RESEARCH COMMUNICATIONS
High fluoride in groundwater of
Palghat District, Kerala
E. Shaji*, Bindu, J. Viju and D. S. Thambi
Central Ground Water Board, Kedaram, Thiruvananthapuram 695 004,
India
High-fluoride groundwaters are present in the hard-
rock aquifers of Palghat District, Kerala especially in the
eastern part. The phreatic zone comprises weathered to
partly weathered crystallines, and the deeper aquifer is
formed by fractured crystallines. Both phreatic and
deeper aquifers have high fluoride (F– ). In dug wells,
F– concentration ranges from 0.2 to 5.75 ppm with the
highest being at Kopanur in Chittoor taluk. In the
deeper aquifers the highest concentration of 3.12 ppm
is observed at Chinnamoolathara. Other high fluoride
concentration areas are Eruthenpathy, Anakatti and
Vannamada in the district. The country rock, horn-
blende biotite gneiss, is identified as the source of this
high fluoride for both phreatic as well as deep aqui-
fers. Saturation indices with respect to CaF2 were cal-
culated; all the samples are saturated with respect to
fluorite. The water quality is analysed by the Piper
diagram and the common ion noticed is Na+. Alkaline
water depleted in calcium, longer residence time of
water in the aquifer zone, and intensive irrigation are
favourable factors for the dissolution of fluorine-
bearing minerals in groundwater. Dental fluorosis is
observed from the Chittoor taluk. Since groundwater
finds domestic use remedial measures including rain-
water harvesting are needed in the area.
Keywords: Dental fluorosis, fluoride, groundwater, hard-
rock aquifers.
FLUORIDE (F– ) concentration is an important aspect of
hydrogeochemistry, because of its impact on human
health. The recommended1 concentration of F– in drinking
water is 1.50 mg/l. Low F– content (< 0.60 mg/l) causes
dental caries, whereas high (>1.20 mg/l) fluoride levels re-
sult in fluorosis2 . Hence, it is essential to have a safe limit
of F– concentration of between 0.60 and 1.20 mg/l in
drinking water 2 . The Bureau of Indian Standards (BIS)3
prescribed a limit between 1.0 and 1.5 mg/l. In India,
about 62 million people are at risk of developing fluorosis
from drinking high F– water 4 . The problems are most
pronounced in Andhra Pradesh, Bihar, Gujarat, Madhya
Pradesh, Punjab, Rajasthan, Tamil Nadu and Uttar
Pradesh5. Groundwater samples were collected from Pal-
ghat District, Kerala, India. The samples were analysed
for fluoride along with other chemical parameters. High
fluoride concentration is observed from the eastern part
of Palghat District (E. Shaji, unpublished). This study has
*For correspondence. (e-mail: shajicgwb@yahoo.co.in)
240
been carried out as part of the regular Annual Action Plan
of Central Ground Water Board (CGWB), Kerala Region
during 2002–03.
Palghat (Palakkad) District is situated more or less in
the central part of Kerala. It is bounded in the north by
Malappuram District, in the east by Coimbatore District
(Tamil Nadu), in the south by Trichur District and in the
west by parts of Trichur and Malappuram districts. The
Palakkad District lies between 10°21′–11°14′N lat. and
76°02′ and 76°54′E long. The total geographical area of
the district is 4480 sq. km (Figure 1).
There are four types of soils in the district, namely lat-
erite soil, virgin forest soil, black cotton soil and alluvial
soil.
Laterite soil is seen in major parts of Ottappalam,
Alathur, Chittoor and Palakkad taluks. It is the most pre-
dominant soil type in the midland and gap areas. Laterites
on high grounds are more compact when compared to the
low-lying areas.
Virgin forest soil is seen in Mannarkad taluk and in
forest areas. The soil is rich in humus and organic matter.
Black cotton soil is seen in Chittoor and Attapady Valley
of the Mannarkad taluk (fluoride-affected area), which is
used for the cultivation of cotton. The soil exhibits mud
cracks and has high water-retaining power.
Alluvial soil is seen in the valleys. Palakkad District is
underlain by rocks of the Archaean metamorphic com-
plex. They include the granulite group, the gneisses and
the schists. Intrusives of pegmatites and quartz veins are
also common in the northeastern parts of the district.
The general geological succession encountered in the
district is given below:
Recent: Top soil, valley fill and riverine alluvium.
Sub-recent: Laterite.
Archaean: Pegmatites, quartz vein, dolerite, gabbro,
granites, quartz-mica schist, hornblende biotite
gneiss, ultramafics, charnockite khondalites
and calc-granulites.
The Archaean crystallines are the major rock types en-
countered in the district. Charnockites, hornblende gneiss,
migmatites and gneisses occupy a major part of the dis-
trict. Schistose rocks associated with hornblende biotite
gneiss are mainly seen in the Chittoor and Attapady area,
in the northeastern parts of the district (Figure 1).
Groundwater occurs in all the geological formations
from Archaean crystalline to Recent alluvium. Groundwa-
ter occurs in phreatic condition in the laterite, alluvium and
in weathered crystallines. It is in semi-confined to con-
fined condition in the deeper fractured rocks. However, in
the eastern part of Palghat District (study area), both the
phreatic and deeper aquifers tap only the crystallines. The
phreatic zone comprises weathered to partly weathered
crystallines, and the deeper aquifer is formed by the frac-
tured crystallines. In the study area, laterization is limited
CURRENT SCIENCE, VOL. 92, NO. 2, 25 JANUARY 2007

