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Spatial variability of fluorine in agricultural


soils around Sidhi District, Central India
Article in Journal of the Geological Society of India February 2016
Impact Factor: 0.6 DOI: 10.1007/s12594-016-0391-z

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JOURNAL GEOLOGICAL SOCIETY OF INDIA


Vol.87, February 2016, pp.227-235

Spatial Variability of Fluorine in Agricultural Soils around


Sidhi District, Central India

BIJENDRA KUMAR1, ASMAA NAAZ1, KRITI SHUKLA1, CHANDRAVIR NARAYAN1,


GOVIND SINGH2, ALOK KUMAR3, AL RAMANATHAN3 and ANSHUMALI1*

Laboratory of Biogeochemistry, Department of Environmental Science and Engineering, Indian School of Mines,
Dhanbad 826 004, Jharkhand, India
2
National Mineral Development Corporation, P.O. Donimalai, Bellary (Dt.) - 583 118, Karnataka, India
3
School of Environmental Sciences, Jawaharlal Nehru University, New Delhi-110 067, India
*Email: malijnu@gmail.com

Abstract: The systematic and comprehensive geochemical analysis of fluoride (F) in twenty agricultural soil samples
was carried out to understand spatial variability, mechanism of retention and release, and the areas of potential risk due
to high concentrations of F in soil around Sidhi District, Central India. The spatial variations in physico-chemical
parameters revealed significant difference in the methods of cultivation due to geomorphological constraints, availability
of surface water and ground water etc., in the study area. The north and small pocket in central Sidhi were rich in fertile
soils due to availability of surface and ground water. The southern and eastern Sidhi were rainfed areas, hence, the
monocropping system by traditional methods showed less impact on the soil physico-chemical parameters. The soil F
varied from 366.94 to 1178 mg/kg and 2-4 times greater than the background soil value (320 mg/kg) of the world. The
pollution indexes were > 1 indicating prevalence of elevated soil fluorine.
Keywords: Soil fluorine, Fertilizers, Geogenic, Silicate minerals, Madhya Pradesh
INTRODUCTION

The total fluoride (F) concentration in soils are often


derived from parent material, whereby its distribution in soil
profiles is a function of soil- forming process, of which
the degree of weathering and clay content are the most
prominent factors. The average fluoride content of most soils
world-wide has been documented as 329 mg/kg (KabataPendias et al., 1992). In general, the lowest F contents are
found in sandy soils in humid climate, whereas higher F
concentrations occur in heavy clay soils and in soils from
weathered mafic rocks (Fuge and Andrews, 1988).
The Al, Ca, Fe, P, pH, soil organic matter and clay content
of soils are the major parameters that control fluoride fixation
through adsorption, anion exchange, precipitation, formation
of mixed solids and complexes (Fluhler et al. 1982).
Generally, greatest adsorption of fluoride by soil mineral
components is always at an acidic pH, or at about pH 6 to 7
(Larsen and Widdowson, 1971; Perroilt et al., 1976; Chhabra
et al., 1980; Omueti and Jones, 1980). The high solubility
of fluoride in acid soils is often associated with the
occurrences of readily soluble fluorides such as NaF
and NH4F, where as AlF3 is known to be of low solubility.
Fluoride in soil is primarily associated with the soil colloid

or clay fraction. The clay and organic carbon content as


well as the pH of soil are primarily responsible for the
retention of fluoride in soils (Omueti and Jones, 1977).
Most of the fluoride in the soil is insoluble and, therefore,
less available to plants. However, high soil fluoride
concentrations or low pH, clay and/or organic matter can
increase fluoride levels in soil solution, increasing uptake
via the plant root. If fluoride is taken up through the root,
its concentrations are often higher in the root than in the
shoot, due to the low mobility of fluoride in the plant.
Symptoms of fluoride toxicity include emaciation, stiffness
of joints, abnormal teeth and bones, lowered milk production
and detrimental effects on the reproductive capacity of
animals.
Soil is the medium from which plants and animals
directly or indirectly derive their nutrients and food,
however, information regarding the concentrations of
fluoride in the cultivated soils of the Sidhi district is limited
or unavailable. In view of this no attention has ever been
drawn to address the problem of soil fluorine toxicity due
to its elevated concentration in the agricultural soils. In this
connection, the present work aims at the determination of
spatial distribution of soil fluoride and to understand the

