308 0.013 0.377 0.959
lows: 318 3.02 0.199 0.761

COH + F− ↔ CF + OH− (6) Temperature (K) Temkin constant

However, the difficulty with this mechanism is at higher pH values

A (L mg−1) b (J mol−1) R2
there would be competition between the OH− and F− ions for the ac-
tive sites of adsorbent. 298 0.45 1783.7 0.927
308 0.41 1686.9 0.904
318 0.38 1336.6 0.968
3.2.5. Effect of temperature on fluoride removal
The rate of diffusion of adsorbate molecules through the boundary
Temperature (K) D-R constant
layer and internal pores of adsorbent will increase with respect to in-
crease in temperature due to decrease in the thickness of boundary qm (mg g−1) K (mol2 kJ−2) E (kJ mol−1) R2
layer [23]. So, the effect of temperature on the fluoride adsorption rate
298 2.27 3.44 0.38 0.986
onto prepared activated carbon was investigated at three different
308 2.53 4.07 0.35 0.985
temperatures, i.e. 298, 308 and 318 K and presented in Fig. 10. 318 8.42 8.18 0.25 0.939
With the jamun seed derived activated carbon the adsorption ca-
pacity was found to be higher at 25 °C up to the fluoride ion con-
centration of 5.5 mg L−1, but there is no significant variation in the
adsorbent performance at the temperatures of 25 and 35 °C. Later at
higher concentrations, maximum capacity was attained at 45 °C and if
we increase the temperature further to 55 °C, desorption occurred. At
much higher solution concentrations i.e., beyond 10 mg L−1, the lesser
temperatures were found to be favorable for adsorption.

3.3. Adsorption isotherms, kinetics and thermodynamics study

3.3.1. Adsorption isotherms study

Adsorption isotherm data reveals the distribution of adsorbate mo-
lecules between the solid phase and liquid phase when the adsorption
process reaches the equilibrium. We can predict the adsorption capacity
by analyzing the isotherm data and this is one of the key parameters
required to design the adsorption system [24]. The experimental ad-
sorption equilibrium data of F− ions onto jamun seed resultant acti-
vated charcoal was fit into the linearized isotherm models of Freun- Fig. 11. Dubinin-Radushkevich plots for fluoride adsorption onto activated jamun seed
dlich, Temkin, and Dubinin-Radushkevich. The mathematical carbon at different temperatures.
descriptions of these models are given by the following equations
[24–26]: 1
log qe = log Kf + log Ce
Freundlich adsorption isotherm: n (7)

Kf (mg g−1) and n are Freundlich isotherm constants related to ad-

sorption capacity and adsorption intensity.
Temkin adsorption isotherm:
qe = B ln Ce + B ln A (8)

RT
B=
b (9)
−1 −1
A (L g ) and b (J mol ) are Temkin isotherm constants where b is the
heat of adsorption.
Dubinin-Radushkevich (D-R) adsorption isotherm:
ln qe = ln qm − Kε 2 (10)

1
ε = RT ln(1 + )
Ce (11)

1
E=
2K (12)
Fig. 10. Effect of temperature on adsorption of fluoride ions onto prepared activated
carbon.
Where qm is the D-R theoretical maximum adsorption capacity

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Fig. 12. Kinetic modeling of F− adsorption onto AJS

(a) Pseudo-first-order model (b) Pseudo-second-
order model (initial F− concentration: 10 mg L−1,
pH:3, Temperature: 298 K).

Table 2
Kinetic constants for fluoride adsorption onto jamun seed derived activated carbon.

Initial Fluoride Concentration (mg L−1) Pseudo-first-order model Pseudo-second-order model

qe,exp (mg g−1) k1 (min−1) qe,cal (mg g−1) R2 qe (mg g−1) K2 (g mg−1 min−1) R2

10 2.5 0.02 1.094 0.941 2.675 0.036 0.997

with D-R isotherm because the R2 values (varied from 0.986 to 0.939)
are higher for D-R isotherm than both Freundlich and Temkin iso-
therms. The values of K and qm were calculated from the slope and
intercept of ln qe verses ε2 plots as shown in Fig. 11.
The values of E were found as 0.38, 0.35 and 0.25 kJ mol−1 at ex-
perimental temperatures, which confirms that the F− adsorption onto
prepared jamun seed derived activated carbon is physisorption in
nature (E < 8 KJ mol−1 indicates physical adsorption). The major
advantage of physisorption is it provides better regeneration scope
[27].

