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Hydrogeochemical evaluation of high-fluoride

groundwaters: a case study from Mehsana District,
Gujarat, India
a

S. D. DHIMAN & ASHOK K. KESHARI

Department of Civil Engineering , Birla Vishvakarma Mahavidyalaya , Vallabh

Vidyanagar, 388 120, Gujarat, India E-mail:
b

Department of Civil Engineering , Indian Institute of Technology Delhi , Hauz Khas, New
Delhi, 110 016, India E-mail:
Published online: 19 Jan 2010.

To cite this article: S. D. DHIMAN & ASHOK K. KESHARI (2006) Hydrogeochemical evaluation of high-fluoride
groundwaters: a case study from Mehsana District, Gujarat, India, Hydrological Sciences Journal, 51:6, 1149-1162
To link to this article: http://dx.doi.org/10.1623/hysj.51.6.1149

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Hydrological SciencesJournaldes Sciences Hydrologiques, 51(6) December 2006

1149

Hydrogeochemical evaluation of high-fluoride groundwaters:

a case study from Mehsana District, Gujarat, India

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S. D. DHIMAN1 & ASHOK K. KESHARI2

1 Department of Civil Engineering, Birla Vishvakarma Mahavidyalaya, Vallabh Vidyanagar 388 120, Gujarat, India
dhimansanjay18@hotmail.com
2 Department of Civil Engineering, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110 016, India
akeshari@hotmail.com

Abstract Groundwater quality problems have emerged in many geographical areas due to natural
environmental processes and human intervention in the geosystems. Hydrogeochemical appraisal of
fluoride contaminated groundwater in Mehsana District, Gujarat State, India is carried out by means of
groundwater quality investigations together with X-ray diffraction analysis of soil samples in the
delineated high fluoride areas. Results show that fluoride has negative relationships with calcium,
whereas relationships with sodium, alkalinity and sulphate are positive. Results obtained from aqueous
speciation modelling using PHREEQC reveal that the groundwater is undersaturated with fluorite and
oversaturated with calcite. The factor analysis indicates that sodium plus potassium bicarbonate groundwater have high factor loading for fluoride, whereas that for calcium chloride and magnesium chloride
groundwater is low. The plausible geochemical reactions in the study area are precipitation of calcite
and dissolution of dolomite, carbon dioxide and sulphate minerals with ion exchange.
Key words aqueous speciation modelling; fluoride; groundwater; Gujarat, India; hydrogeochemistry

Evaluation hydrogochimique deaux souterraines fortes teneurs en fluorures:

une tude de cas de la Rgion de Mehsana, Gujarat, Inde
Rsum Des problmes de qualit de leau souterraine sont apparus dans de nombreuses rgions
gographiques cause de processus environnementaux naturels et de lintervention humaine dans les
gosystmes. Lvaluation hydrogochimique de leau souterraine contamine par des fluorures de la
Rgion de Mehsana, dans lEtat Indien de Gujarat, est mene grce des observations de qualit de
leau souterraine et des analyses par diffraction de rayons X dchantillons de sol issus des zones qui
prsentent de fortes teneurs en fluorures. Les rsultats montrent que les fluorures ont des relations
ngatives avec le calcium, et positives avec le sodium, lalcalinit et les sulfates. Les rsultats de la
modlisation de la spciation aqueuse avec PHREEQC rvlent que leau souterraine est sous-sature en
fluorures et sur-sature en calcite. Lanalyse factorielle indique que le sodium plus le bicarbonate de
potassium de leau souterraine ont un facteur de charge important pour les fluorures, mais faible pour les
chlorures de calcium et de magnsium. Les ractions gochimiques plausibles de la zone dtude sont la
prcipitation de la calcite et la dissolution de la dolomite, du dioxyde de carbone et des minraux
sulfats avec changes ioniques.
Mots clefs modlisation de spciation aqueuse; fluorure; eau souterraine; Gujarat, Inde; hydrogochimie

INTRODUCTION
Occurrence of fluoride (F-) in groundwater has drawn global attention as ingestion of
water with fluoride concentration above 1.5 mg L-1 may result in dental or skeletal
fluorosis. The maximum tolerance limit of fluoride in drinking water specified by the
World Health Organization (WHO, 1984) is 1.5 mg L-1. High fluoride concentration in
the groundwater has been reported in many parts of Indian subcontinent and is
becoming a serious concern for the drinking water supply (Jacks et al., 2000, 2005;
Keshari & Dhiman, 2001). Studies reveal that infants, children and adults in the study
area of Mehsana District are exposed to high doses of fluoride from groundwater
(Chinoy et al., 1992; Dhiman & Keshari, 2003). Normally, fluorine, because of its
high reactivity, exists in the form of fluoride in natural waters (Leung & Hrudey,
1985). Fluorine occurs mainly as free fluoride ion (F-) in natural waters, though
Open for discussion until 1 June 2007