0016-7622/2016-87-2-227/$ 1.00 GEOL. SOC. INDIA

228

BIJENDRA KUMAR AND OTHERS

mechanism of fluorine enrichment in the agricultural soils


in the Sidhi district, Central India.
STUDY AREA

The Sidhi District is situated on the north-eastern


boundary of the Madhya Pradesh State, India which lies
over a transitional area between the Indo-Gangetic plain in
the north and the Deccan plateau in the south. It is situated
between 2247.5' and 24 42.10' north latitude and 8118.40'
and 8248.30' east latitude (Fig. 1). The physiography is
characterized by low hill, extensive plateaus and river valleys
such as Son river valley which is a depository of the
Gondwana rocks. Topographically the district can be divided
into three zones, Vindhyan hills or Kaimour range,
Gondwana zone and Archean zone. Clay minerals like
kaolinite, halloysite, diaspore, gibbsite, nacrite, and dicktite

etc. were derived by the localized weathering of arkosic


metasediments (Mehrotra et al., 1979). The average
elevation of the area is 311 m above MSL. The climate of
the area is tropical monsoon type with three distinct seasons
namely hot and dry summer (March-June), monsoon (JulySeptember), and winter (November - February). The average
annual rainfall varies from 1000-1200 mm, peaks in the
months of July and August. The total population of the area
is 11, 26,515 spread with a density of 110/km2 (Census,
2011).
The total land cover in the Sidhi district is 10,536 km2
among which the forest area covers 40% (Land Records
and Settlement, 2011). The portion of the land used for
agricultural purpose is 47% but only 17% of the land used
for agricultural purpose has assured supply of water for
irrigation and the rest of the agricultural land is dependent
on rainfed irrigation and produces only one crop a year.

Fig. 1. Map of study area showing geology and sampling locations.


JOUR.GEOL.SOC.INDIA, VOL.87, FEB. 2016

SPATIAL VARIABILITY OF FLUORINE IN AGRICULTURAL SOILS AROUND SIDHI DISTRICT, CENTRAL INDIA

The land is largely undulating terrain, which often has steep


gradients not ideal for cultivation; the valleys along the major
rivers like the Son and the Gopad have fertile soils. The
crops grown are rice, maize, barley, pigeon pea and jute in
kharif season, and wheat, mustard and lentil in rabi season.
Sugarcane and cotton are also grown. The natural vegetation
comprises of tropical dry deciduous forests.
SAMPLING AND LABORATORY ANALYSIS

Twenty soil samples (0-20 cm depth) were collected from


agricultural lands (Table 1) cultivated by modern tools and
techniques in the catchment of Son and Gopad rivers, and
traditional techniques in the rainfed, hilly and forest areas
(Fig. 1). The sampling was carried out in the dry summer
season 12-13June 2013. All the soil samples were stored in
acid-cleaned HDPE bottles in frozen state using portable
ice box to minimize the biogeochemical alterations and
transported to the laboratory for analytical processing. All
soil samples were air-dried, crushed by wooden stick and
the gravel and relict bodies were picked out.
The pH and electrical conductivity (EC) were measured
on a 1:2.5 and 1:5 soil: water (w/v) ratio, respectively
(Allison and Moodie, 1965); soil organic carbon and organic
matter content was determined by the Walkley and Black
dichromate oxidation method (Nelson and Sommers, 1982);

