Bonfring International Journal of Industrial Engineering and Management Science, Vol. 4, No.

2, May 2014 72



ISSN 2277-5056 | 2014 Bonfring

Abstract--- Excessive fluoride concentrations have been
reported in groundwaters of more than 20 developed and
developing countries including India where 19 states are
facing acute fluorosis problems. Various technologies are
being used to remove fluoride from water but still the problem
has not been rooted out. The present study was undertaken for
the determination of fluoride ions in drinking water in the
Agras urban as well as rural region. Batch tests on
groundwater samples from the different sites as St. Johns
College Chemistry Department, Trans Yamuna, Gokulpura
and Dareshi that contained 2.0, 2.5, 3.5 and 4.2 mg/l of
fluoride respectively were conducted using bagasse dust (BD),
bagasse flyash (BF), aluminium treated bagasse flyash (ABF),
buffalo bone powder (BP) and clam shell powder (SP). The
tests were also carried out with 1.9, 3.8, 4.75 and 9.50 mg/l
NaF solutions. The work aimed to evaluate the feasibility of
using these biomaterials for the removal of fluoride ions from
groundwater to make it fit for drinking or industrial use.
Defluoridation was in the order of SP > BP > ABF > BF >
BD over a wide range of initial concentration 1-10 mg/l at
sorbent dose range 1-20 g/l, pH 6.0, temperature 25C, rpm
150 for 5 h. The sorption increased with increasing contact
time and sorbent dose but the equilibrium was attained after 4
h for most of the sorbents. Groundwater samples showed 2 to
10% lower removal as compared to standard NaF solutions
under similar conditions. The clam shell was found to be the
best of all the fluoride removing agents studied here.
Keywords--- Defluoridation, Fluorosis, Groundwater, Low
Cost Adsorbent
I. INTRODUCTION
CESS fluoride, wherever present in groundwater in India, is
mainly in the concentration range of 1.5 to 6.5 mg/l
against itsits desirablelimit of 1 mg/l and
maximumpermissible limit of 1.5 mg/l in drinking water
[3][5][8][11-14]

Dr. N. Gupta, Assistant Prof., Dept. of Chemistry, R.B.S. Engineering &
Technical Campus, Bichpuri, Agra/UPTU, Agra, India. E-mail:
namrata_g28@ymail.com
Dr. V. Gupta, Res. Sch., Dept. of Chemistry, St. Johns College,
Agra/DBRA, Uni. Agra, India. E-mail: vijetaankitgupta@gmail.com
Dr. A.P. Singh, Prof& Director, Dept. of Food Tech., R.B.S. Engineering
& Technical Campus, Bichpuri, Agra/UPTU, Agra, India
R. P. Singh, School of Chemical Sciences, St. Johns College, Agra, India

DOI: 10.9756/BIJIEMS.10299
Potable water should have 0.6 to 1 mg/l of fluoride for
substantial protection against tooth decay. If fluoride is totally
absent in drinking water, it causes dental caries. Continuous
high intake of fluoride results in mottled teeth, skeletal
fluorosis and sometimes severe osteosclerosis. Agra city and
nearby villages have been reported to have very high fluoride
in groundwater, for example upto 22 ppm in Akola Block,
18.3 in Bichpuri Block and 8.9 ppm in Shamsabad Block.
Fluoride enters into the body through a variety of sources
viz. water, air, food, medicines and cosmetics. Water and
food, mainly agricultural crops are contaminated with fluoride
as the earth crust in India is heavily loaded with fluoride
containing minerals such as fluorspar, fluorapatite, phosphatic
nodules, topaz etc. As a result of the rich mineral content,
fluoride leaches out and contaminates the water and earth/soil
in general and groundwater in particular.
Many investigations have been conducted using different
materials and methods for fluoride removal [1-2][6][9-
10]Mehrotra et al., [15], Singh et al., [16][17-19], Yang et al.,
[20]. The numerous methods for defluoridation can be
grouped in physical and chemical categories. Numerous
chemical methods based on the principle of precipitation,
adsorption, ion-exchange, electrochemical and membrane
process have been described for the fluoride removal. Most of
these methods are cost intensive and biological defluoridation
of drinking water cannot be a good alternative on health
grounds. Methods of addition of alum, lime and bleaching
powder followed by rapid mixing, flocculation and filtration,
called Nalagonda technique, has been adopted in several
Indian States. Polyaluminium chloride (PAC) is reported to be
a substitute for commercial alum because it produces less
sludge than alum. All available alums increase the sulphate or
chloride ion concentration except PAC [4]. The work,
therefore, aimed to evaluate the feasibility of using bagasse
dust (BD), bagasse flyash (BF), aluminium treated bagasse
flyash (ABF), buffalo bone powder (BP) and clam shell
powder (SP) for the removal of fluoride ions from
groundwater to make it fit for drinking or industrial use.
II. METHODOLOGY
BD and BF were obtained from Chhata Sugar Company
Limited, Chhata, Mathura. Buffalo bone was procured from
Khatikpara, Agra. Clam shell was collected from Miramar
Beach, Goa. Natural and easily available materials particularly
agro cum industrial wastes like BD and BF, and animal
residues such as buffalo bone or clam shell were thoroughly
Defluoridation of Groundwater using Low Cost
Adsorbent like Bagasse Dust, Aluminium Treated
Bagasse Flyash, Bone Powder and Shell Powder
N. Gupta, V. Gupta, A.P. Singh and R. P. Singh