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1150

S. D. Dhiman & Ashok K. Keshari

fluoride complexes of Al, Be, B and Si are also encountered under specific conditions.
Strunz (1970) reported about 150 fluorine-bearing minerals (63 silicates, 34 halides,
22 phosphates and 30 others), but many minerals may contain minor amounts of Freplacing OH- or O2-. The main natural sources of fluoride in soil are fragments of
minerals, such as apatite, cryolite, fluorite or fluorspar and topaz (Al silicates
containing F), fluormica (phologopite), epidote, phosphorite, tremolite and villuanite.
These can be supplemented by anthropogenic input from industrial sources. Industries
which use raw materials containing even small amounts of fluorine can release enough
gaseous (HF, SiF4) and/or particulate fluorides (AlF3 Na3AlF6, CaF2) to enhance
elemental levels in the surrounding areas. Pollutant sources include: manufacturers of
bricks, iron-based fertilizers and glass; coal-fired power stations; and aluminium
smelters (Handa, 1975; Wedepohl, 1978; Matthes & Harvey, 1982; Deer et al., 1983;
Pickering, 1985; Hem, 1986; Handa, 1988; Gaumat et al., 1992; Gaciri & Davies,
1993, Rao, 1997).
The occurrence of fluoride has been reported in both igneous and sedimentary
rocks. The concentration of F- ranges from 30 to 21000 ppm in amphiboles present in
metamorphic rocks, and pegmatite intrusions also cause high fluoride in groundwater
(Srikanth et al., 2002). Several minerals, such as sepiolite and palygorskite, also
control the fluoride distribution in groundwater in many geographical regions. Geochemical reactions, namely precipitation/dissolution, aqueous complexation, sorption,
dissolution and exsolution of gases, and changes in groundwater flow pattern significantly affect the distribution of geochemical species in natural aqueous systems. Wang
et al. (1993) proposed a dynamic model that predicts the features of calcrete as a
function of any desired climatic changes in temperature, wet/dry relative durations,
PCO2 and water table position and slope in the semiarid regions.
In the recent past, factor analysis has been used by many investigators for
identifying the interrelationships between the chemical constituents (Dawdy & Feth,
1967; Mellout & Collin, 1992; Brown, 1993; Cameron, 1996; Evans et al., 1996;
Grande et al., 1996; Subbarao et al., 1996; Gupta et al., 1999, Adams, et al. 2001;
Jeong, 2001; Kundu et al,. 2001; Wang et al., 2001; Reghunath et al., 2002; Farnham
et al., 2003; Liu et al., 2003; Stuben et al., 2003). In this study, hydrogeochemical
evaluation of high-fluoride groundwaters in Mehsana District, Gujarat State, India is
carried out (a) to characterize fluoride contamination in the groundwater; and (b) to
identify plausible geochemical reactions under the prevailing hydrogeological
conditions, as well as their role in mobilizing fluoride concentration.
DESCRIPTION OF THE STUDY AREA
Mehsana District in Gujarat State (as per administrative boundaries, 1980) is located in
the western part of India between 23022409N and 71267251E (Fig. 1). It is
primarily an agricultural district with a total cultivable area of 0.75 106 ha, which is
83 % of the total reported area. Only about 2% of the area of the district is under
forest, which is mainly concentrated in Kheralu and Sami talukas. The net area sown
during 1993/94 was 78%. The principal crops under cultivation are millet (bajra),
cotton, and tall millet (jowar). The rivers Sabarmati, Saraswati, Rupen and Banas flow
through the study area. The normal annual precipitation ranges from 500 mm in the
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India

Gujarat
Mehsana district

Fig. 1 Map of Mehsana District, Gujarat State, India.

