Batch Studies of Water Defluoridation Using Fishbone Charcoal

Author(s): Devendra S. Bhargava and Shri D. J. Killedar

Source: Research Journal of the Water Pollution Control Federation, Vol. 63, No. 6 (Sep. -
Oct., 1991), pp. 848-858
Published by: {wef}
Stable URL: https://www.jstor.org/stable/25044074
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 Batch studies of water defluoridation using
fishbone charcoal
Devendr? S. Bhargava, Shri D. J. Killedar

ABSTRACT: Fishbone charcoal adsorbs fluoride from aqueous solu
tions. In this study, the effect of variables such as the contact time, size
of the adsorbent, initial solute concentration, pH, and dose of adsorbent
on the fluoride adsorption by the fishbone charcoal in a batch system is
investigated. Related relationships between variables evolved. The amount
of fluoride adsorbed per g of adsorbent increased with increase in initial
fluoride concentration for a given particle size. Fluoride removal was
found to be a function of pH and time. An empirical relationship is
obtained to predict the fraction of fluoride remaining in solution at any
time and pH. Another empirical relationship has been attempted to es
timate the percentage of fluoride removal at any time for known values
of the adsorbent dose and the initial solute concentration under the
observed simulated field test conditions. The equilibrium fluoride con
centration decreased with increasing adsorbent doses at any given initial
solute concentration. Further, the observed equilibrium concentration
and the fluoride adsorption capacity (expressed as the amount of fluoride
adsorbed per unit weight of fishbone charcoal) poorly correlated in
Langmuir and Freundlich isotherms. A linear relationship between these
parameters has evolved. Res. J. Water Pollut. Control Fed., 63, 848
(1991).
KEYWORDS: activated carbon, adsorption, fluoride, isotherms,
modeling, pH.
Fluoride in drinking water can cause beneficial or detrimental
effects, depending on its concentration and total amount ingested
(Sorg, 1978). Beneficial effects of fluoride include its capability
to prevent dental caries at an optimum concentration of ap
proximately 1.0 mg/L in the water. An excessive fluoride con
centration in water, however, causes dental or skeletal fluorosis
(Sorg, 1978). Water defluoridation methods include adsorption,
ion exchange, and precipitation. Processed animal bones and
bone charcoal were among the early defluoridating materials as
the bone was known for its affinity for fluoride (Maier, 1947).
Fish bones can be considered as yet another material for the
preparation of bone charcoal. Presently, adequate data are not
available with respect to fluoride removal and the use of fishbone
charcoal.
In batch adsorption systems, some significant factors that effect
the adsorption process include the adsorbent dose, solute con
centration, contact time, and pH. Scientific evaluation of de
fluoridation media or related processes should be based on lab
oratory studies using the samples of the actual water to be treated
(Harmon and Kalichman, 1965). To simulate field conditions,
test fluoride solutions were, therefore, prepared in tap water to
investigate the feasibility of fishbone charcoal and develop em
pirical relationships between significant process parameters.
Literature Review
Fluoride removal from aqueous solutions by various defluori
dation methods can be achieved through processes such as ad
sorption, ion exchange, or precipitation. Little research has been
done on the subject of fluoride removal and little effort has been
made to develop theoretical design models based on theories
and principles of removal mechanisms involved (Benefield et
al, 1982). Consequently, the design of fluoride removal pro
cesses is, in many cases, largely empirical and based on past
experience (Benefield et al, 1982).
Different materials used for defluoridation methods include
activated carbon, bone charcoal, tricalcium phosphate, synthetic
ion exchangers, activated alumina, alum, and lime. The main
works on fluoride removal from water by different researchers
include Choi and Chen (1979), Maier ( 1971 ), Boruff ( 1934),
Wu and Nitya (1979), Hao and Huang (1986), Savinelli and
Black ( 1958 ), and Culp and Stoltenberg ( 1958 ). A comprehen
sive review on the subject has been presented elsewhere (Sorg,
1978; Maier, 1947; and Killedar and Bhargava, 1988a and b).
Bone charcoal is ground animal bones that are carbonized at
high temperatures ( 1000-1600?C) to remove all of the organics.
Bone charcoal is composed of calcium phosphate (78% ), calcium
carbonate (9%), carbon (11%), iron and aluminum (0.5%),
magnesium (0.2%), nitrogen (1%), and residue insoluble in acid
(0.3%). Bone charcoal consists of a skeleton of calcium phos
phates and carbonates, cellular in structure with a great number
of minute tubes and channels. The skeleton is lined or coated
with carbon in a state of fine subdivision and high activity. The
adsorptive power of bone charcoal resides in its activated carbon
content because when the carbon is burned off, the calcium
phosphate skeleton has little or no decolorizing power, although
it will adsorb dissolved salts (Mantell, 1968 ). Properties of bone
charcoal are dependent on the kind of bones used and the way
they are stored before processing (Mantell, 1968).
Smith and Smith (1937) have suggested that the removal
mechanism of fluoride by bone charcoal is a ligand/ion-exchange
phenomenon in which the carbonate complex radical of the
apatite-comprising bone, Ca(P04)6*CaC03 is replaced by flu
oride to form an insoluble fluorapatite as shown in equation
( 1 ). In regeneration of material with sodium hydroxide, hydro
apatite probably becomes a hydroxy apatite and the fluorides
are removed in the form of soluble sodium fluoride. Hydroxy
apatite subsequently becomes available as an ion-exchange ma
terial by the replacement of its hydroxy radical with fluoride.
Ca(P04)6 CaC03 + 2F" -* Ca(P04)6 CaF2 + C03" ( 1 )
Detailed study of this exchange mechanism (Smith and Smith,
1937) has not been widely reported. Complex surface formations
on minerals have been studied by Choi and Chen ( 1979) and
Hao and Huang (1986). Choi and Chen (1979) suggested that
the aquo and hydroxy groups on the surface of adsorbents may
be responsible for the adsorption of fluoride through an ion