Figure 1. Geology of the study area.
and alluvium is restricted to river beds and no dug well
taps these zones. Moreover, this area has been subjected
to a high degree of deformation, which has given rise to
network/intersection fractures; this can be traced surfi-
cially. This intersecting nature of lineaments suggests
that the water-yielding zones for phreatic and deeper aq-
uifers are interconnected in hydraulic continuity. Thus the
mechanism of fluoride release for both the aquifers is the
same since the aquifer is one and the same, i.e. country
rock, hornblende biotite gneiss. In this area the depth of
the well ranges from 6 to 18 m bgl. The diameter ranges from
1 to 5 m and water level ranges from 3 to 15.0 m bgl.
CURRENT SCIENCE, VOL. 92, NO. 2, 25 JANUARY 2007
RESEARCH COMMUNICATIONS
Water samples collected from dug wells, bore wells,
and Kerala Water Authority (KWA) pumping wells were
subjected to fluoride analysis along with other parameters
in the Regional Chemical Laboratory, CGWB (Table 1).
The highest concentration in the phreatic zone (5.75 ppm)
is observed from Kopanur. This is a domestic dug well
which taps the weathered zone and the water is being
used for drinking. Dental fluorosis has been observed in
children in this area. The highest concentration of fluo-
ride (3.12 ppm) in deeper aquifers is observed from
Chinamoolathara. The fluoride-affected areas are shown
in Figure 2.
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RESEARCH COMMUNICATIONS
The water supply wells of KWA located at Vannamada
and Eruthenpathy also show higher values of fluoride.
This water is being supplied to the local people for drink-
ing purposes. Dental fluoride is being reported from
Vadakarapathy and Eruthenpathy panchayats by the Pri-
mary Health Centres under the Public Health Department,
Govt of Kerala. This study also shows that the most af-
fected are those below the age of 18 years.
In general, apatite and fluorite, besides replacement of
hydroxyl by fluoride ions in mica, hornblende and soil
that mostly consists of clay minerals, are major sources
of F– in circulating water 6–8 . The country rocks contain
apatite (0.2–1.20%), fluorite (0.1–1.49%) and biotite (0.21–
8.22%), which could be the possible sources of fluoride
in groundwater. Lithogenic sodium (LNa+), i.e. the net
Na + acquired by groundwater from the chemical weather-
ing of rock-forming minerals, is used as an index of the
weathering of minerals9 . The weathering activity charac-
terized by alternate wet and dry conditions of the semi-
arid climate is responsible for leaching fluoride from the
minerals present in the soils and rocks7 . The eastern part
of Palghat District is a rain-shadow region with an aver-
age annual rainfall of 1200 mm, against the district aver-
age of 2400 mm, and is a canal command area. Intensive
and long-term irrigation in the area is probably another
factor that causes weathering and leaching of F– from the
soils/weathered rocks. Easy accessibility of circulating
Figure 2. Map showing high-fluoride areas.
242
water to the weathered products during irrigation dis-
solves and leaches the minerals, contributing F– to the
groundwater 10 . Jacks et al. 11 reported that in Coimbatore
District, Tamil Nadu, dark-coloured minerals in rocks
contain 180–2600 mg/kg F– and the relative stability of
flourapatite during the weathering process indicates that
the main source of fluoride in groundwater is from micas,
hornblende and pyroxene. The country rock in the fluoride-
affected areas of Palghat and Coimbatore is hornblende
biotite gneiss. The chemical weathering of hornblende
biotite gneiss coupled with other factors are favourable for
the release of fluoride in the groundwater.
The groundwater geochemistry is examined based on
saturation with respect to fluorite and its nature as re-
vealed by the Piper diagram.
Saturation indices with respect to CaF2 were calculated
for the 15 samples. The solubility product for fluorite at
25°C and 1 atmosphere was taken as 10–10.96, computed by
Nordstrom and Jenne12 . The ionic strength ranged from
0.01 to 0.07. Here the extended Debye–Huckel equation
was used to calculate the activity coefficients at each
ionic strength, and the saturation index was calculated
with the activities of Ca2+ and F– instead of their concen-
trations. A range of values for saturation index near zero
are generally considered to be within the equilibrium
zone for a mineral 13 . Saturation Index ± 5% (logKmineral )
is considered here. Accordingly, it is found that all the
samples are saturated with respect to fluorite. The com-
puted saturation index and ionic strengths are given in
Tables 1 and 2. That is, all the samples are at or near
equilibrium with fluorite and this controls the concentra-
tion of its constituents in the groundwater. In other
words, when the water is saturated with respect to fluorite
or is at equilibrium with fluorite, the low calcium concen-
tration leads to higher fluoride concentrations. This is in
accordance with our data.
Water-quality interpretation is attempted by plotting in
the Piper diagram. The anions and cations of 15 samples
were plotted in the piper diagram. The different distribu-
tion pattern of the water samples is shown in Figure 3 and
the types of water along with saturation index are given
in Table 2. A close analysis of the fields of the Piper dia-
grams (Figure 3 and Table 2) reveals that fluoride con-
centration is comparatively less in samples where no
single cation or anion dominates (sample nos 1, 2, 3, 10
and 14 which are of Ca2+Na+HCO–3Cl– type). The common
ion noticed in all the water types is Na+. The fluoride
concentration is comparatively more in water types where
Na + is the dominant cation (sample nos 11, 8, 13 and 7,
except sample no. 12 of Na +HCO–3 type with fluoride
concentration of 1.67 mg/l, Figure 3). The fluoride con-
centration is also comparatively less in the Ca2+Na +Cl –
and Ca 2+Na +HCO–3 water types (sample nos 6, 4, 9 and 5,
except sample no. 15 with a fluoride concentration of
2.66 mg/l, Figure 3). This could mean that if there is more
sodium in the sample, the lesser would be the calcium
CURRENT SCIENCE, VOL. 92, NO. 2, 25 JANUARY 2007
 Table 1. Results of chemical analyses