west to 900 mm towards the east. About 97% of the total annual rainfall occurs during
the Southwest Monsoon from June to mid-September. On average, there are 31.3 rainy
days, of which 29.4 occur during JuneSeptember (Kumar, 1998). The average annual
rainfall of the district is 603 mm for the 31-year period (19651995) and severe
droughts occur with a frequency of 16%. The average temperature is 40C during
summer and 10C during winter. The mean annual value of potential evapotranspiration for the study area can be taken as 1677 mm, based on the measurements
recorded at Ahmedabad meteorological station. The relative humidity in the region is
between 60 and 80%, and the mean wind speed during summer (MayJuly) is about
18.7 km h-1.
The geological setup for the district shows thick alluvium almost throughout the
study area, and the Ajabgarh metasedimentary rocks occupy a small area in the
northeastern portion (Fig. 2). The latter consist of calc-gneiss and para-gneiss, which
have been intruded by basic rocks. The granites occur in the northeastern part and are
highly weathered, giving rise to clay formation. Over the granites lie the Himmatnagar
formation, comprising sandstone, conglomerate and shale. These formations are also
highly weathered. The tertiary rocks are not exposed anywhere in the district as they
are overlain by thick soil and alluvium. The geological cross-sections reveal that the
average thickness of sandy clay may be 3540 m at a depth of 125 m below the ground
surface. A sandy clay lens of 15 m thickness is also observed at about 50 m below the
ground surface in the southeastern part of the study area. The main mineral resources
in the district are china clay and fire clay. Occurrence of bentonite beds in the alluvial
deposits may be the result of deposition of bentonite, washed from the granitic terrain,
towards the east and northeast by winds (Phadtare, 1981). The five main types of soil
in the district are: saline-alkali soil, calcareous sandy loams, calcareous sandy soil,
non-calcic brown soils and non-calcic red-brown soils (UNDP/CGWB, 1976), as
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S. D. Dhiman & Ashok K. Keshari

Fig. 2 Geology map of Mehsana district.

Fig. 3 Generalized soil map of Mehsana District.

shown in Fig. 3. The unconfined aquifer thickness ranges from 35 to 125 m. The transmissivity of the unconfined aquifer ranges between 30 and 1000 m2 day-1. The specific
capacities of wells are between 23 and 714.1 m2 day-1. The depth of wells ranges from
8 to 18.5 m below ground level (b.g.l.) and depth to water level in open wells varies
from 5 to 14 m b.g.l. The yield of wells is in the range 30120 m3 day-1 (Kumar,
1998). Tube wells, with depths of 60350 m, and discharges of 17285184 m3 day-1,
are the main abstraction structures in the district. The uppermost confined aquifer
consists of medium- to coarse-grained sands and gravel, locally interstratified with
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Table 1 Hydrochemical parameters (June, 1980).

Location
Bhandu
Bhatson
Bheesal Vasana
Charasanph-2
Charasanphi
Dabhoda
Gadha
Gilosan
Kamalpura
Karoda
Khimiyana
Lunawa
Malekpur
Mehsana
Nedra
Pamol
Patan
Sariyad
Sipur
Titodan
Unawa
Vadnagar
Veerpur
Veragram
Visnagar
Wagrod

pH
8.1
7.65
8.2
7.65
7.9
8.3
7.9
8.2
8.5
8.5
8.15
8.5
8.75
8.6
8.45
7.9
7.65
8.05
7.8
8.6
8.1
8.05
8.25
8
8.5
7.95

Ca
2.59
3.59
2.19
5.18
3.39
0.99
5.98
2.79
1.79
0.99
3.79
1.39
2.99
1.99
0.59
0.79
3.79
4.49
1.59
3.59
7.58
0.99
0.79
2.59
1.39
7.48

Mg
9.21
19.09
2.96
5.02
2.63
0.98
3.37
4.19
2.63
1.97
3.62
1.56
6.00
3.37
2.22
1.56
6.33
2.88
1.97
4.60
24.03
2.96
1.97
4.77
1.97
3.53

Na
26.54
30.02
14.0
27.32
17.31
4.22
13.40
16.01
4.00
53.04
7.52
7.00
2.30
16.40
4.78
8.52
26.02
15.01
15.79
5.22
19.53
82.07
8.79
35.55
18.79
6.22

K
1.79
6.57
0.20
0.41
0.28
0
0
0.20
0.10
0.84
1.79
0
0
0
0.10
0
1.99
0.12
0
0.07
1.68
15.95
0
0.99
1.09
1.79

F
0.03
0.12
0.08
0.01
0.01
0.1
0.07
0.04
0.03
0.05
0.03
0.05
0.09
0.04
0.05
0.06
0.07
0.00
0.2
0.06
0.03
0.3
0.09
0.02
0.00

Cl
33.0
39.99
8.01
33.98
17.99
1.80
14.80
11.0
3.80
39.9
5.61
2.98
2.00
8.91
2.90
2.39
19.80
11.59
7.81
3.41
35.39
42.39
4.20
30.99
10.2
11.98

SO4
1.79
8.59
1.20
0.29
1.79
15.0
1.70
2.49
0.89
4.10
1.20
0.72
0.70
3.10
0.70
0.41
3.70
7.37
0.89
0.79
4.49
20.48
1.06
6.10
1.99
1.60