229

the cation exchange capacity (CEC) by ammonium acetate


method; the total soil fluoride was obtained using the alkaline
fusion method (McQuaker and Gurney, 1977). The total
carbon (TC) and total nitrogen (TN) by Elemental Analyser
(Thermo Flash 2000). The elements (Al, Fe, Ca, Mg, Mn,
and P) were analysed by the ICP-OES (Leeman Profile Plus)
at NMDC, Donimalai, Karnataka. The particle size analysis
was carried out by Microtrac S3500 analyzer in Jawaharlal
Nehru University.
To assess the degree of pollution of fluorine in soils,
single factor pollution index (SFPI) method was used
(EPAC, 2005): Pi = Ci/Si, where Pi is the single factor
pollution index of fluorine, Ci is the content of fluorine in
soils at the sampling site and Si is the evaluative standard
value of fluorine. The background value (320 mg/kg) of the
world was taken as references to determine the starting value
and contamination levels of soils (Alina and Henryk, 1984).
The descriptive statistical analysis was carried out by the
SPSS (version 16.00). The fluorine spatial distribution
pattern map was produced by using the Arcview (9.3)
software for ordinary kriging interpolation.
RESULTS AND DISCUSSION

Table 2 present the results of physico-chemical


parameters of agricultural soil samples of the Sidhi district.

Table 1. Description of soil sampling locations in Sidhi district


Sample
ID

Location

Latitude

Longitude

Elevation
(m)

SSS-1

Jogipur

N2424.483'

E08155.26'

309.67

SSS-2

Devra

N2424.972'

E08155.671'

295.96

SSS-3

Rajdiha

N2424.717'

E08159.745'

265.48

Mode of irrigation, cropping system and


major crop(s)

Geology and land use


pattern
Dharwar, Agricultural land

Rainfed, mono cropping system, wheat

Dharwar, Agricultural land


Archean, Agricultural land

SSS-4

Kunvri

N2425.312'

E08202.426'

291.38

Dharwar, Forest area

SSS-5

Baheri

N2426.100'

E08206.550'

325.83

Dharwar, Forest area

SSS-6

Kukraon

N2430.497'

E08208.781'

225.85

Archean, Agricultural land

SSS-7

Chamrauha

N2432.162'

E08207.831'

244.14

Dharwar, Agricultural land

SSS-8

Ganghaut

N2432.276'

E08202.914'

256.94

Vindhyan, Agricultural land

SSS-9

Ghaunghra

N2431.398'

E08200.386'

253.28

Ground water, surface water, rain water,

SSS-10

Kirauha

N2430.230'

E08158.091'

248.71

double cropping system, wheat and paddy

SSS-11

Badigawan

N2429.088'

E08152.416'

274.32

Vindhyan, Agricultural land

SSS-12

Tikat Kalan

N2427.136'

E08134.664'

290.16

Vindhyan, Agricultural land

SSS-13

Bhitari

N2423.953'

E08135.010'

277.06

Dharwar, Agricultural land


Dharwar, Forest area

Vindhyan, Agricultural land


Vindhyan, Agricultural land

SSS-14

Pathera

N2421.566'

E08152.809'

306.62

SSS-15

Barambaba

N2416.322'

E08153.790'

387.09

Archean, Forest area

SSS-16

Mahkhor

N2407.246'

E08150.571'

419.70

Permian, Forest area

SSS-17

Bhadaura

N2406.127'

E08152.350'

347.47

SSS-18

Dhupkhad

N2400.393'

E08152.510'

355.70

SSS-19

Dudhmania

N2357.901'

E08146.257'

393.49

Permian, Forest area

SSS-20

Karvahi

N2403.883'

E08141.262'

455.06

Permian, Forest area

JOUR.GEOL.SOC.INDIA, VOL.87, FEB. 2016

Permian, Forest area


Rainfed, mono cropping system, wheat

Permian, Forest area

silt loam
silt loam
silt loam
silt loam
silty clay
silt loam
silt loam
silt loam
silt loam
silt loam
silty clay loam
silt loam
silt loam
silt loam
silt loam
loam
silt loam
loam
loam
silt loam
30.91
35.63
35.93
35.46
32.26
37.33
35.74
37.20
37.57
36.61
37.57
39.01
35.92
35.61
34.26
41.28
38.40
39.23
40.25
38.55
36.73
0.82
0.59
0.69
0.33
0.32
0.26
0.41
0.25
0.32
0.51
0.35
0.19
0.31
0.33
0.48
0.09
0.13
0.07
0.08
0.18
0.33
0.62
0.88
0.67
0.26
0.19
0.27
0.32
0.26
1.19
0.88
0.28
0.20
0.21
0.24
0.32
0.16
0.16
0.12
0.13
0.20
0.37
6.6
6.6
7.6
7.8
7.1
8.0
6.8
7.2
7.9
7.9
7.8
7.6
6.9
7.3
7.5
6.9
6.9
6.8
7.1
7.6
7.3
SSS1
SSS 2
SSS 3
SSS 4
SSS5
SSS6
SSS7
SSS8
SSS9
SSS10
SSS11
SSS12
SSS13
SSS14
SSS15
SSS16
SSS17
SSS18
SSS19
SSS20
Mean