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through an ion-exchange process. Hao and Huang ( 1986) pre
sented a surface complex formation model to describe the re
moval of fluoride by activated alumina and proposed that the
reaction between fluoride and activated alumina can be described
by the formation of surface complex A1F or A1F2, depending on
the surface loading (that is, the mass rate of fluoride to activated
alumina dose).
Bone charcoal was used as a defluoridating agent at the Britton,
South Dakota, plant, which operated from 1948 until the city
switched to a new source of supply in 1971. Fluoride removal
was reported to be pH dependent, and it was found that lowering
the pH of the raw water would increase cycle lengths by a factor
of more than two. Bone charcoal, however, is acid soluble, so
an operating pH of 7.1 was selected to provide reasonably good
fluoride removal while minimizing media loss. The system pro
duced a treated water with an average fluoride content of 1.5
mg/L from a raw water source having a fluoride concentration
of 6.7 mg/L (Maier, 1971). Bone charcoal has been successfully
used in many full-scale installations for defluoridation of drinking
water in Southern California (Harmon and Kalichman, 1965).
Bone charcoal prepared out of animal bones has been used
as the defluoridating material in fixed bed column systems re
ported above. The use of fishbone charcoal and the results of
feasibility studies either in batch or column systems have not
been widely reported.
Experimental Methodology
Fishbone charcoal was indigenously prepared by carbonizing
cleaned and pulverized fish bones in an electric furnace in a
closed retort at 1000?C for 2 hours. Cooled material was sieved
to obtain six sample sizes having geometrical mean diameters
(d) of 0.714 mm (600-850 pm), 0.461 mm (355-600 /mi),
0.253 mm ( 180-355 pm), 0.150 mm ( 125-180 pm), 0.106 mm
(90-125 pm), and 0.549 mm (355-850 pm). This material was
thoroughly washed with distilled water, oven dried at 103?C,
and dessicated and stored in air-tight containers. The specific sur
face area (Method, 1986) of the 0.549-mm material was deter
mined to be 85 m2/g. The bulk density was determined to be
1.8g/cc.
A stock solution of 100 mg/L of fluoride was prepared in
distilled water as per "Standard Methods" (1985). Standard flu
oride solutions of 5 mg/L, 10 mg/L, 20 mg/L, and 50 mg/L
were obtained by dilution of the stock solution with distilled
water. These standard solutions were used in batch experiments
to study the effects of particle size, initial solute concentration,
and pH. Batch adsorption runs aimed at studying the effects of
pH, initial solute concentration, and dose of adsorbent under
simulated field conditions. Test fluoride solutions having differ
ent fluoride concentrations of 3.0 mg/L, 6.5 mg/L, 10.0 mg/
L, 20.0 mg/L, and 30.0 mg/L were also prepared by adding
appropriate quantities of sodium fluoride in the tap water. The
tap water used had a pH of 7.9-8.1; 170 mg/L total dissolved
solids; 112 mg/L CaC03 (indicating hardness); 44 mg/L cal
cium (as Ca++); 10 mg/L chloride (as Cl~); 1.6 mg/L sulphate
(as S04"~); 75 mg/L CaC03 (indicating alkalinity); and less
than 0.10 mg/L fluoride (as F~). The interference of competing
ions and presence of calcium in the tap water is determined to
be negligible on the basis of a trial test run conducted to evaluate
the fluoride removal through adsorption on the fishbone char
coal. Noninterference is further supported because no CaF2 pre
September/October 1991 849
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_Bhargava and Killedar
cipitates were visually observed in test solutions when prepared
in tap water.
Batch adsorption studies were performed through jar tests at
room temperature, 20 ? 2?C. Several sets of jar test data were
obtained to study the effects of several variables such as the size
of adsorbent, initial solute concentration, pH, dose of adsorbent,
and initial solute concentration. In each set, five jars containing
the fluoride solution of required concentration were stirred at
approximately 100 rpm. Samples were collected at predeter
mined times from each jar of the respective sets and were filtered.
The residual fluoride concentration in each sample was deter
mined through Model 901 Orion Ion Analyser using the specific
ion electrode.
The details of the test sets along with their respective test
condition are summarized in Table 1.
Discussion
Batch adsorption data are analyzed to determine the effects
of the contact time, particle size, initial solute concentration
(C0), pH, and adsorbent dose ( Ws) on fluoride removal through
its adsorption on fishbone charcoal.
Effect of contact time and adsorbent particle size. The effect
of contact time on fluoride removal of five adsorbent sizes?
sizes I, II, III, IV, and V having geometrical mean diameters (d)
of 0.714, 0.461,0.253,0.150, and 0.016 mm, respectively?was
investigated for an initial fluoride concentration of 10 mg/L.
Residual fluoride concentrations determined at the various con
tact times for the stated adsorbent sizes are tabulated in Table
2. Percentages of fluoride removal at different times were worked
out using data presented in Table 2 and a plot was prepared
between the percentage of fluoride removed versus the contact
time for different adsorbent sizes as shown in Figure 1. From
Figure 1, it can be observed that the percentage removal of flu
Table 1 ?Details of jar tests for batch adsorption studies.
No. Variable studied and its range Test conditions
Set I Size of adsorbent C0 = 10 mg/L,
(size I to size V) Ws = 4 g/L, and
pH = 7.00
(distilled water base).
Set II Initial solute concentration (C0) Ws = 6 g/L,
(5, 20, 50, and 100 mg/L) size = size IV, and
pH = 7.00
(distilled water base).
Set III pH Co=10mg/L,
(2, 4, 6, 8, and 10) Ws = 8
size = size VI
(distilled water base).
Set IV pH C0 =11 mg/L,
(2, 4, 6, 8, and 10) Ws = 8 g
size = size VI
(tap water base).
Set V to Initial solute concentration and Si
Set IX adsorbent dose pH = 8.00
C0 = 3.0, 6.5, 10.0, 20.0, and (tap water base).
30.0 mg/L
Ws = 2,4,8, 16, and 32 g/L
Bhargava and Killedar_