CO3
0.8
0.8
0.8
1.6
0.8
0.8
1.6
1.2
-

HCO3
4.19
8.39
9.39
3.39
3.6
3
5.80
9.19
2.60
10
9
4.39
6.19
8.19
3.19
7.4
11.8
4.60
10
7.60
9.19
37.8
5.60
5.4
10.2
5.60

NO3
0.74
2.67
0.25
0.45
0.32
0.25
0.96
0.54
0.51
0.29
0.38
0.32
0.12
0.29
0.19
0.17
3.16
0.22
0.40
0.30
4
0.5
1.29
1.74
0.96
0.32

EC
4150
6870
1860
3920
2520
625
2330
2265
850
6110
1630
920
990
2105
790
1050
3790
2310
1845
1230
5854
10025
1200
4720
2280
1935

All concentrations (exc. pH) in meq L-1; EC in mmhos cm-1 at 25C.

clay lenses and is separated from overlying and underlying aquifers by beds of clay
and sandy clays. The confined aquifer is found at a depth of 78162 m below the
ground surface. The groundwater quality parameters of the unconfined aquifer reported
by Phadtare (1981) for various locations are given in Table 1.
FIELD AND EXPERIMENTAL INVESTIGATIONS
Groundwater quality monitoring was carried out for 21 well locations in the study area
during June and October 2002. The details of well locations, well type and depth of
wells are given in Table 2. The soil samples were also collected for mineralogical
investigation. A Global Positioning System (GeoExplorer 3.0; Trimble GPS) was used
for locating wells in the study area. Chemical analysis was conducted following the
APHA standard methods (APHA, 2000). In situ measurements were taken for pH and
temperature using portable meters (Eutech, Singapore). The chemical constituents,
namely calcium and total hardness, were determined by EDTA titration method and
alkalinity was measured by titrating with sulphuric acid. Fluoride, potassium, sulphate
and iron concentrations were measured using a spectrophotometer and an ion-selective
electrode was used for the measurement of chloride. The SPADNS method was used
for fluoride determination. Regression analysis between sodium and chloride was
carried out using the hydrochemical data presented by Phadtare (1981), Krupanidhi et
al. (1986) and Kumar (1998). This gave an r2 value of 0.9. Using this relationship
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S. D. Dhiman & Ashok K. Keshari

Table 2 Well location, type and depth of well.

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Location

GPS observations
Latitude, N

Longitude, E

Ambavada
724036.92
235266.29
Badarpur
723934.65
234949.57
Dabhoda
724155.08
235657.65
Gathaman
723940.28
235306.71
Gorisana
724249.37
235330.84
Gunja
723507.10
234442.92
Hirwani-Moti
723256.16
235236.01
Jaska
72328.10
234914.6
Kahipur
723953.86
234453.63
Karbatia
724255.34
234616.49
Kheralu
723738.77
235345.5
Malekpur-1
723556.7
234606
Malekpur-2
723602
234611.38
Mandali
722950.45
235919.58
Sipor
723947.3
235027.58
Sundhia
723513.86
235023.8
Umta
723335.08
234651.25
Vadnagar
723754.8
234737.23
Vaghvadi
724439.17
235255
Varetha
724111.70
23580.016
Vithoda
723247.12
2355 16
DW: dug well; DB: dug-cum-bored well; TW: tube well.

Altitude
(m a.m.s.l.)
190
179.7
236.1
176.7
190
150
145.5
126.8
148.6
174.3
186
151.8
147.5
179.2
179.6
163.6
131.8
153
191.5
212.2
180

Well
type

Depth of
well
(m b.g.l.)

TW
TW
DB
TW
TW
TW
DW
DB
TW
TW
TW
TW
DW
TW
TW
DB
TW
DW
DW
TW
DW

151.5
75.75
36.36
90.9
56.06
272.7
15.15
18.78
66.6
69.7
60.6
121.7
10.5
90.9
75.7
21.2
75.7
19.7
30.3
63.6
16.9

between Na+ and Cl-, the concentrations of Na+ were calculated for the observed data
of June 2002 and October 2002 from the Cl- concentrations. The cationanion balance
error of 18 samples collected in June and October 2002 is within the permissible limit
of 5% and the remaining three samples with higher ion balance error were not
considered in the study.
Soil phase analysis
The soil samples were collected from Dabhoda, Malekpur, Sipor, Umta, Vadnagar and
Vaghwadi villages in the Mehsana District using a hand auger from a depth of 60 cm
b.g.l. Mineralogical characterization of soil samples was carried out using a D-8
advanced powder X-ray diffractometer (Bruker, Germany) at the National Physical
Laboratory (NPL), New Delhi and PW 1710/00 powder X-ray diffractometer (Philips,
Holland) in the Textile Technology Department, Indian Institute of Technology, Delhi.
The X-ray diffractometry (XRD) patterns were obtained from the D-8 and PW1710/00
diffractometers using Cu K radiation equipped with a diffracted-beam monochromator in the range 560 2 and 1060 2, respectively. The voltage and current
were kept at 40 kV and 30 mA, respectively. The scanning rate was kept at 2 per
minute. The qualitative identification of the crystalline phases was carried out by
studying the peaks in the diffractograms.
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Hydrogeochemical evaluation of high-fluoride groundwaters