0.16
0.11
0.22
0.26
0.90
0.60
0.30
0.13
0.13
0.21
0.12
0.08
0.07
0.29
0.18
0.07
0.08
0.06
0.06
0.10
0.210

3.96
3.92
3.14
4.01
1.72
1.52
2.46
1.87
2.02
2.20
2.65
32.79
1.65
7.20
3.07
43.66
6.45
34.34
41.34
3.02
10.15

80.22
76.66
81.04
76.44
53.31
77.87
80.06
84.41
83.89
77.45
70.10
56.10
70.25
76.53
78.93
45.91
77.06
51.03
47.10
74.77
70.96

15.82
19.42
15.82
19.55
44.97
20.61
17.48
13.72
14.09
20.35
27.25
11.11
28.10
16.27
18.00
10.43
16.49
14.63
11.56
22.21
18.89

1.01
1.28
1.59
1.09
1.02
1.93
1.38
1.67
1.26
1.07
0.77
0.61
1.16
1.53
1.33
0.74
1.07
0.24
1.19
0.99
1.14

1.75
2.22
2.05
1.88
1.71
3.32
2.39
2.86
2.17
1.66
1.32
1.07
2.01
2.65
2.31
1.28
1.83
0.43
2.05
1.71
1.97

16.54
18.50
18.00
17.00
16.30
20.38
18.64
19.10
16.82
16.32
15.74
12.96
18.25
18.86
19.39
13.17
17.04
7.65
18.49
16.76
16.75

413.56
618.64
505.08
486.44
403.56
1178.00
640.68
749.15
606.77
396.61
394.91
381.36
574.58
725.42
627.11
389.83
430.84
366.94
561.01
412.03
543.13

1.24
1.46
1.09
1.06
1.24
2.80
1.27
1.18
1.00
1.88
0.61
0.71
0.84
1.84
1.50
2.58
0.49
0.34
1.11
0.83
1.25

0.11
0.14
0.10
0.98
0.10
0.26
0.20
0.12
0.09
0.13
0.13
0.12
0.14
0.19
0.14
0.20
0.09
0.10
0.14
0.09
0.18

11.27
10.43
10.90
1.08
12.40
10.77
6.35
9.83
11.11
14.46
4.69
5.92
6.00
9.68
10.71
12.90
5.44
3.40
7.93
9.22
8.72

8.38
6.63
7.38
6.56
7.45
3.89
6.18
5.53
4.39
3.54
4.87
2.98
5.90
5.96
7.82
2.83
3.59
3.22
3.14
4.25
5.22

0.03
0.03
0.05
0.02
0.03
0.04
0.05
0.02
0.04
0.06
0.03
0.04
0.02
0.05
0.03
0.02
0.01
0.02
0.02
0.02
0.03

0.15
0.12
0.10
0.11
0.11
0.05
0.06
0.04
0.07
0.06
0.06
0.05
0.11
0.07
0.07
0.02
0.03
0.02
0.03
0.04
0.06

Mg
%
Ca
%
Mn
%
P
%
Al
%
C:N
TN
%
TC
%
F
mg/kg
CEC
Cmol/kg
SOM
%
SOC
%
Clay
%
Silt
%
Sand
%
EC
mS/cm
pH
Sample
ID

Table 2. Results of physico-chemical parameters of agricultural soils samples of Sidhi district

Fe
%

Si
%

Texture

BIJENDRA KUMAR AND OTHERS

8.11
5.90
4.28
6.41
8.10
3.72
3.53
4.27
5.81
5.45
3.22
3.02
4.31
4.71
5.07
2.30
1.53
1.73
1.34
2.64
4.27

