Journal of Hydrology 405 (2011) 235–247

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Journal of Hydrology
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Hydrochemical analysis of salinization for a tannery belt in Southern India

N.C. Mondal a,⇑, V.P. Singh b,c
a
Environmental Geophysics Group, National Geophysical Research Institute, Council of Scientific & Industrial Research, Uppal Road, Hyderabad 500 606, India
b
Department of Biological & Agricultural Engineering, Texas A & M University, College Station, TX 77843-2117, USA
c
Department of Civil & Environmental Engineering, Texas A & M University, College Station, TX 77843-2117, USA

a r t i c l e i n f o s u m m a r y

Article history: This paper deals with hydrochemical analysis of groundwater salinization due to untreated effluents from
Received 25 April 2010 80 functioning tanneries forming a tannery belt in Southern India. A total of 29 groundwater samples
Received in revised form 4 March 2011 were collected and analyzed. Results show that total dissolved solids (TDS), chloride (Cl), and sodium
Accepted 11 May 2011
(Na+) significantly deteriorated groundwater quality. Concentrations of analyzed hydrochemical constit-
Available online 2 July 2011
This manuscript was handled by L. Charlet,
uents were wide ranging, suggesting that hydrochemistry was controlled by several intermixing pro-
Editor-in-Chief, with the assistance of Eric C. cesses, such as saline water mixing, anthropogenic contamination, and water–rock interaction.
Gaucher, Associate Editor Therefore, cumulative probability distributions of selected groundwater were analyzed and accordingly,
waters were classified into three types, i.e., (1) type-I waters (28%): water–rock interaction; (2) type-II
Keywords: waters (17%): saline water mixing; and (3) type-III waters (55%): significant anthropogenic pollution.
Groundwater pollution An index, called ‘saline water mixing index’ (SWMI), was also developed based on the concentration of
Saline water mixing index (SWMI) Na+, Mg2+, Cl, and SO2
4 originating from the untreated tannery effluents and entering into groundwater
Tannery industries for evaluating the relative degree of salinization. Most waters affected by the effluents had SWMI val-
Southern India ues >2.5 and 1.0 based on the 1st and 2nd threshold values, respectively. Further, correlation matrix of
different chemical constituents with TDS showed that a correlation coefficient of 0.99 was observed
between TDS and Cl, Na+, and Mg2+; and 0.98, 0.97, 0.85, and 0.83, between TDS and, respectively,
SO2 2+ + 
4 , Ca , K , and NO3 . It was found that the quality of groundwater around the tannery cluster deteri-
orated mainly due to the extensive use of salts.
Ó 2011 Elsevier B.V. All rights reserved.

1. Introduction
Tannery industry is common in many parts of the world and it
pollutes groundwater and eco-systems (Sadler et al., 1994; Jordao
et al., 1997; Cassano et al., 1999; Kennedy, 1999; Bajza and Vrcek,
2001; Khwaja et al., 2001; Chattopadhyay et al., 2004; Gagneten
and Ceresoli, 2004; Apte et al., 2005; Mondal et al., 2005; Tariq
et al., 2005; Zahid et al., 2006; Gowd and Govil, 2008; Kumar
and Riyazuddin, 2008, 2010; Naeem et al., 2008; Leghouchi et al.,
2009; Mahmoud, 2009; Sankaran et al., 2010; Tarcan et al.,
2010). For example, of many areas in India, Dindigul town in
Southern India, mainly a hard rock area, is known for leather
industries some of which were established in 1939 (Peace Trust,
2000), and these industries have since been spreading. At present
more than 80 tanneries are well established, and most of these
are located along Madurai, Vattalagundu and Ponmandurai roads
passing through Dindigul town. These industries have been known
to be a considerable source of groundwater pollution and to cause
⇑ Corresponding author. Tel.: +91 40 23434700/2608; fax: +91 40 23434651.
E-mail addresses: ncmngri@yahoo.co.in (N.C. Mondal), vsingh@tamu.edu (V.P.