RESULTS AND INTERPRETATION

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Fluoride hydrogeochemistry and aqueous speciation modelling

Concentrations of various groundwater quality parameters obtained for samples collected in June and October 2002 are shown in Table 3. The water type for each sample is
also indicated. It is evident that groundwater is mainly of types Na-HCO3, Ca-HCO3
and Mg-HCO3. The area with high fluoride concentration in the unconfined aquifer
was delineated using hydrochemical data of June 1980. The calcium concentration
ranges between 12 and 152 mg L-1 and fluoride between 0.14 and 5.6 mg L-1. High
fluoride concentration in the groundwater is observed in the northeastern part of
Table 3 Hydrochemical parameters for June and October 2002 (concentrations are in meq L-1).
Location
June 2002:
Ambavada
Badarpur
Dabhoda
Gathaman
Gorisana
Hirwani-Moti
Jaska
Kahipur
Karbatia
Malekpur -1
Malekpur -2
Mandali
Sipor
Sundhia
Umta
Vadnagar
Vaghvadi
Varetha
October 2002:
Ambavada
Badarpur
Dabhoda
Gathaman
Gorisana
Hirwani-Moti
Jaska
Kahipur
Karbatia
Malekpur-1
Malekpur-2
Sipor
Sundhia
Umta
Vadnagar
Vaghvadi
Varetha

pH Ca

Mg

Na

Cl

SO4

CO3

HCO3

Water type

7.5
8
7.8
8
8.6
7.8
7.5
8
7.8
7.5
8
7.8
8.1
8.1
7.6
9.1
8
8

6.39
1.07
2.31
2.07
5.03
2.07
4.92
1.55
2.32
3.27
6.79
4.74
1.67
2.79
2
1.20
1.59
1.15

7.22
0.32
3.05
2.64
2.81
3.25
0.68
0.84
1.56
2.32
2.81
7.26
2.53
2.24
2.48
0.40
1.20
3.45

2
8.9
1.97
12.5
13.4
1.7
1.63
8.9
1.97
11.23
1.92
1.78
9.62
1.93
11.9
9.97
9.8
2.25

0.8
0.13
0.23
0.10
0.18
0.15
0.13
0.13
0.10
0.56
0.15
0.13
0.13
0.15
0.13
0.18
0.13
0.10

0.10
0.09
0.05
0.09
0.09
0.11
0.02
0.07
0.08
0.09
0.02
0.08
0.09
0.17
0.07
0.06
0.09
0.03

3.82
2.26
1.53
3.08
3.97
1.55
2.07
2.14
1.6
3.07
3.0
3.35
2.47
1.4
2.9
2.6
2.2
1.9

3.0
1.25
0.20
2.37
8.54
0.29
0.83
1.04
0.41
6.45
1.45
2.16
1.62
0.13
2.7
4.5
1.12
0.29

1.6
0.8
-

9.18
10.16
5.90
8.68
6.72
4.42
5.08
7.27
4.91
13.11
7.14
7.64
9.57
4.52
9.37
4.6
8.85
5.18

Mg-HCO3
Na- HCO3
Mg- HCO3
Na- HCO3
Na-SO4
Mg- HCO3
Ca- HCO3
Na- HCO3
Ca- HCO3
Na- HCO3
Ca- HCO3
Mg- HCO3
Na- HCO3
Ca- HCO3
Na- HCO3
Na- HCO3
Na- HCO3
Mg- HCO3

7.2
7.7
7.7
7.5
7.2
8.2
7.8
7.7
7.6
8.6
7.9
8
7.1
7.7
7.8
7.6
7.8

6.81
0.60
2.80
6.49
1.76
2.40
5.41
2.60
2.72
0.88
7.24
5.21
2.12
5.61
2.40
2.72
2.00

2.79
15.4
0.76
2.24
0.8
7.51
0.87
1.39
2.31
2.15
0.8
12.4
1.43
2.20
1.52
6.96
2.6

12.82
2
8.9
11.7
12.5
1.7
1.7
9.7
1.5
10.5
1.9
10.6
1.62
11.3
11.9
9.9
1.65

0.04
0.13
0.13
0.13
0.13
0.15
0.13
0.13
0.13
0.18
0.53
0.13
0.13
0.13
0.13
0.15
0.15