Sample Ec µs/cm at TH as Ca Mg Na K CO 3 HCO3 SO 4 Cl F NO3 I S.I

nos Location Source pH 25°C CaCO3 mg/l

1. Muthalamada DW 7.21 919 280 48 39 89 1.4 0 305 18 121 1.51 26 0.01 –0.28
2. Eruthenpathy BW 7.97 2020 510 84 73 268 11 0 695 227 199 1.58 2.3 0.03 –0.05
3. GUPS RV Puthoor BW 7.67 1940 660 112 92 180 14 0 561 300 192 1.63 4.9 0.03 +0.1
4. Athikodu DW 7.65 3800 980 212 109 430 2.4 0 659 134 918 1.73 22 0.06 +0.36

CURRENT SCIENCE, VOL. 92, NO. 2, 25 JANUARY 2007

5. Vannamada BW 8.13 1320 440 68 66 120 11 0 537 188 64 1.64 0.3 0.02 –0.09
6. Nadupeni DW 8.08 4320 1300 230 176 455 21 0 451 522 908 1.6 101 0.07 +0.32
7. Kodumthirapalli DW 7.9 3830 600 80 97 620 3.3 0 622 207 800 2.82 2.4 0.06 +0.36
8. Kopanur DW 9.0 1826 120 12 22 415 1.5 144 555 53 206 5.75 4.6 0.03 +0.22
9. Villoonni DW 7.9 1191 320 40 54 142 8.5 0 586 51 78 1.75 3.7 0.02 –0.26
10. Kollamkodu DW 8.1 1348 300 48 44 176 6.4 0 403 89 192 1.6 6.3 0.02 –0.26
11. Vattalakki West DW 8.25 1110 210 36 29 160 6 0 488 28 49 2.04 0 0.02 –0.18
12. Puzhappalam BW 8.09 1493 290 24 56 214 9.2 0 573 43 163 1.67 2.2 0.02 –0.53
13. Chinnamoolathara BW 8.50 2000 340 28 66 338 8.6 60 537 218 227 3.12 2.5 0.03 +0.06
14. Anakatti BW 8.12 1446 340 28 66 154 1.4 0 464 188 149 1.84 36 0.02 –0.37
15. Kulukkur BW 8.25 638 150 24 22 62 6.5 0 281 24 37 2.66 0 0.01 –0.09

DW, Dug well; BW, Bore well; I, Ionic strength, SI, Saturation index.