Singh).
health problems among local people (Paul Basker, 2000; Mondal
and Singh, 2010).
Processing of leather requires large amounts of fresh water
along with various chemicals (i.e., lime, sodium carbonate, sodium
bi-carbonate, common salt, sodium sulfate, chrome sulfate, fat li-
quors, vegetable oils, and dyes). Tanning every 10 kg of raw skin re-
quires about 350 l of fresh water (CLRI, 1990). Wastewater,
discharged for 100 kg of skins and hides, and the various chemicals
used in tanning, varies from 3000 to 3200 l. The biggest polluting
material in the tanning industry and also very difficult to get rid
off is common salt. For every 10 kg of salted hides and skins pro-
cessed, 2–3 kg of salt is removed. In addition, while pickling an-
other 1 kg of salt is removed (Peace Trust, 2000). The tannery
waste is always characterized by its strong color (reddish to dull
brown), high BOD, high pH, and high dissolved solids. Tannery
effluents, being voluminous and highly puerile, when discharged
untreated, damage the normal life of a receiving stream and seri-
ously affect the groundwater table of that locality, if allowed to
percolate into the ground for a prolonged period.
Other major chemical constituents of waste resulting from the
tanning industry are sulfide and chromium. These chemicals mixed
with water are discharged from the tanneries. They pollute ground-
water permanently and make it unfit for general consumption,

0022-1694/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhydrol.2011.05.058
236 N.C. Mondal, V.P. Singh / Journal of Hydrology 405 (2011) 235–247
including drinking and irrigation. It has been established that a sin-
gle tannery can pollute groundwater within a radius of 7–8 km
(Bhaskaran, 1977). The total dissolved solids (TDS) value in ground-
water can be as high as 39,100 mg/l. Sodium and chloride are the
dominant chemicals present in groundwater, which make it unsuit-
able for any purpose (Mondal and Singh, 2010). Among the dis-
2
solved constituents, Na+, Ca2+, Mg2+, HCO 3 , and SO4 are in excess
of standard values for either drinking or irrigation (WHO, 1984).
Of course, pollution in this area housing tanneries is also affected
by geogenic and other anthropogenic activities.
Thus, the objective of this study was to undertake a hydrochem-
ical analysis for determining the causes of groundwater quality
change in the tannery belt. In order to discriminate the effect of
salinization, an Index ‘SWMI’ was developed and applied in this
study.
2. Description of the study area
The study area is a drought prone hard rock terrain, and is lo-
cated in Southern India. It lies between 10° 130 4400 and
10° 260 4700 N latitudes and 77° 530 0800 and 78° 010 2400 E longitudes
(see Fig. 1), and encompasses an area of about 209 km2. The area is
characterized by undulating topography with hills located in
southern parts, sloping towards north and northeast. The highest
elevation (altitude) in the hilly area (Sirumalai Hill) is of the order
of 1350 m (amsl), whereas in plains it ranges from 360 m (amsl) in
the southern part to 240 m in the northern part. No perennial
streams exist in the area, except for short distance streams encom-
passing 2nd and 3rd order drainage (Mondal and Singh, 2004).
Fig. 1. Location map representing drainage pattern and sampling points.
Runoff from precipitation within the area ends in small streams
flowing towards the main Kodaganar River.
Normally, sub-tropical climate prevails over the study area
without sharp variations. The temperature increases slowly in
summer months to a maximum in May after which it drops slowly.
The mean of maximum temperature ranges from 36.5 °C to 41.8 °C
and in hills, it ranges from 7.9 °C to 21.8 °C. The mean of minimum
temperature varies from 17.4 °C to 24 °C and in hills it varies from
6 °C to 8.5 °C. The season-wise normal rainfall values during the
period from January 1971 to December 2007 shows that about
4.11% of the annual rainfall falls in winter (January and February),
15.77% in summer (March–May), 31.39% in the southwest mon-
soon period (June–September), and 48.73% in the northeast mon-
soon period (October–December). The average annual rainfall is
of the order of 905.3 mm for the period of 1971–2007.