Table 2?Effect of contact time and particle size on in 480 minutes, total percentages of removal are 21
fluoride removal: initial fluoride concentration = 10 mg/L 30.00, 35.20, and 56.30% for sizes I, II, III, IV, and
(DW base) and adsorbent dose = 4 g/L. tively. These figures suggest that the fluoride adsorpt
charcoal is a function of size of the adsorbent.
Residual fluoride concentration, mg/L To explore the dependency of the adsorption rate
size, the plots were prepared between the residual flu
Size I Size II Size III Size IV SizeV
centration versus contact time for the different adso
Time, (0.714 (0.461 (0.253 (0.150 (0.106
min mm) mm) mm) mm) as shown in Figure 2. It can be observed from Figure
mm)
rate of change in fluoride concentration is proporti
10.00 9.60 9.51 9.28 9.08 8.54 fluoride concentration remaining (residual concen
30.00 9.00 8.82 8.63 8.48 7.66 solution, which can be mathematically expressed ac
60.00 8.90 8.52 8.48 7.90 7.12 the following first-order equation:
120.00 8.72 8.22 8.16 7.88 6.22
180.00 8.65 8.08 7.54 7.43 5.84 dC
360.00 7.90 7.26 dt ?(C) (2)
7.44 7.23 4.77
480.00 7.88 7.22 7.00 6.48 4.35
or
540.00 7.86 7.20 6.98 6.46 4.34
dC
dt = KFi(C) (3)
oride is increasing with time and attained almost an equilibrium
condition (at which the rate of adsorption of solute is equal to
Where
the rate of desorption) in approximately 480 minutes for all dC _ rate of change in fluoride concentration in solution,
adsorbent sizes. A decreasing removal rate, particularly toward ~d7 ~ mg/L;
the end, indicates a possible monolayer of fluoride ions on the
KFl = rate constant, min-1;
outer interface of the fishbone charcoal, and pore (interparticle)
diffusion onto the inner surface of the adsorbent particles through
C = fluoride concentration in solution, mg/L; and
t = contact time, min.
the film due to continuous agitation maintained during the ex
periments. It is also seen from Figure 1 that the rate of increase Minus signs in equations (2) and (3) indicate that the rate of
of fluoride removal is as much as 180 minutes, though the rate reaction decreases as the fluoride concentration remaining in
significantly decreases beyond 180 minutes until the equilibrium solution decreases. Rearranging equation (3), we get
stage is attained. It is apparent that it is not worthwhile to con
dC
tinue adsorption beyond 180 minutes. (4)
These variations in the rate of removal may be occurring due
to the fact that, initially, all of the adsorption sites are vacant,
Integrating equation (4), with boundary conditions of C = C0
the solute concentration gradient is high; and due to an affinity
at t = 0 and C = C, at / = /:
of the adsorbent for the solute, the rate of fluoride uptake is high
for a contact time ranging from 0.0 to 180 minutes. Afterwards, \n(C,) = -KFrt + ln(C0) (5)
due to a decrease in adsorption sites, the fluoride uptake rate
or
on the adsorbent decreases significantly, resulting in less removal
of the solute. The overall percentage of fluoride removal at up log(C,) = -KF-t + log (C0) (6)
to 480 minutes seems to be increasing from the coarser to the
finer size of the adsorbent as depicted in Figure 1. For example,

Initial fluoride concentrai ion , Co=10-0mg/L

Dose of adsorbent ,WS = 4Q/L
pH=7.0
Size l (d =0.714 mm) Distilled water base
Size II (d =0-461 mm) (D.W. base)
80 Size III (d = 0-253 mm)
Sire IV (d =0-150 mm)
Size V (d = 0-106 mm)

Size V ( d = 0.106mm)
20

60 240 300 3 60 420 480 540 180 240 300 360 420 480 540
Time I m in Time ; min

Figure
Figure 1?Variation of fluoride removal versus time2?Variation
for of residual fluoride conce
different adsorbent sizes. versus time for different adsorbent sizes.