3.3.2. Adsorption kinetics study

Fig. 13. Van’t Hoff plot of fluoride ion adsorption onto jamun seed activated carbon.
(mg g−1), K is D-R isotherm constant related to adsorption energy
(mol2 kJ−2), ε is Polanyi potential and E is the mean free energy of
adsorption (kJ mol−1).
qe is adsorption capacity of activated carbon at equilibrium
(mg g−1), Ce is equilibrium concentration of adsorbate (mg L−1) and R
is the universal gas constant (8.314 J mol−1 K−1). The isotherm con-
stants of the above-mentioned models obtained by least square method
are listed in Table 1. The fitting of these isotherms is judged based on
the value of regression coefficient (R2).
By comparing the results presented in Table 1, adsorption of
fluoride ions onto prepared activated carbon was found to be well fitted
Adsorption kinetics describes the adsorption mechanism of ad-
sorbate on adsorbent and it depends on the nature of adsorbent,
structural properties, adsorbate concentration and adsorbent-adsorbate
interactions. To understand the mechanism of F− ions onto jamun seed
resulted activated carbon, the data were tested with pseudo-first-order
and pseudo-second-order kinetic models. The linear form of kinetic
equations is as follows [25]:
Pseudo-first-order model:
k1 t
log(qe,exp − qt ) = log qe, cal −
2.303 (13)
Where qe,exp (mg g−1) is the adsorption uptake at equilibrium, qt
(mg g−1) is the amount of fluoride adsorbed on the adsorbent at the
time of t, k1 (min−1) is the first-order rate constant, qe,cal and k1 were
calculated from the intercept and slope of log (qe–qt) versus t plot as
presented in Fig. 12(a).
Pseudo-second-order model:

Table 3
Thermodynamic parameters of F− adsorption onto jamun seed activated carbon.

Temperature (K) ΔG° (kJ mol−1) ΔS° ( × 10−3 kJ mol−1 K−1) ΔH° (kJ mol−1)

298 2.8 −42.98 −9.95

308 3.3
318 3.7

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Table 4 Fluoride concentration of the samples was measured as 2.65, 3.1 and
Comparison of various biomass-derived carbons used for fluoride ion removal. 3.2 mg L−1. The prepared adsorbent reduced the fluoride concentration
from above-mentioned values to the permissible level by using 15 g L−1
Adsorbent Adsorption capacity (mg g−1) Reference
of adsorbent dose for 50 ml of sample, pH = 3, contact time = 120 min
Tea ash 3.75 [11] and temperature = 298 K. For field water sample the adsorbent dosage
Banana peel 0.31 [12] was higher compared to the synthetic samples because of its less re-
Coffee husk 0.29 [12]
moval capacity at the lower concentrations as well as the presence of
Bael shell 2.45 [13]
Coconut shell 0.96 [30] co-anions viz., Cl− and NO3− which competes for active sites of ad-
Morringa indica 0.23 [31] sorbent.
Jamun seed (activated) 3.65 Present work
Jamun seed (inactivated) 0.80 Present work 3.6. Comparison with other biomass derived adsorbents