0.2
0.18
0.08
0.19
0.18
0.005
0.03
0.05
0.10
0.08
0.06
0.04
0.18
0.04
0.07
0.14
0.18

3.95
2.6
1.47
3.75
3.25
2.22
2.21
1.98
1.47
2.53
2.95
3.12
2.52
1.92
3.09
3.38
2.09

6
1.04
0.83
5.21
2.3
0.83
0.83
1.04
0.83
1.67
1.04
2.3
2.08
0.83
2.5
6.67
1.25

1.6
-

13.44
15.73
7.21
10.82
13.83
8.72
4.85
7.21
5.05
5.18
6.50
10.1
12.13
6.06
8.85
7.54
12.20

Na- HCO3
Mg- HCO3
Na- HCO3
Na- HCO3
Na- HCO3
Mg- HCO3
Ca- HCO3
Na- HCO3
Ca- HCO3
Na- HCO3
Ca- HCO3
Na- HCO3
Ca- HCO3
Na- HCO3
Na- HCO3
Na- HCO3
Mg- HCO3

Copyright 2006 IAHS Press

1156

S. D. Dhiman & Ashok K. Keshari

Ca
Mg
Na
K
F
Cl
HCO3
SO4
NO3
EC
pH

Ca
1
0.53
0.13
0.06
0.36
0.25
0.16
0.15
0.41
0.13
0.40

Mg

Na

Cl

HCO3

SO4

NO3

EC

1
0.12
0.22
0.04
0.54
0.02
0.10
0.80
0.48
0.27

1
0.78
0.50
0.82
0.77
0.63
0.18
0.92
0.26

1
0.70
0.58
0.88
0.75
0.18
0.80
0.25

1
0.17
0.75
0.58
0.02
0.42
0.13

1
0.42
0.43
0.48
0.94
0.45

1
0.64
0.09
0.7
0.10

1
0.13
0.62
0.14

1
0.45
0.40

1
0.37

pH

Mehsana District and decreases in the southwestern part. Dissolved fluoride is less than
1 mg L-1 in the southwestern part where clay content is high. Moreover, calcium concentration in the groundwater is less in the northeastern part of the district and increases in
the southwestern part. The correlation coefficients among various groundwater quality
parameters were obtained to investigate their interdependence. The correlation matrix for
the hydrochemical data of June 1980 is shown in Table 4. This shows that fluoride has a
negative relationship with calcium, magnesium, nitrate and pH, while the relationship
with sodium, potassium, bicarbonate alkalinity, sulphate, chloride and EC is positive.
High fluoride concentration occurs in sodium-bicarbonate waters. The upper limits of
the point distribution for observed fluoride and calcium concentrations (combined
hydrochemical data of June 1980, June 2002 and October 2002) form a hyperbolic curve
that suggests solubility of calcium- and fluoride- containing minerals controls the
fluoride concentration (Fig. 4). High fluoride with very low calcium and magnesium in
water may be due to prior precipitation of CaCO3 from water and only limited
incorporation of fluoride in the calcite structure, so that there is always a net balance of
fluoride in the solution, as suggested by Rao et al. (1993).
The calcite content in the soils of Mehsana District ranges from 0.1 to 10.28%. The
pH of these soils varies from 7 to 9. The hydraulic conductivity of the soil ranges from
zero for saline and alkali soils in the western part to more than 7 cm h-1 for calcareous
sandy soils towards north and west. The results of XRD analysis for the soil samples
were as follows: the crystalline phases identified in the soil samples of Dabhoda and
Jun-80
Jun 02
Oct-02

8
Calcium, meq L -1

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Table 4 Correlation coefficients matrix for June 1980 hydrochemical data.

6
4
2
0
0

0.1

0.2
Fluoride, meq L

0.3

0.4

-1

Fig. 4 Relationship between calcium and fluoride concentration.

Copyright 2006 IAHS Press

Hydrogeochemical evaluation of high-fluoride groundwaters

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SI Fluorite

Calcium meq L -1
2
4
6

1157

Jun-02
Oct-02
8

Jun-80

0
-1
-2
-3
-4
-5
-6

Fig. 5 Plot of saturation indices of fluorite vs calcium concentration.