850 Research Journal WPCF, Volume 63, Num

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 _Bhargava and Killedar

Where
60 _ Size of adsorbent = Size IV (d =0.150 mm)
Ct = residual fluoride concentration at any time t, mg/L, Dose of adsorbent,Ws = 6g/L , pH = 7-0 (D.W. base)
and _ Co =5.0mg/L
50
KF = rate constant, min-1.

Through the regression of data shown in Figure 2, rate constants

40
were determined as 1.445 X 10~4 mir
Co=20.0mg/L
2.068 X 10"4 min"1, 2.369 X and 5.229 X 10"
min-1 for sizes I, II, III, IV, and V, respectively. From the above 30
values it can be concluded that rate constants are increasing
with decreasing adsorbent size. To obtain the correlation between Co=50.0mg/Lr
20
rate constant and size, a plot was prepared as shown in Figure Co=100.0mg/L
*_- ?- -
3. The plot shown in Figure 3 follows a relationship of the type
shown in equation ( 7 ), manifesting a coefficient of correlation 10
of 0.932.

log KF = 0.058 3.90 (7) 60 120 180 240 300 360 420 4?0
(-:) Time : m i n

In equation (7), KF represents the rate constant in min-1 and
d is the geometrical mean diameter of the adsorbent in mm.
Equation (7) can be used to compute the rate constant for a
given particle size of the adsorbent under observed test condi
tions. It can also be inferred from Figure 3 that the rate of ad
sorption varies inversely to some power of the particle size man
ifesting (Weber, 1972) intraparticle transport.
Effect of contact time and initial solute concentration. The
effect of contact time for the varying initial fluoride concentra
tions of 5.0, 20, 50, and 100 mg/L was also determined for
adsorbent size IV (d = 0.150 mm) with an adsorbent dose of
6.0 g/L. Plots between the percentage of fluoride removed and
contact time for the various initial fluoride concentrations are
shown in Figure 4. It is seen from the plots of Figure 4 that the
percentage of fluoride removal is increasing with time and almost
reaches equilibrium conditions in approximately 180 minutes
of contact. These curves also show that the equilibrium time is
7 xio
C0 =10.0 mg/L
6 x 10 Ws = 4g/L
pH= 7.0 (D.W. Base)
5 *10
4 x 10
c ~4
5 3 xlO
-4
Z XlO
o L of the test solutions prepared in distilled water (D
CL
i * i?4|
0 0.1 0.2 0-3 0.4 0.5 0.6 0-7
Figure 4?Percent fluoride removal versus con
for different initial fluoride concentrations.
independent of the initial fluoride concentration, p
cause the adsorption sites of the adsorbent (a consta
for the various initial fluoride concentrations) were
in almost the same time.
The overall percentage removal of fluoride at 180
for different initial fluoride concentrations of 5, 20,
mg/L are 50.2, 34.35, 18.5, and 15.2, respectively. T
of fluoride adsorbed was determined as 0.41, 1.14,
2.53 mg/g, respectively, for the above said initial fl
centrations. From these figures, it is apparent that f
size and dose of the adsorbent, the overall percentage
at equilibrium time decreases with increase in initi
concentration. This is probably due to the fact that f
adsorbent dose, the total available adsorption sites ar
thereby adsorbing almost the same amount of fluoride a
manifesting a decrease in the percentage of removal
oride corresponding to an increased initial fluoride
tion. The actual amount of solute adsorbed per gr
adsorbent, however, increased with increasing initial
centration due to a greater driving force, resulting in
sorption (and at a higher time rate) at higher solute
tions. Thus, for a given adsorption site (or adsorben
solute removal of the solute would increase with in
concentration, but the solute removal (expressed as a
of the initial concentration and not the absolute val
decrease with increasing initial concentrations.
Effect of contact time and pH. The effect of contac
fluoride removal at different pH values of 2, 4, 6, 8,
investigated for initial fluoride concentrations of 10 a
water (TW), respectively. The adsorbent dose in eac
kept constant at 8 g/L. The pH value was adjusted
dilute hydrochloric acid (HC1) or sodium hydroxid
to the test solution.

Geometric mean diameter , dThe variation of the fraction of fluoride remaining

I mm
(C) (the ratio of Ct, the residual concentration at an
Figure 3?Variation of rate constant to
versus
C0, the geometrical
initial fluoride concentration) at different
mean diameter. pH values (for the distilled and tap water base solution

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Bhargava and Killedar_

in Figure 5. It is seen from Figure 5 that the residual fluoride
concentration is dependent on both the pH and the contact time.
It is also observed from Figure 5 that the values at a given pH
and time for the fluoride solutions of distilled water base and
tap water base are nearly equal, which implies, as before, that
no significant interference is caused when the fluoride solutions
were prepared with the stated tap water base.
The C value decreases with contact time at any pH value and
increases with pH at any time. Each plot in Figure 5 is seen to
follow a first-order reaction represented by equation (8).
ln(C) = -kt (8)
In equation (8), k is the rate constant (h_1). The values of the
rate constant k at different pH values were obtained through a

1.0

X-x Distilled water base , Co=10.0mg/L

0.9h
o-o Tap water base > Co=110mg/L
Dose of adsorbent, Ws = 8 g/L

--??pH = 10

=?pH = 2
0 _L _L
12 3 4 5 6 10
Time : hr
Figure 5?Variation of C with time at various pH values.