230

The pH of soil samples varied from 6.6-8.0 with scarce


differences in mean soil pH between sites. Particle size
analysis of soil samples showed a diversified range of sand,
silt and clay as 1.52-43.66 %, 45.91-84.41 % and 10.4344.97 %, respectively, with silt as the most dominating
fraction. The soil organic carbon (SOC) and soil organic
matter (SOM) at different locations were found to be ranging
from 0.24-1.93 % and 0.43-3.32 %, respectively. Across all
locations CEC showed significant spatial variation ranging
from 7.65-20.38 Cmol/kg. The soil fluoride concentrations
ranged from 366.94 to 1178 mg/kg.
Biogeochemistry of Agricultural Soils

The CEC showed positive relationship with SOC and


SOM an indication of stable physic-chemical conditions,
microbial immobilization, insignificant leaching and
translocation as dissolved or particulate organic carbon
and poor chances of soil erosion in the summer season
(Fig. 2). The C:N ratio varied from 1.08-14.46 and the
average C:N ratio was 8.72 indicating sequestration of
8.72 units of C requires, in the most soils, something close
to one unit of N, the addition of which would almost
inevitably be associated with emission of N2O, thus
cancelling part of the desired effect on climate change
(Batjes 1996).
The high Si/Al ratio in rainfed soil samples shows
dominance of siliceous materials mainly formed by quartz
sands and silt which contain only silica (Fig. 3a). Increase
in Si/Al ratio may be related to enhanced input of quartz
due to incongruent dissolution of silicate minerals and
formation of new solid phases mainly oxy-hydroxides of
Al, Fe, Mn, (Tardy et al., 2004). As a whole, the relatively
low Si/Al ratio in the perennial area may be used as indicators
of non-silicate nature of agricultural soil in the Sidhi district.
The high Fe/Al ratio indicates presence of significant
amounts of dissolved iron, as a result of chemical weathering
of soils in the northern Sidhi district (Fig.3b). The rainfed
dependent cultivation shows relatively small Fe/Al ratio
indicating low iron loss rate from primary silicates. The low
Ca/Al ratios indicate Ca is a minor constituent of agricultural
soils (Fig. 3c). The positive relationship between Ca/Mg
and Ca/Al (Fig. 4a) suggests Mg is mainly associated with
the aluminosilicate fractions (Lopez et al., 2006). The
positive statistical relationship between P/Al and Fe/Al
(Fig. 4b) indicate that the authigenic iron oxy-hydroxides
have a high capacity to adsorbed phosphorus onto their
surface (Likjlema, 1980; Lopez et al., 1996). Thus,
precipitation and accumulation of authigenic iron-oxides
causes a corresponding increase in P/Al and Fe/Al and seem
to be the main process explaining the variability observed
JOUR.GEOL.SOC.INDIA, VOL.87, FEB. 2016

SPATIAL VARIABILITY OF FLUORINE IN AGRICULTURAL SOILS AROUND SIDHI DISTRICT, CENTRAL INDIA

231

Fig. 2. The non-linear relatiosnhip between (a) SOC versus CEC, (b) SOM versus CEC.

in the agricultural soils of Sidhi district. This reflects that


the increase of phosphate concentration due to fertilizer
application over the back ground composition is linked with
the increase in iron across the same background material.
Spatial Distribution and Pollution Evaluation of Soil
Fluorine

The soil fluoride concentrations in the Sidhi district were


much higher than 320 mg/kg found in worldwide soils (Alina
and Henryk, 1984). The high concentrations may be
associated with geogenic and anthropogenic sources in
Sidhi district. Jha et al. (2008) reported total soil F
concentrations varied from 322 to 456 mg/kg in surface soils
around suburb of Lucknow. Jha (2013) studied the
geochemical characteristics and the spatial distribution of
the fluoride in the soils of Indo-Gangetic plains and found
that total fluoride ranged from 248 to 786 mg/kg with a mean
of 515.1 mg/kg.
In order to depict the spatial variability of soil fluorine
in the district, ordinary kriging procedure was used to create
the spatial distribution map. From Figure 5, it can be seen
that soil fluoride has distinct geographical distribution, with
high concentrations in the north and a small pocket in central
portion of the Sidhi district. This may be due to double
cropping system which (include paddy and wheat cropping)
demands excess fertilizer application, induced weathering