Umta are quartz (-SiO2) and calcite (CaCO3). The soil sample of Malekpur is highly
crystalline material and contains quartz as the main crystalline phase with calcite and
sodium calcium aluminium silicate anorthite(Na, Ca) (SiAl)4O8 as the phases. The soil
samples of Sipor, Vaghwadi and Vadnagar are also highly crystalline material and
contain quartz as the main crystalline phase with calcite and sodium aluminium silicate
albite (NaAlSi3O8) as the next phases. Aqueous speciation modelling was carried out
using PHREEQC (Parkhurst & Appelo, 1999) geochemical code. The saturation indices
of fluorite were computed for all three sets of temporal data, sampled as well as earlier
hydrochemical data. Figure 5 shows the plot of these saturation indices vs calcium concentrations. It shows that the groundwater is oversaturated with calcite, having a
saturation index of 0.061.74 with equilibrium state at Umta. The groundwater is
undersaturated with fluorite, having a saturation index of 0.03 to 4.87.
Multivariate analysis
The factor analysis was carried out using the hydrochemical data of June 1980 for the
unconfined aquifer of the study area. These data constitute a larger data set as compared
to the sampled data of June and October 2002, and were considered for the multivariate
analysis without combining with the sampled data to make the homogeneous data set
with reference to dynamic changes in hydraulic stresses, land-use characteristics and
pollutant sources. The chemical constituents considered for factor analysis for the unconfined aquifer were calcium, magnesium, sodium, potassium, bicarbonate alkalinity,
sulphate, chloride, fluoride, nitrate, pH and electrical conductivity (EC). The carbonate
alkalinity concentration was not considered for factor analysis. The principal component
analysis was carried out using SPSS (Statistical Package for Social Services) software.
The two-factor model results reveal that the first two eigenvalues extracted from the
matrix account for more than 72% of total variance, which shows that the hydrochemical
data are well posed. A varimax rotated component matrix with Kaiser (1958)
normalization was used for principal component analysis. The interpretation of factors
was made in terms of the square of the coefficients of that factor. The distributions of
factor scores for Factor 1 and Factor 2 for the geographical locations are shown in
Fig. 6(a) and (b), respectively. The rotated component matrix for the geochemical data
is given in Table 5. There is almost identical loading for sodium, potassium and
bicarbonate. Therefore, the variance in the chemical composition of the hydrochemical
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1158

S. D. Dhiman & Ashok K. Keshari

(a)

(b)
Fig. 6 Distribution of scores of (a) Factor 1 and (b) Factor 2 in the geographical area.

system is controlled by sources of sodium and bicarbonate. For Factor 1, the sum of
squares of sodium and potassium (1.62) approximates that of bicarbonate, sulphate and
chloride (1.8). Thus, the combined relationship suggests that there is more than one
component or more than one solid phase that adds or removes sodium, potassium,
bicarbonate, sulphate and chloride into the groundwater. The presence of negative
correlations indicates that some components are controlled by equilibrium with the
minerals in the aquifers. Thus, there is a reaction path by which one set of chemical
products replaces another set. Factor 2 shows that the sum of squares of calcium and
magnesium (1.29) approximates that of nitrate and chloride (1.13). The combined
relationship suggests that there is more than one component or more than one solid
phase that adds or removes calcium, magnesium, chloride and nitrate. For Factor 2,
there is no replacement mechanism as there is lack of mutually exclusive components.
The origin of nitrate may be from the use of urea fertilizer. Factor 2 shows calcium
chloride and magnesium chloride waters. Moreover, it is observed that there is
negative correlation between calcium and fluoride for both the factors. For
Copyright 2006 IAHS Press

Hydrogeochemical evaluation of high-fluoride groundwaters

1159

Table 5 Rotated component matrix.

Component
1
0.28
4.7 10-2
0.89
0.91
0.78
0.59
0.80
0.91
0.18
7.9 10-2
0.80

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Parameter
Ca
Mg
Na
K
F
Cl
SO4
HCO3
pH
NO3
EC

2
0.74
0.86
0.23
0.17
0.22
0.67
4.2 10-2
2.7 10-2
0.58
0.83
0.54

Factor 1, probably there is dissolution of fluorite and precipitation of calcite, whereas

for Factor 2, the decrease in fluoride may be due to adsorption on clay surfaces. Thus,
these results obtained from factor analysis help in understanding the possible grouping
of chemical constituents in the groundwater.
Geochemical reactions
The actual changes in concentrations of chemical species as a function of sulphate concentration help in obtaining the information on the possible geochemical reactions that
may be occurring in the study area. To investigate this, analysis was carried out using
the hydrochemical data of June 1980, June 2002 and October 2002. The increase in
calcium and magnesium as sulphate increases, and the increase in sulphate and
decrease in pH are shown in Fig. 7(a)(c). The groundwater in the study area is
saturated with calcite and dolomite, and dissolution of anhydrite adds calcium to the
groundwater, causing precipitation of calcite. Calcite precipitation causes the pH to
decrease due to release of H+ ions from bicarbonate during incorporation of carbonate
in calcite. The decrease in the CO2 in the solution leads to dissolution of dolomite and
CO2 dissolution, thereby increasing the magnesium concentration in the solution. The
mass of the anhydrite and dolomite dissolved in the process exceeds the mass of calcite
precipitated, resulting in a net increase in the dissolved calcium as shown in Fig. 7(a).
The geochemical equations for possible reactions in the aquifer are as follows:
CaSO4
HCO-3
Ca+2 + CO-23
CaMg(CO3)2
CO2(g)
NaCl
KCl