X
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ISSN 2277-5056 | 2014 Bonfring

washed with distilled water, sun dried for 5 h, crushed and
sieved through a standard sieve to collect fine powders with
particles smaller than 100 mesh. To prepare ABF, BF was
kept in contact with 0.1 N NaOH for half an hour, washed
with distilled water, dried in the oven at 110C for 1 h, mixed
with 2% Al
2
(SO
4
)
3
solution to keep it submerged and allowed
to stand for 30 minutes. The white precipitate of Al(OH)
3
so
formed was dissolved by adding a minium of 1:1 HCl till a
clear solution was obtained (pH 3.5). The solution was left
overnight. The BF was then separated, washed until free Al
3+

and dried at 115C for 6 h. This was referred to here as ABF.
Groundwater samples were collected from tube wells at
130 different locations in Agra city between April 5 to 25,
2011. The collection was done in 1-litre precleaned plastic
bottles between 6 to 10 a.m. The fluoride concentration was
determined in the samples the same day within 4 hours
(Clesceri et al., [7]) using an Orion 720 A
+
pH/ISE Meter after
calibrating the ion selective electrode (ISE) for fluoride with
four NaF working standards of 0.01, 0.001, 0.0001 and
0.00001 M, i.e., 190, 19, 1.9 and 0.19 ppm fluoride
concentration respectively. These standards were prepared
from a stock solution of 0.1 M or 1900 mg/l fluoride
concentration by diluting it 10 times successively, i.e., by
adding 45 ml distilled deionized water (DDW) to 5 ml of the
stock or a standard of higher concentration. The stock solution
of 0.1 M or 1900 ppm fluoride concentration was prepared by
dissolving (42 0.1 50)/1000 = 0.21 g of AR grade
anhydrous NaF from CDH, India in 50 ml of DDW. To each
of the 4 standards 10% by volume of total ionic strength
adjusting buffer TISAB-3 supplied by Orion was added, i.e.,
0.5 ml TISAB-3 was added to 5 ml of a standard solution or
water sample whose fluoride concentration was to be
determined. The results of groundwater analysis for fluoride
are listed in Table 1. The samples were classified as A, B, C,
D and E with fluoride concentration ranges 0-1, 1-2, 2-3, 3-4
and >4 mg/l respectively. Four groundwater samples of C, D
and E types were taken for fluoride removal.
The removal was studied by transient batch tests. In a 100-
ml polypropylene bottle with screw cap, 0.5 g of sorbent was
added. The pH was adjusted using 0.1N HCl. The bottle was
shaken in an orbital shaker at 150 rpm for 5 h at room
temperature. A separate bottle was used for control with
untreated sorbent to demonstrate whether there was any
fluoride uptake by other sources such as the wall of the
centrifuge tube. The contents were centrifuged at 2000 rpm
for 10 min and the supernatant liquid was filtered using a 0.45
membrane filter. The filtrate was analysed for the F ions.
Experiments were triplicated and results averaged. Unless
otherwise stated all experiments were conducted at room
temperature.