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regression of data shown in Figure 5. The variation of the eval
uated values of the rate constant k with pH (for distilled water
and tap water base fluoride solutions) is shown in Figure 6. It
is seen from Figure 6 that the k value decreased with increasing
pH values such that at a pH of 2 and 10 (for distilled water
base), the k values are 235 XlO-3 and 32 X 10"3/h, respectively.
It implies that the rate of fluoride removal shall be faster at lower
pH values and slower at the normally encountered pH values
of 7.5 to 8.5 of potable waters. This is probably due to a neu
tralization of the negative charge at the activated fishbone carbon
surface by the greater hydrogen ion concentration at lower pH
values, thus reducing hindrance to diffusion of the negatively
charged fluoride ions onto the increased active surface of the
fishbone charcoal (Weber, 1972). Maier (1971) also observed
that the fluoride removal by bone charcoal was dependent on
pH such that the removal efficiency was greater at lower pH
values of raw water. Faust and Aly ( 1987) observed that the
uptake rate of 3-dodecyclbenzene sulphonate on a 0.126-mm
Columbia LC carbon was faster at low pH ( 1.91 and 4.04 ) than
at higher pH (6.02, 7.79, and 8.73) (Faust and Aly, 1987).
The plot of rate constant k versus pH (Figure 6) yields a
relationship shown in equation (9).
k = ax + b\ J_
pH
In equation (9), ax and bx are coefficients. The values of a\ and
b\ were determined through the regression analysis of data in
Figure 6 and were found to be 0.015 and 0.462 (for distilled
water base) and 0.006 and 0.44 (for tap water base), respectively,
with a coefficient of correlation of 0.962 and 0.967. These coef
ficients, fli and b\, are representative of given observed test con
ditions (that is, for Ws = 8 g/L and C0 = 10 mg/L [DW base],
or WsICo = 800 and C0 = 11 mg/L [TW base], or WJC0
= 727, respectively). This suggests that the rate constant is not
only a function of pH but at a given pH it shall also vary with
the Ws\C0 ratio value.
The substitution of equation (9) in equation (8) yields equa
tions (10a) and (10b) for DW and TW bases, respectively.
ln(C) = - 0.015 + 0.462
pH
(?)
ln(C) = - 0.006 + 0.440
Equations (10a) and (10b) enable the prediction of C value at
any time t in the pH range of 2 to 10 under the observed test
conditions.
0.3
Ws = 8.0 g/L
-Co=10 mg/L (D.W. base) Size VI
-c 0-2
ft?
a
:0 = 11 mg/L ( T. W. base)
^* 0-1 -
Figure 6?Variation of the rate constant with pH.
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Bhargava and Killedar
The test runs for evaluating the effect of other variables were
carried out in the pH range of 7 to 8, which is the commonly
encountered pH of most waters. However, to attain a better
efficiency, the pH of wastewaters can be lowered for desired
effects.
Effect of adsorbent dose and initial solute concentration on
fluoride removal. Batch adsorption studies were conducted to
determine the effects of adsorbent dose ( Ws) and the initial solute
concentration on the fluoride removal (at different contact times)
and also on the equilibrium fluoride concentration.
For each value of C0 (3.0, 6.5, 10.0, 20.0, and 30.0 mg/L),
the remaining fluoride concentrations were determined at
different times by varying the Ws values to 2, 4, 8, 16, and
32g/L.
The plots of percentage of fluoride removal versus time for
the above-stated C0 and Ws values are shown in Figures 7 to 11.
Curves in Figures 7 to 11 show an increasing trend of fluoride
removal (%) with time. Further, it can be observed that at any
time t for a given C0 value the percentage fluoride removal in
creased with increase in the Ws value. This is obvious because
at the higher dose of adsorbent due to the increased surface area,
more adsorption sites are available, causing higher fluoride re
moval.
(9)
It can also be seen from Figures 7 to 11 that at any time t for
a given Ws value, the percentage of fluoride removed decreased
with an increase in C0. This is probably due to the fact that for
a fixed adsorbent dose, the total available adsorption sites are
limited, thereby adsorbing almost the same amount of fluoride
and manifesting a decrease in percentage removal of the fluoride
corresponding to an increased initial fluoride concentration.
Each plot shown in Figures 7 to 11 follows a relationship of
the type:
^ = a + b-t (11)
In equation ( 11 ), R represents the percentage fluoride removed
at time, t, and a and b are coefficients. Through a regression
analysis of the data shown in Figures 7 to 11, values of a and b
were determined and are tabulated in Table 3 with their coef
ficients of correlation ( r).
Trial plots between the values of a versus C0 did not show
(10a)
any correlation for any Ws value. Hence, average values of a
were plotted against Ws and the plot shown in Figure 12 seems
to follow the relationship of the type shown in equation (12).
(10b)
a = ^k (12)
In equation ( 12), c and d' are coefficients. Their values are de
termined as 0.231 and 0.330, respectively, manifesting a coef
ficient of correlation of 0.999 through the regression of data
shown in Figure 12.
From Table 3, it can be seen that values of b are increasing
with C0 for all values of Ws. Values of b were plotted against C0
for a possible correlation for all values of Ws. A sample plot
relating b and C0 is shown in Figure 13 and this plot was made
for Ws = 8 g/L. The plot presented in Figure 13 follows the
relationship of the type,
b = ^TF (13)
Bhargava and Killedar__^_^___

C0 = 3.0 mg/L C0 =10-0mg/L

pH= 80 (T.W. base)
Size VI Ws = 32g/L ^Ws = 16g/L |_ pH = 80 (T.W. base)
Size VI
-^ /.. A Ws= 32g/L^

Figure 9?Variation of fluoride removal versus time at

Figure 7?Variation of fluoride removal versus time at various Ws values for C0 = 10.0 mg/L.
various IV, values for C0 = 3.0 mg/L.