t 1 t Table 4 shows the comparison that has been made between the
= +
qt k2 qe 2 qe
−1 −1
Where k2 (g.mg min ) is the rate constant of second-order ad-
sorption, qe and k2 were determined from the slope and intercept of t/qt
versus t plot as shown in Fig. 12(b).
Constants determined for the kinetic models are presented in
Table 2. The regression coefficient (R2 = 0.997) for the pseudo-second-
order adsorption model is higher than the value obtained for pseudo
first-order kinetics (R2 = 0.941) and closer to unity. However, the R2
value of the pseudo first-order model is not satisfactory. In addition,
adsorption capacity calculated (qe = 2.675 mg g−1) from the second-
order kinetics is in good accordance with the experimental adsorption
capacity of F− ions (qe,exp = 2.5 mg g−1). So, the F− adsorption onto
jamun seed derived activated carbon is well fitted with pseudo-second-
order reaction kinetic model.
3.3.3. Adsorption thermodynamics study
Investigation of thermodynamic parameters (Gibbs energy change
(ΔG°), enthalpy change (ΔH°) and entropy change (ΔS°)) plays an im-
portant role in estimating the adsorption mechanism. The mentioned
parameters were determined using the following equations [28]:
jamun seed derived activated carbon and other biomass-based carbon
(14)
adsorbents for the fluoride removal. Maximum adsorption capacity was
used as a parameter for comparison. The defluoridation capacity of AJS
was found to be superior over other adsorbents except for tea ash.
4. Conclusion
The activated carbon prepared from the jamun seed was successfully
used as an adsorbent for defluoridation of synthetic and field water
samples. Following conclusions can be drawn from the results of pre-
sent study:
• High surface area carbon material was obtained by the pyrolysis of
jamun seed powder upon the addition of KOH as activating agent.
• Protonated surface hydroxyl groups of prepared adsorbent partici-
pated in the defluoridation process.
• The equilibrium isotherm data are fitted well to Dubinin-
Radushkevich model and adsorption kinetics could be well re-
presented by pseudo-second-order kinetic model. Thermodynamic
investigation reveals the non-spontaneity and exothermic nature of
adsorption.

ΔGo = −RT ln K o
ΔS o ΔH o
ln K o = − 2 h) respectively.
R RT
−1 −1
Where R is the universal gas constant (8.314 J mol K ), T is the
absolute temperature (K) and Ko is the thermodynamic equilibrium
constant. The values of ΔH° and ΔS° were determined from the slope
and intercept of Van’t Hoff plot of ln Ko versus 1/T as shown in Fig. 13
and are summarized in Table 3.
The positive values of ΔG° suggests that adsorption process is non-
spontaneous and it requires some energy from an external source for the
adsorption reaction. The negative value of ΔH° suggests that the ad-
sorption phenomenon is exothermic while the negative entropy value
implies a lesser degree of randomness at the solid-solution interface
[28]. It causes the adsorbate molecules to escape from the solid phase to
liquid phase, therefore the amount of adsorption will decrease [29].
(15) • The minimum and maximum uptake of F− ions were found to be
0.1 mg g−1 and 1.25 mg g−1 at the concentrations of 2.7 mg L−1
and 20.04 mg L−1 (dose: 6 g L−1, pH: 3, temperature: 25 °C, time:
(16)
• Recycling of activated carbon is feasible due to 96% of desorption.
•
Maximum removal efficiency of PJS was measured as 3% (initial F−
concentration: 10 mg L−1, dose: 2 g L−1, pH: 3, time: 2 h), because
of the availability of less surface area of adsorbent (as confirmed by
BET analysis).
Moreover, the decreasing of fluoride concentration from real
groundwater samples to the permissible limits shows the scope of
prepared adsorbent on a real-time basis. Hence, it can be concluded that
the as-prepared jamun seed derived activated carbon have the potential
to be effectively used for fluoride removal from water.
Contribution

3.4. Desorption study
Regeneration is an important step to develop a cost-effective ad-
sorbent for fluoride removal. Desorption experiments were carried at
different pH values (4–11) with fluoride loaded adsorbents and deso-
rption efficiency was found to be 96% beyond the pH of 6. It indicates
that the recyclability of the jamun seed resulted activated carbon is
possible and henceforth recommended.
3.5. Field studies
The applicability of prepared jamun seed derived activated carbon
was tested with three different real water samples collected from the
nearby fluoride affected villages (Nalgonda district, Telangana, India).
CSS planned the work while RA and SS performed all the experi-
ments. All authors analysed the data and prepared the manuscript.
Acknowledgement
RA acknowledges Dr. Manohar Kakunuri for his valuable discus-
sions and suggestions, which significantly improved the quality of this
manuscript. CSS acknowledges Indian Institute of Technology,
Hyderabad for providing necessary research facilities.
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