Table 1: Concentration of fluoride in Agra Ground Water
Area No. of samples
Mean conc. of
F

(mg/l)
Standard
deviation
Type*
Ram Bagh 12 1.6 1.2 B
Trans Yamuna 7 2.6 1.2 C
Water Works 7 1.7 0.4 B
Balkeshwar 7 1.5 0.4 B
Kamla Nagar 5 2.0 0 B
Belanganj 4 0.9 0.1 A
Tajganj 9 2.9 0.1 C
Dareshi 6 4.2 0.2 E
Agra Fort 3 3.3 0 D
Shahjahan Park 2 4.1 0.1 E
PeepalMandi 4 2.5 0.1 C
Surya Nagar 2 2.1 0 B
New Agra 4 2.9 0.1 C
Dayalbagh 3 2.6 0.4 C
Transport Nagar 7 2.8 0.3 C
Nehru Nagar 3 2.2 0 B
Sanjay Place 4 1.8 0.2 B
B.M. Khan 8 2.3 0.2 C
Gokulpura 3 3.0 0 D
Nai Ki Mandi 5 3.5 0.3 D
Raja Ki Mandi 10 2.0 0 B
WazirPura 9 3.8 0.3 D
Shahganj 3 1.7 0.2 B
Khandari 3 1.9 0.2 B
*Type indicates type of groundwater samples with fluoride
concentration ranges A = 0-1, B =1-2, C = 2-3, D = 3-4 and
E = > 4 mg/l.
The removal was studied by transient batch tests. In a 100-
ml polypropylene bottle with screw cap, 0.5 g of sorbent was
added. The pH was adjusted using 0.1N HCl. The bottle was
shaken in an orbital shaker at 150 rpm for 5 h at room
temperature. A separate bottle was used for control with
untreated sorbent to demonstrate whether there was any
fluoride uptake by other sources such as the wall of the
centrifuge tube. The contents were centrifuged at 2000 rpm
for 10 min and the supernatant liquid was filtered using a 0.45
membrane filter. The filtrate was analysed for the F

ions.
Experiments were triplicated and results averaged. Unless
otherwise stated all experiments were conducted at room
temperature.
Batch tests on groundwater samples from St. Johns
College Chemistry Department, Trans Yamuna, Gokulpura
and Dareshi that contained 2.0, 2.5, 3.5 and 4.2 mg/l of
fluoride respectively, were conducted using BD, BF, ABF, BP
and SP at rpm 150, pH 6.0 and temperature 25C for 5 h. The
tests were also carried out with 1.9, 3.8, 4.75 and 9.50 mg/l
NaF solutions (Table 2). At the interval of 1 h, an aliquot of 5
ml mixed solution or control was filtered for fluoride analysis
(Table 3). To study the effects of the sorbent dose, the sorbent
was varied as 1, 5, 10 and 20 g sorbent/l of fluoride solution
(Table 4). To examine whether the filters used during the tests
Bonfring International Journal of Industrial Engineering and Management Science, Vol. 4, No. 2, May 2014 74



ISSN 2277-5056 | 2014 Bonfring

adsorbed or released fluoride, several filtered and unfiltered
samples were also compared.
Table 2: Effect of Initial Fluoride Concentration on %
Sorption by BD, BF, ABF, BP and SP at Sorbent Dose 10 g/l,
rpm 150, pH 6.0 and 25
o
C for 5 h

Table 3: Effect of Contact Time on % Fluoride Sorption by
BD, BF, ABF, BP and SP at Fluoride Concentration 4.2 ppm,
Adsorbent dose 10g/l, rpm 150, pH 6.0 and 25oC for 5 h

Table 4: Effect of Sorbent dose on the Removal of Fluoride
with BD, BF, ABF, BP and SP at Fluoride Concentration 4.2
ppm, rpm 150, pH 6.0 and 25
o
C for 5 h