In equation (13), e and / are coefficients. Values of e and /

R \ 0.231 +0.33 Ws )
were determined through the regression of data given in Table

0
3 and are presented with their coefficients of correlation in Table w,
4. Table 4 shows that e and / vary with Ws. Therefore, coeffi
cients e and / were correlated with Ws, yielding the relationships
/[fe44 X l(T3 + 6.785 X l(T3^
H.
W,
fe
shown in equations (4) and (5).
016 7 + 0.014IF,
\t (16)
Ws
e = (14)
g+hWs In equation ( 16), R is the fluoride removal (%), ? is the time
(min), C0 is the initial fluoride concentration (mg/L), and Ws
and
is the adsorbent dose (g/L).
Ws The empirical relationship shown in equation (16) can be
f= i+JWs (15) exploited to predict the percentage fluoride removal at any time
t for chosen values of Ws and C0 for observed test conditions.
In equations (14) and ( 15) g, h, i, and./' are coefficients. Their The robustness of the relationship presented in equation (16)
values are 5.455 X 10"3, 6.785 X 10-3, 0.016 7, and 0.014, is indicated by the high coefficients of correlations, which vary
respectively, with coefficients of correlation of 0.998 and 0.991 from 0.970 to 0.991 when tested for the five cases having different
through the regression of data presented in Table 2. C0 and Ws values (for example, the combinations C0 = 3.0 and
Substitution of equations (12),(13),(14), and ( 15 ) in equa Ws =S,Co = 6.5 and Ws = 32, C0 = 10.0 and Ws = 8, C0 = 20.0
tion (11) yields the relationship given in equation ( 16) to de and Ws = 16, and C0 = 30.0 and Ws = 32).
termine the percent removal of fluoride (R) at any time t for Effect of adsorbent dose and initial solute concentration on
given values of Ws and C0. the equilibrium fluoride concentration. To investigate the effects
of adsorbent dose and initial solute concentration on the equi
librium fluoride concentration {Ce\ a critical examination of
the various curves shown in Figures 7 to 11 indicate that for
C0 = 6.5 mg/L
pH = 8-0 (T.W. base)
Size VI
W5 = 32g/L
Ws = 16g/L

Ws = 8 g/L

Ws =2 g/L

0 60 120 180 2 40 300 360 420 480 540

Time : m in

Figure 8?Variation of fluoride removal versus time at Figure 10?Variation of fluoride removal versus time at
various IV, values for C0 = 6.5 mg/L. various W8 for C0 = 20.0 mg/L.

854 Research Journal WPCF, Volume 63, Number 6

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 Bhargava and Killedar

100
C0 = 30-0 mg/L
pH = 8-0 (T.W. base)
80 Size VI
Ws=32g/L
- -#^?_?.
^WsH6g?L_
Ws= 8 g/L
-*?--*?

Ws = 49/L
-a-o

- Ws = 2g/L
- ?

J -L
240 300 360 420 480 540
Time : m i n
Figure 11?Variation of fluoride removal versus time at various W, values for C0 = 30.0 mg/L.

each adsorbent dose and given initial concentration, fluoride
removal increases with time and reaches an almost equilibrium
condition in approximately 480 minutes. The rate of increase
of fluoride removal is greatest at up to 240 minutes. At longer
times, this rate decreases and appears to approach equilibrium.
Table 3?Values of coefficients a and b with respective
coefficients of correlation (r) for different values
of IV, and C0.
From a practical and economical point of view, an equilibrium
time of 240 minutes was selected to represent equilibrium con
ditions, and the corresponding equilibrium concentration values
(at the selected equilibrium time of 240 minutes) are obtained
from Figures 7 to 11 and are tabulated in Table 5. It is pointed
out that an error of approximately 1-10% for C0 = 3.0 to 30.0
mg/L may occur by choosing a contact time of approximately
240 minutes instead of the more accurate equilibrium time of
approximately 480 minutes.