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RESEARCH COMMUNICATIONS
Table 2. Results of Piper diagram and its relation to saturation index

Water type Sample no. F– (mg/l) Ionic strength Saturation index

+
Na HCO–3 11 2.04 0.02 – 0.18
8 5.75 0.03 + 0.22
12 1.67 0.02 – 0.53

Na+ HCO–3Cl– 13 3.12 0.03 + 0.06

Na+ Cl– 7 2.82 0.06 + 0.36

Ca2+Na+ Cl– 6 1.6 0.07 + 0.32

4 1.73 0.06 + 0.36

Ca2+Na+ HCO–3 15 2.66 0.01 – 0.09

9 1.75 0.02 – 0.26
5 1.64 0.02 – 0.09

Ca2+Na+ HCO–3Cl– 1 1.51 0.01 – 0.28

2 1.58 0.03 – 0.05
3 1.63 0.03 + 0.1
10 1.6 0.02 – 0.26
14 1.84 0.02 – 0.37

Figure 4. Scatter plot showing pH vs F– .

ride values show an increase in Na/Ca ratio. This is because

Figure 3. Piper diagram.
content and consequently an increase in the levels of
fluoride. Conversely, as calcium levels increase sodium
and fluoride levels decrease.
Results from groundwater obtained from the eastern
part of Palghat District suggest that the country rocks, in
which fluorine is strongly absorbed in soils consisting
mostly of clay, are the main sources of F– . There is a
positive correlation between fluoride content and pH in
the groundwater (Figure 4). High fluoride is also related
to residual alkalinity (Ca2+ < HCO3 )11 and saturation with
respect to fluorite. Hardness is less than alkalinity in
many samples. The groundwater samples with high fluo-
of lowering of Ca activity in the area. In the Kopanur
area, the groundwater sample shows high Na, which
might have been released from the weathered soil. Alka-
linity of the circulating water depleted in calcium is
mainly responsible for the high incidence of F– . The
longer residence time of water in the aquifer zone, caused
by a high rate of evapotranspiration and a weathered zone
of low hydraulic conductivity, are the supplementary fac-
tors that activate the dissolution of fluorine-bearing min-
erals to further increase F – content in the groundwater.
The high fluoride in the study area is derived primarily
from the country rock, i.e. hornblende biotite gneiss, since
no man-made pollution is noticed in the area. The alkaline
water depleted in calcium is capable of releasing F– from
the fluorine-bearing minerals. Intensive and long-term
irrigation, comparatively low rainfall, an alkaline environ-
ment, longer residence time of water in the aquifer zone
and a low rate of dilution are favourable factors for the

244 CURRENT SCIENCE, VOL. 92, NO. 2, 25 JANUARY 2007


dissolution of fluorine-bearing minerals in the ground-
water. That is, all the samples are at or near equilibrium
with fluorite and this controls the concentration of its
constituents in the groundwater. In other words, when the
water is saturated with respect to or is at equilibrium with
fluorite, the low calcium concentration leads to higher
fluoride concentrations. A close analysis of the fields of
the Piper diagrams reveals that fluoride concentration is
comparatively less in samples where no single cation or
anion dominates. This could be taken to mean that if
there is more sodium in the sample, the lesser would be
the calcium content and consequently an increase in the
levels of fluoride. Conversely, as calcium levels increase
sodium and fluoride levels decrease. Dental fluorosis is
observed in the Chittoor taluk. Since local people are de-
pendent on groundwater for domestic use remedial meas-
ures, including rainwater harvesting, are needed in the
area.
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Indian Standard Institute, 1983.
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ACKNOWLEDGEMENTS. We thank Dr Saleem Romani, Chairman,
CGWB and S. R. Tamta, Regional Director, CGWB, Kerala Region for
encouragement. We also thank the officers of CGWB; V. Kunhambu,
V. N. Sreelatha, G. Sreenath, Tony Eapen, Vidya B. Nair, for their
inputs. Dr A. P. Pradeepkumar, University College is thanked for his
critical comments.
Received 31 December 2005; revised accepted 17 August 2006
245