3. Geological and hydrogeological characteristics
Geologically the study area is occupied with Archaean granites
and gneisses (Balasubrahmanian, 1980; Chakrapani and Manickyan,
1988). These formations, including granite, granodiorities, gneissic
granite and gneisses (Krishnan, 1982), are the most widespread
groups of rocks which are mainly composed of gray and pink feld-
spar with quartz grains, biotite and hornblende (Barker et al.,
2001). The formations are crossed by sets of joints and fractures,
which have also caused weathering of coarser rocks. Weathering oc-
curs due to mechanical and mostly chemical processes that take
place, while water in the fractures interacts with the formation.
The shallow hard and massive rocks are exposed mostly in the
 N.C. Mondal, V.P. Singh / Journal of Hydrology 405 (2011) 235–247
southern part. Another most dominant formation is charnokite (see
Fig. 1), which is found in the extreme southern and southeastern
parts of the Sirumalai hill acting as a no flow boundary, because it
is less weathered, jointed and or fractured (PWD, 2000). There are
many lineaments which are oriented mainly in the NNE–SSW,
NEE–SWW, and NW–SE directions, but the major lineament is run-
ning in the NNE–SSW direction for several kilometers situated
northwest of the Dindigul town along Kodaganar River (see Fig.1).
The weathered zone facilitates the movement and storage of
groundwater through a network of joints, faults, and lineaments,
which form conspicuous structural features.
Groundwater occurs mostly in weathered and fractured zones
under unconfined, semi-confined and or confined conditions
(Singh et al., 2003). In this area, the depth of bedrock varies from
4.00 to 27.68 m below the ground level (bgl), which was achieved
from geophysical survey and the existing lithologs data (PWD,
2000; Singh et al., 2003). The thickness of weather zone varies from
3.10 to 26.62 m, whereas soil thickness ranges from 0.52 to 5.35 m.
Fig. 2. Fence diagram showing shallow aquifer system.
237
The weathered zone distribution has been shown in Fench diagram
(see Fig. 2). It was confirmed that the value of weathered zone
ranges between 13.00 m and 26.62 m in the western part of Dindi-
gul town, which is highly dense with the tannery clusters. In the
French diagram, the maximum thickness of weathered zone
(=26.62 m) is encountered at VES.15, whereas the soil thickness
is 1.05 m in the center of tannery cluster.
Groundwater is being extracted from the weathered zones
through open wells, dug-cum-bore wells and bore wells for irriga-
tion, domestic and industrial purposes. Such shallow weathered
zones may not be stable sources of groundwater for meeting large
demands for groundwater (Singh et al., 2003). The depth to water
table was found to vary from 1.00 to 24.30 m (bgl) in February
2009. It was > 10.00 m (bgl) in the southern part, whereas in the
center of tannery cluster it was <3.00 m (bgl). This water level var-
ied from 1.00 to 6.00 m (bgl) around the tannery cluster and was
between 6.00 to 10.00 m (bgl) in the northern and eastern parts
of Dindigul town. The water level contour maps for February
238 N.C. Mondal, V.P. Singh / Journal of Hydrology 405 (2011) 235–247
2009 had been prepared with the aid of SURFER v.8.0 (2002), Gold-
en Software, Inc., using the kriging method (see Fig. 3). This figure
shows that the groundwater flows towards the NW direction in the
southern part, whereas in the northern part it flows in the N and
NE directions. The transmissivity varied from 10–140 m2/day,
whereas the specific yield ranged from 0.002 to 0.004 (Mondal
and Singh, 2009).