Values of a, b, and r 1.4 n-1-1-r

Initial F" Doses of adsorbent (IV,), g/L pH = 8.0 (T.W.

concentration 1.21
Si^e vi
(C0), mg/L 2 4 8 16 32
3.0 a = 1.022 1 0.184 2 0.199 9 0.091 6 0.031 9 i.oh
b = 0.015 9 0.0116 0.010 7 0.010 3 0.010 3
r = 0.991 7 0.999 9 0.999 7 0.999 8 0.999 9 0.8
6.5 a = 0.846 4 0.634 1 0.353 3 0.134 6 0.066 8
6 = 0.036 5 0.0210 0.013 9 0.0115 0.010 7 > C6h
r = 0.999 4 0.998 2 0.999 6 0.999 9 0.999 9
10.0 a= 1.0121 0.9593 0.374 4 0.2149 0.1069 0-4h
b = 0.041 5 0.022 6 0.015 6 0.012 9 0.011 5
r = 0.999 2 0.997 9 0.999 5 0.999 6 0.999 9
0-2
20.0 a = 1.290 1 1.090 6 0.395 9 0.214 2 0.083 9
b = 0.045 2 0.025 7 0.016 4 0.013 7 0.012 1
r = 0.998 7 0.995 2 0.999 3 0.999 8 1.000 0 0 4 8 12 16 20 24 28 32
30.0 a = 0.964 2 0.790 5 0.370 7 0.239 9 0.174 7 Dose of adsorbent , Ws *.
b = 0.049 4 0.033 6 0.018 6 0.014 8 0.013 8
r = 0.999 1 0.999 0 0.999 9 0.999 7 0.999 8 Figure 12?Variation of avera
versus dose of adsorbent.

September/October 1991 855

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Bhargava and Killedar_

24X103 ?i-1-1 Table 5?Equilibrium fluoride concentrations for the

Ws = 8.0 different adsorbent doses at selected equilibrium time of
g/L
pH = 8.0 240 minutes.
(T. W. base)
20
Size VI
Initial fluoride Adsorbent dose ( W,), g/L
concentration
(C0), mg/L 2.0 4.0 8.0 16.0 32.0

Equilibrium fluoride concentrations (Ce), mg/L

3.0 1.63 0.58 0.41 0.23 0.13

6.5 4.90 3.77 2.25 1.12 0.57
10.0 7.78 6.22 4.01 2.66 1.61
20.0 16.00 13.17 8.74 6.14 3.86
30.0 24.36 21.62 14.82 11.13 9.13

0 4 8 12 16 20 24 28 32
In equation (18), A x and Bx are coefficients and their values
Initial fluoride concentration
were determined ,to be C0:
0.2316mg/ Lrespectively,
and -1.877 5,
through the regression
Figure 13?Variation of coefficient b versus of C0 and dx.initial
This relationshipfluoride
has a
concentration. coefficient of correlation of 0.995. Substitution of equation (18)
in equation (17) yields an empirical equation shown in equa
tion (19):
It is apparent from data in Table 5 that equilibrium concen
trations decrease with increasing adsorbent doses for any C0
? = fixed
value. This is obvious because for a -?- + [exp(0.213 6 - 1.877
initial log C0)]WS
solute (19)
concen
tration, increasing adsorbent doses provide greater surface area,
In equation (19), Ce hence
resulting in higher fluoride removals, and C0 are, respectively,
decreasing the equilibrium equilib
and initial fluoride
rium fluoride concentrations. It was also observed that concentrations in mg/L, and Ws is the the
dose equi
librium fluoride concentrationof adsorbent
is a function in g/L. Equation ( 19) canof be used
a, tothe
predict the
ratio of
equilibriummg/L)
ads?rbate concentration (fluoride, fluoride concentration (Ce) for any given value ofconcen
to adsorbent
C0 (in theat
tration (activated alumina, mg/L) rangeaof given
3.0 to 30.0 mg/L)C0 and Ws
value(in the range
( Wu of and
2.0 to 32.0 g/L) forthat
Nitya, 1979). They similarly observed observed test
the conditions. High coefficients
equilibrium flu
oride concentrations decreasedof with
correlation (0.950 to 0.990 for C0 = 3.0 to
decreasing a30.0 mg/L) man
values. Using
ifest the strength for
data in Table 5, plots were prepared of presentedCe relationships.
against Similarly, such
Ws em with
pirical relationships can be
respect to various C0 values to see possible correlations. Figureobtained for the different adsorbate
14 contains one such plot for C0adsorbent=systems
3.0formg/L, other chosen experimental
which conditions.
indicates
A plot of Ce versus
a relationship shown in equation (17) (using the boundary C0:WS was also prepared from data in con
dition Ce = C0at Ws = 0). Table 5 and presented in Figure 16. The plot shows a wide scatter
around the line of best fit for the correlation between these two
1 1 parameters shown in equation (20).
(17)
3/ Co
In equation ( 17 ), d\ represents a coefficient. Through a regression C, = 2.19X 103 -7
yys
(20)
of the data presented in Table 5, the values of the coefficient d{
were determined for each of the C0 values and a plot of C0 versus
d{ is shown in Figure 15, which indicates the relationship shown 2.0,
in equation (18):
Co=3.0 mg/L
1.6
\ogdx = A, +BX log C0 (18) pH = 8-0 (T. W. base)
Size VI
'Z 1.2
Table 4?Values of coefficients e and f with respective
coefficients of correlation (r) for different values of W8.
c 0-8
o
Dose of Values of constants e, f, and r o

Si. adsorbent E
No. (W,),g/L e 3 0-41

2.00 97.11 16.86 0.988

4.00 133.34 50.84 0.996 8 12 16 20 24 28 32
8.00 144.38 50.36 0.997 Dose of adsorbent , W^: g
16.00 131.01 64.16 0.998
32.00 145.55 69.98 0.995 Figure 14?Variation of equilibrium concentration at dif
ferent adsorbent doses.