of soils and irrigation of cultivated land by surface and


groundwater rich in dissolved fluoride. In the study area,
the groundwater fluoride concentrations were beyond
permissible limit (> 1.5 mg/l) in the pre-monsoon and
monsoon seasons, however, ponds and seasonal streams
showed dissolved fluoride < 1 mg/l (Kumar, 2014).
Geomorphologically, the Sidhi area exposes the oldest rock
units of Tonalite-Trondjhemite series formed during (3.72.9 Ga) representing the ancient crust (Roy and
Bandyopadhyay, 1990). The sand gravel, bauxite, china clay,
fireclay, limestone, gold, low-grade copper, coal and graphite
minerals are extracted in the district (Mishra et.al, 2013).
Sporadic and some concentrated occurrence of granite veins
were reported in the district. Fluoride ions from these
minerals leach into the groundwater and contribute to high
fluoride concentrations (Karunakaran, 1974; Chidambarm
et al., 2012). The element fluorine is always present in
phosphatic fertilizers, soils and plants and falls by two orders
of magnitude at each stage in the sequence:
fertilizer>soil>plant (Larsen and Widdowson, 1971).
Superphosphate, which contains between 1 and 3 % F, makes
a significant contribution to fluorine content of agricultural
soils. The major part of the Sidhi district confirmed that the
spatial distribution of soil fluoride (< 400 to 600 mg/kg)
was controlled by properties of parent rocks than
anthropogenic fluoride input.

Fig.3. Spatial variability of elemental ratio (a) Si/Al, (b) Fe/Al and (c) Ca/Al.
JOUR.GEOL.SOC.INDIA, VOL.87, FEB. 2016

232

BIJENDRA KUMAR AND OTHERS

Fig.4. Linear relationship between elemental ratios (a) Ca/Mg versus Ca/Al, (b) P/Al*1000 versus Fe/Al.

Fig.5. Spatial variability of soil fluorine in Sidhi district.

The single pollution indexes (Pi) of soil fluoride were >


1 shows prevalence of soil fluoride toxicity in the Sidhi
district (Fig. 6). The lack of Pi between > 0.25 and < 1
indicates that soils are not normal according to soil health
quality index (Zhang, 2010). The Pi of soil fluoride in the
south and some pockets of northwest are found between >1
and <1.5, the Pi of north and central Sidhi vary from 1.5 to
2.5. This situation arose due to intensive cropping round
the year, a sign of local fluorine epidemic areas. Zhang et
al. (2010) reported Pi > 1 in the farmland around lead-zinc
mine in the Karst region of Guangxi, China. The
distributional patterns of high soil fluoride concentrations
were located in the limestone, shale and sandshale areas in
the Guangdong province, China (Zhu et al., 2007). Tripathy
et al. (2005) used spatial distribution of the soil fluoride
contamination index to classify the highly contaminated,
moderately contaminated and uncontaminated zones in
Nayagarh District, Orissa.
Mechanism of Soil Fluorine Enrichment

Fig.6. Spatial distribution of soil fluorine single pollution index


in Sidhi district.

The positive relationship between F and SOM (Fig. 7a),


and between F and SOC (Fig. 7b) shows significant biogenic
control of F cycle. Similarly, the positive relationship
between CEC and F reveals the occurrence of soil fluorine
exchange reactions on clay surfaces (Fig. 7c). Further, soil
F values > 400 mg/kg show greater response to the organic
matter and CEC. Rao and Pal (1978) reported that the
presence of fluoride in the plant litter and soils decreases
the growth and activity of microorganisms resulting in
greater accumulation of organic matter in the soils. However,
in some tropical soils, organically bound F (monofluorinated
compounds) may occur and affect its higher availability to
plants (Kabata-Pendias, 2011). The origin of these
compounds might be attributed to the synthesis by certain
microorganisms (Kabata-Pendias and Pendias, 1999).
Factor analysis of soil fluoride along with physicochemical parameters indicates four factors (Table 3). The
total variability accounted for four factors was 87.03 %.
JOUR.GEOL.SOC.INDIA, VOL.87, FEB. 2016

SPATIAL VARIABILITY OF FLUORINE IN AGRICULTURAL SOILS AROUND SIDHI DISTRICT, CENTRAL INDIA

233

Fig.7. Linear relationship between (a) SOM and F, (b) SOC and F and (c) CEC and F.