Ca+2 + SO-24
H+ + CO-23
CaCO3
Ca+2 + Mg+2 + 2CO-23
CO2(aq)
Na+ + ClK+ + Cl-

(1)
(2)
(3)
(4)
(5)
(6)
(7)

where (g) in (5) refers to the gaseous phase and (aq) to the aqueous phase.
Copyright 2006 IAHS Press

S. D. Dhiman & Ashok K. Keshari

Jun-80
Jun-02
Oct-02

8
6
4
2

(a)

0
0

10

20

Magnesium, meq L -1

Calcium, meq L -1

1160

Jun-80
Jun-02
Oct-02

30
25
20
15
10
5
0

30

(b)
0

10

4
2

(c)

0
10

20

Sulphate, meq L -1

30

meq L

Jun-80

40
-1

Bicarbonate alkalinity,

Jun-80
Jun-02
Oct-02

30

Sulphate, meq L -1

10

pH

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Sulphate, meq L-1

20

Jun-02
Oct-02

30
ion exchange

20
10

dedolomitization

(d)

0
0

10

20

30

Sulphate , meq L -1

Fig. 7 Plot of calcium, magnesium, pH and bicarbonate alkalinity as a function of

sulphate.

Although the trends in calcium, magnesium and pH with sulphate are evident in
the groundwater of the northeastern part of Mehsana District, there is variation in the
temperature and other reactions in addition to dedolomitization or dissolution of
carbonates. Dedolomitization is a specific geochemical process and has been reported
by Plummer et al. (1990) and Kloss & Goebelbecker (1992). The plot of bicarbonate
alkalinity as a function of dissolved sulphate concentration (Fig. 7(d)) shows that bicarbonate alkalinity is decreasing with increase in sulphate, and is possibly indicative
of dedolomitization or carbonate dissolution. Cation exchange with calcium and
magnesium cations could contribute to additional bicarbonate on the flow path with
uptake of calcium and magnesium and release of sodium from exchange sites on clay
minerals causing dissolution of carbonate minerals. The molal concentrations of
sodium plus potassium are slightly more than the concentration of chloride. This is
indicative of presence of evaporites. These waters have high bicarbonate concentration. Thus, there is a tendency to form sodium-bicarbonate waters. For the groundwater
in the study area of Mehsana District, the sodium bicarbonate water is derived from the
dissolution of carbonate minerals. Further investigations using scanning electron
microscope (SEM) and microprobe analysis for soil samples, although not carried out
in the present study, may ascertain the dedolomitization process.
CONCLUSIONS
High fluoride concentration in groundwater, ranging in between 1.5 and 5.6 mg L-1, is
observed in large parts of the Mehsana District, Gujarat, India, and is a matter of
concern for drinking water supply since it exceeds the maximum permissible fluoride
concentration of 1.5 mg L-1 for public water supply systems. Dissolved fluoride is
usually less than 1 mg L-1 in the southwestern part of the district, whereas the
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Hydrogeochemical evaluation of high-fluoride groundwaters

1161

northeastern region is the most affected area, having fluoride concentrations of more
than 2 mg L-1 in some areas. It is observed that fluoride has a negative correlation with
calcium, magnesium, nitrate and pH, while a positive correlation is observed with
sodium, potassium, bicarbonate alkalinity, sulphate, chloride and EC. Factor analysis
revealed that sodium bicarbonate waters have high fluoride, whereas calcium chloride
and magnesium chloride waters have low factor loading for fluoride. Results obtained
from aqueous speciation modelling reveal that the groundwater is oversaturated with
calcite, indicating precipitation of calcite, and undersaturated with fluorite, possibly
indicative of its dissolution. The results of X-ray diffraction analysis of soil samples
show the presence of quartz, calcite, albite and anorthite as the main crystalline phases.
The geochemical reactions in the study area indicate precipitation of calcite and
dissolution of dolomite, carbon dioxide and sulphate-bearing minerals with ion
exchange.
Acknowledgements The authors are grateful to the reviewers for their constructive
and thoughtful comments and suggestions, which have helped in improving the quality
of the paper significantly.
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Received 22 August 2003 accepted 26 June 2006

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