856 Research Journal WPCF, Volume 63, Number 6

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lOOxlO3
240 pH = 8.0 (T.W. base)
Size VI
80
12 16 20 24 28 32
mg/L
Initial fluoride concentration, C0
Figure 15?Variation of the coefficient d-, with initial flu
oride concentration.
Equation (20) manifests a coefficient of correlation of 0.881,
which is lower than correlation coefficients manifested by equa
tion (19). This shows that equation (19) represents a more ra
tional correlation between these parameters.
Relationship between qe and Ce. Data in Table 5 were analyzed
to find possible relationships between values of qe (amount of
fluoride adsorbed per unit weight of the fishbone charcoal, mg/
g) and Ce (equilibrium fluoride concentration, mg/L). Trial
linear plots of 1 ?qe versus 1 ?Ce and log qe versus log Ce did not
show any correlation, implying that observed data do not appear
to fit into the Langmuir or Freundlich isotherms. Therefore,
when a plot of qe versus Ce was prepared as shown in Figure 17,
it corresponded to a linear relationship shown in equation (21),
manifesting a coefficient of correlation as high as 0.963.
qe = 0.256 4 + 0.099 lCe
The intercept of equation (21) suggests that when Ce = 0, qe
= 0.256 4 =
c0 - O Co
, which theoretically implies that for
Ws Ws
a complete fluoride removal ( Ce = 0) the C0: Ws ratio may equal
pH =8-0 (T. W. base)
Size VI
4 6
Co/Ws
Figure 16?Variation of Ce with C0:W8.
September/October 1991 857
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Bhargava and Killedar
0.256 4. In actual practice, a Ce = 0 condition may not, however,
be achieved although aCe = near zero situation may occur at
stated or lower C0:WS ratios.
Practical Utility
The empirical relationships developed in this study can be
utilized to assess the fluoride removal efficiency of fishbone
charcoal with relation to various variables such as the initial
solute concentration, adsorbent dose, time, and pH for a given
set of test conditions. Such studies can be useful in the design
of low-cost water treatment systems for fluoride removal in small,
isolated communities.
Similar empirical equations can be obtained for different ad
sorbate-adsorbent systems for desired test conditions.
Conclusions
Fishbone charcoal has affinity for fluoride. Fluoride removal
for a given adsorbent size increased with time until it attained
an equilibrium condition in approximately 480 minutes. The
rate of increase of fluoride removal is approximately 180 minutes,
while the rate has significantly decreased beyond 180 minutes,
leading to a slower approach to equilibrium.
Rate constants increased with decreases in particle size of the
adsorbent and the relationship is established between them.
For a given dose and adsorbent size, the amount of fluoride
adsorbed per gram of adsorbent was found to increase with in
creasing initial fluoride concentrations.
Fluoride removal was found to be a function of both the pH
and time. Removal increased with time for all pH values, while
it decreased with increase in pH at a given time.
An empirical relationship is developed to predict the fraction
of fluoride remaining in solution at any time t in the pH range
of 2 to 10 for observed test conditions.
The percentage of fluoride removal was found to be a function
(21) of adsorbent dose and time at a given initial solute concentration.
It increased with time and adsorbent dose. The percentage of
fluoride removal at higher initial solute concentrations decreased
with time and adsorbent dose.
An empirical relationship has been obtained to predict the
percentage fluoride removal at any time for a given value of
adsorbent dose and at desired initial fluoride concentrations for
observed test conditions.
The equilibrium fluoride concentration was found to decrease
with increase in adsorbent dose at a given initial solute concen
pH = 8-0 (T.W. base)
Size VI
0-4
10 0|
Figure 17?Plot of qe versus Ce.
Bhargava and Killedar_
tration. An empirical relationship is evolved to predict the equi
librium fluoride concentration at any given value of initial solute
concentration and adsorbent dose under observed test condi
tions.
A linear relationship is obtained between the amount of flu
oride adsorbed per unit weight of adsorbent and the equilibrium
fluoride concentration.
Acknowledgments
Credits. The second author would like to thank the Govern
ment of India and the SGSITS in Indore, India, for deputing
him to the University of Roorkee, India, to do Ph.D. work under
the Quality Improvement Program.
Authors. Dr. Devendr? Swaroop Bhargava is a professor in
the environmental and civil engineering department of the Uni
versity of Roorkee, India. Shri Deepak Jayant Killedar, presently
a reader of civil engineering at the S.G.S. Institute of Technology
and Science in Indore, India, was a QIP research scholar in the
civil engineering department of the University of Roorkee in
India during this work and submitted his Ph.D. under the Quality
Improvement Program.
Submitted for publication August 6,1990; revised manuscript
submitted February 12, 1991; accepted for publication May 10,
1991. The deadline for discussions of this paper is January 15,
1992. Discussions should be submitted to the Executive Editor.
The authors will be invited to prepare a single Closure for all
discussions received before that date.
References
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water Treatment. Prentice-Hall, Inc., Englewood Cliffs, N. J.
Boruff, C. S. ( 1934) Removal of Fluorides from Drinking Waters. Ind.
Eng. Chem., 26, 69.
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All use subject to https://about.jstor.org/terms
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858 Research Journal WPCF, Volume 63, Number 6