The first factor contributes 36.61 % of the total variance


and was strongly loaded on clay (+0.62), Al (+0.90), Fe
(+0.77), Mg (+0.89) and Mn (+0.92) indicating dominance
of clay minerals and indicates geogenic origin of the
elements in the agricultural soils, subject to various degrees
of alterations by monocropping and/or double cropping
systems. Li et al. (2007) found that the repeated events of
sawing and harvesting alter soil aggregates and accelerate
the weathering of primary and secondary minerals. The
second factor contributed 28.86 % of the total variance and
was strongly loaded on F (+0.90), SOC (+0.91), SOM
(+0.98), CEC (+0.88) and silt (+ 0.58). This reveals the
biogeochemical cycling of F takes place on reactive clay
surface rich in silicate minerals, oxy-hydroxides and organic
matter. The factor 3 explains 12.11 % of the total variance,
with loading of silt (+ 0.51), Ca (+ 0.52) and Mg (+ 0.82).
This indicates the abundance of alkali and alkali earth
elements in the soils controls the carbonate formation and
alkalinity in the agricultural soils. The factor 3 explains 9.45
% of the total variance, with loading of only pH (0.89).
Table 3. Factor analysis of physico-chemical parameters
Parameter
F
pH
SOC
SOM
CEC
Sand
Silt
Clay
Al
Mg
Si
Fe
Ca
Mn
% of variance
Cumulative%
of variance
Eigen value

Factor
2
3

-.11
.90
-.03
.07
-.15
.18
.13
.89
.17
.91
.18
.04
.12
.98
.04
.07
.29
.88
.03
.09
-.66
-.47
-.13
-.42
.38
.58
.51
.23
.62
-.07
-.60
.40
.90
.26
.04
-.19
.77
.17
.52
-.10
-.95
-.16
-.02
.04
.89
.04
.18
.13
.31
.03
.82
.23
.92
.04
.14
-.07
36.61 28.86 12.11 9.45
36.61 65.47 77.58 87.03
5.12

4.04

1.70

1.32

JOUR.GEOL.SOC.INDIA, VOL.87, FEB. 2016

Communalities
0.813
0.850
0.892
0.970
0.856
0.840
0.795
0.906
0.896
0.894
0.931
0.832
0.836
0.875

Factor scores were calculated for each sample and are


given in Table 4, which reflects the importance of a given
factor at that sample site (Dalton and Upchurch, 1978). An
extreme negative number (< -1) reflects an area essentially
unaffected by the process, and positive scores (> +1) reflect
areas that are most affected. Near zero scores demarcate an
area affected to an average degree by the chemical process
represented by that particular factor. Seven sampling
locations in the irrigated areas around northern and
central Sidhi show the factor score > +1, especially Kukraon
village (SSS6) shown by factor 2 and Ghaunghra (SSS9)
village by factor 3. The Pearson correlation also shows
geogenic sources of soil fluoride in the study area (Table
5). The strong geochemical association of F with SOM, SOC
and CEC; SOC with CEC and silt; SOM with silt and CEC;
sand with Si; silt with Ca and Mg; Al with Fe and Mn; Mg
with Fe, Ca and Mn, and Fe with Ca and Mn indicate strong
weathering of parent minerals and accumulation of soil
organic matter promote retention of the fluorine in
agricultural soils.
Table 4. Varimax rotated factor scores
Sample ID