III. EXPERIMENTAL RESULTS/ANALYSIS
Defluoridation was in the order of SP > BP > ABF > BF >
BD over a wide range of initial concentration 1-10 mg/l at
sorbent dose range 1-20 g/l, pH 6.0, temperature 25C, rpm
150 for 5 h. The sorption increased with increasing contact
time and sorbent dose, but the equilibrium was attained in 2 h
for BD, 2.5 h for BF and ABF, 3 h BP and 4 h for SP. The
higher uptake at lower initial concentration can be attributed to
the availability of more isolated fluorideions. Sorption rate is
very rapid during initial period of contact. Groundwater
samples showed 2 to 10% lower removal as compared to
standard NaF solutions under similar conditions.
Larger surface area of adsorbent and smaller size of
adsorbatefavour adsorption. The rate of adsorption is high in
the beginning as sites are available and unimolecular layer
increases.
Adsorption and desorption occur together and rates
become equal at a stage called adsorption equilibrium when
isotherms are applied. That is why there is little increase in %
removal on increasing adsorbent dose from 10 to 20 g/ml of
surfactant solution. The subsequent slow rise of sorption may
be due to adsorption and intra-particle diffusion taking place
simultaneously with dominance of adsorption. With rise in
sorbent dose there is less commensurate increase in adsorption
resulting from lower adsorptive capacity utilization of
adsorbent. This is called 'solid concentration effect' meaning
overcrowding of particles.
Agro cum industrial waste BD contains functional groups
associated with sucrose, lignin, cellulose and proteins as major
constituents, but BF has high carbon content. Many
researchers have found that anion adsorption on such materials
is due to the presence of aquo groups (MOH
2
) and
hydroxo groups (MOH), high surface area and charge on
their tiny particles. The surface chemistry of an oxide in
contact with an aqueous solution is determined to a large
extent by deprotonation or a hydroxyl ion association reaction
(Mehrotra et al., [15]). However, some evidences suggest that
an anion like F

can be adsorbed by ion exchange mechanism

even though the surface is neutral.
MOH + F

> MF + OH

There are several biological by-products in addition to BD
andBF that potentially could be modified with
physicochemical treatments. Grinding increases surface area.
CaSO
4
, Al
2
(SO
4
)
3
, Al
2
O
3
, SiO
2
, alum, lime, polyaluminium
chloride (PAC), silica gel, TiO
2
and CeO
2
may introduce
additional hydroxo groups on BD or BF to be exchanged with
F

. In the first case, base treatment with NaOH (high pH) may
de-esterify ester bound groups from the sorbent surface,
thereby exposing additional functional groups that can bind
F

ions. In the second case, acid treatment with HCl (low pH)
will free multivalent metal cation to capture and complex with
F

ions such as AlF

2+
sorbed on Al
2
O
3
to increase its positive
charge to sorbe F

ions.
Inorganic fluoride compounds have a specific chemical
function on animal bone and tooth causing diseases such as
osteosclerosis and mottled teeth. Approximately half of a bone
is composed of collagen and the remainder is composed of
85% calcium phosphate and 10% calcium carbonate. On the
other hand, a shell contains 90 to 99% calcium carbonate.
These biomaterials may be useful to remove fluoride ions.
Bone of livestock and shell of aquatics have been dealt as
industrial wastes and are available in large quantities. With the
aim of finding a new usage of such unused materials, the
effects of fine powders smaller than 100 mesh of buffalo bone
clam shell were studied. Shell was found to be more effective
than bone because of its very high CaCO
3
content. Both of
these biomaterials seem to remove fluoride ions mostly by
precipitation to form insolution CaF
2
. With bone powder,
fluoride concentration cannot be decreased to meet the
industrial effluent guideline because it works in a narrower pH
and range, gives lower removal and produces an undesired
phosphate ion (Tokunaga et al., 1996). Thus the clam shell
was the best of all the fluoride removing agents studied here.
IV. CONCLUSION AND FUTURE ENHANCEMENT
Defluoridation was in the order of SP > BP > ABF > BF >
BD over a wide range of initial concentration 1-10 mg/l at
sorbent dose range 1-20 g/l, pH 6.0, temperature 25C, rpm
150 for 5 h. The sorption increased with increasing contact
time and sorbent dose but the equilibrium was attained after 4
h for most of the sorbents. The higher uptake at lower initial
Bonfring International Journal of Industrial Engineering and Management Science, Vol. 4, No. 2, May 2014 75



ISSN 2277-5056 | 2014 Bonfring

concentration can be attributed to the availability of more
isolated fluorideions. Sorption rate is very rapid during initial
period of contact. Groundwater samples showed 2 to 10%
lower removal as compared to standard NaF solutions under
similar conditions. The clam shell was the best of all the
fluoride removing agents studied here. The defluoridation may
be enhanced further with help of surfactant remediated low
cost adsorbents.
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