Factor-1

Factor-2

Factor-3

Factor-4

SSS1
SSS2
SSS3
SSS4
SSS5
SSS6
SSS7
SSS8
SSS9
SSS10
SSS11
SSS12
SSS13
SSS14
SSS15
SSS16
SSS17
SSS18
SSS19
SSS20

2.162
1.022
0.677
0.652
1.762
-0.862
0.140
-0.437
-0.076
0.174
0.014
-0.954
0.593
0.009
0.577
-1.472
-0.819
-1.063
-1.566
-0.532

-0.557
0.266
0.277
-0.200
-0.737
2.314
0.833
1.460
-0.020
-0.704
-0.834
-1.265
0.224
1.079
0.661
-0.961
0.107
-2.054
0.348
-0.235

1.182
1.075
1.206
-0.282
-2.774
-0.653
0.091
0.101
1.815
1.091
-0.687
0.271
-1.099
-0.167
-0.034
0.105
-0.197
-0.164
-0.299
-0.579

-1.518
-1.012
0.190
0.712
0.321
0.968
-0.928
-0.324
1.675
1.814
1.414
0.135
-0.438
-0.417
-0.093
-1.176
-0.311
-0.778
-1.239
1.005

234

BIJENDRA KUMAR AND OTHERS


Table 5. Pearson correlation matrix
Parameter(s)
F
pH
SOC
SOM
CEC
Sand
Silt
Clay
Al
Mg
Si
Fe
Ca
Mn

pH

SOC

SOM

CEC

Sand

Silt

Clay

Al

Mg

Si

Fe

Ca

Mn

1.00
0.22
0.76
0.88
0.65
-0.31
0.40
-0.08
0.08
0.02
-0.07
0.02
0.03
-0.06

1.00
0.24
0.20
0.20
-0.27
0.26
0.09
-0.19
-0.05
0.11
0.06
0.20
-0.13

1.00
0.90
0.84
-0.52
0.62
-0.03
0.40
0.39
-0.28
0.20
0.24
0.22

1.00
0.90
-0.53
0.61
0.06
0.32
0.24
-0.28
0.22
0.17
0.17

1.00
-0.61
0.61
0.14
0.44
0.38
-0.38
0.28
0.19
0.32

1.00
-0.84
-0.50
-0.61
-0.59
0.68
-0.60
-0.40
-0.57

1.00
-0.04
0.48
0.60
-0.46
0.39
0.52
0.38

1.00
0.39
0.12
-0.51
0.47
-0.10
0.44

1.00
0.78
-0.90
0.76
0.22
0.82

1.000
-0.78
0.70
0.61
0.79

1.00
-0.88
-0.28
-0.84

1.00
0.50
0.86

1.00
0.40

1.00

CONCLUSIONS

The major cause of higher soil fluoride is not only


weathering of fluoride-rich minerals in the country rocks
but also intensive agricultural activities, a major livelihood
option, accelerated the cycling of soil fluoride. The over-all
contents of pedogenic elements reflect the highly weathered,
dominance of non-silicate forms. The spatial variability in
elemental ratios shows dominance of siliceous materials in
the rainfed soil samples. The high Fe/Al ratio indicates
significant amounts of dissolved iron as a result of chemical
weathering of soils in the northern Sidhi district. The low
Ca/Al ratios indicate Ca is a minor constituent of agricultural
soils. From the distribution of factor scores and loadings, it
is observed that the predominant retention mechanism of
fluorine on clays is supported by fine soil texture, organic
matter and organic carbon. The double cropping systems

augment fluorine toxicity in the northern and central Sidhi.


The major anthropogenic factor responsible for fluorine
enrichment is intensive fertilizer application. In nut shell,
the natural sources are weathering of parent rocks and
irrigation of cultivated land by surface water and ground
water rich in dissolved fluoride.
Acknowledgement: The authors thank the Ministry of
Human Resource Development, Government of India and
Indian School of Mines, Dhanbad for funding the research
work. We are also grateful to the Department of
Environmental Science and Engineering, ISM, Dhanbad for
providing the logistic support to carry out field monitoring
and laboratory analysis. We greatly appreciate the
anonymous reviewers for their valuable comments,
criticisms, and suggestions.

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(Received: 16 April 2014; Revised form accepted: 26 November 2014)

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