4. Materials and methods
4.1. Groundwater sampling and analysis
For evaluation of groundwater quality, 29 water samples were
collected during February 2009 from representative dug wells,
dug-cum-bore wells distributed throughout the area, which were
under use at 0.5 m below the water table, and were pumped for
more than 5 min. Methods of collection and analysis of groundwa-
ter samples followed were essentially the same as given by Browen
et al. (1974) and APHA (1985). Samples were collected in 1 l capac-
ity polythene bottles. Prior to the collection, bottles were thor-
oughly washed with diluted HNO3 acid, and then with distilled
water in the laboratory before filling bottles with samples. Each
Fig. 3. Groundwater level contours (m, amsl) with 5 m interval and flow direction (February 2009) in the tannery belt (Southern India).
bottle was rinsed to avoid any possible contamination in bottling
and every other precautionary measure was taken. WTW portable
EC and pH meters measured hydrophysical parameters, such as pH
and EC, on site. Sodium (Na+) and potassium (K+) were determined
by Atomic Absorption Spectrophotometer (AAS). Total hardness
(TH) as CaCO3, calcium (Ca2+), carbonate ðCO2 3 Þ, bicarbonate
ðHCO 
3 Þ, and chloride (Cl ) were analyzed by volumetric methods.
Magnesium (Mg2+) was calculated from TH and Ca2+ contents. Sul-
fate ðSO2 4 Þ was estimated by Spectrophotometer, whereas nitrate
ðNO 3 Þ was determined by ion chromatography and chromium
(Cr(III)) by AAS. All concentrations are expressed in milligrams
per liter (mg/l), except pH, EC and Cr(III). The EC and Cr(III) concen-
trations were expressed in lS/cm and lg/l, respectively. Analytical
precision for measurements of cations and anions, indicated by the
ionic balance error (IBE), was computed on the basis of ions ex-
pressed in me/l. The value of IBE was observed to be within a limit
of ±5% (Mandel and Shiftan, 1980; Domenico and Schwartz, 1990).
The precise locations of sampling points were also determined in
the field through the development of GARMIN 12 Channel Instru-
ment, based on the principles of Global Positioning System (GPS),
and the exact longitudes and latitudes of sampling points. The
locations of sampling points are shown in Fig.1.
 N.C. Mondal, V.P. Singh / Journal of Hydrology 405 (2011) 235–247
4.2. Statistical approaches
A wide variety of natural processes culminate in a complicated
geochemistry of certain materials, but this can still be reflected in a
set of analytical data. The probability distributions are considered
to be of great importance in dealing with geochemical data (Shaw,
1961; Sinclair, 1976). In order to discriminate the anomalous pop-
ulation whose chemistry was affected locally by salinization and/or
anthropogenic pollution from a background population, cumula-
tive probability distributions of hydrochemical parameters were
constructed. In particular, probability density functions of Cl
and NO 3 concentrations were examined in order to group collected
samples on the basis of saline water mixing and anthropogenic
pollution. If a chosen water quality parameter was affected by a
single process, the probability distribution of its concentration
formed a uni-modal normal or log-normal distribution (Tennant
and White, 1959). The cumulative probability distribution was
then linear on a probability paper. If the plots of a water quality
parameter did not form a linear distribution, the parameter was
considered to be affected by more than one population (process).
For such a case, each population was differentiated by the intersec-
tion points of two neighboring linear populations (Lepeltier, 1969;
Sinclair, 1974). Similarly, log–probability plots were adapted here
to interpret hydrochemical processes.
4.3. Saline water mixing index (SWMI)
For quantitative estimation of the relative degree of saline
water mixing in the native water, a parameter, called saline water
mixing index (SWMI), is proposed, based on concentrations of four
major ionic constituents of the tannery effluent (i.e., Na+, Cl, Mg2+,
and SO2
4 ) as:
C Na C Mg C Cl C SO4
SWMI ¼ a  þb þc þd ð1Þ
T Na T Mg T Cl T SO4
where constants a, b, c, and d denote the relative concentration pro-
portions of Na+, Mg2+, Cl, and SO2
4 between average world ground-
water and local tannery effluent, respectively, which are site
specific; C is the calculated concentration of groundwater samples
in mg/l; and T represents the calculated regional threshold values
of selected ions, which can be estimated from the interpretation
of cumulative probability curves.
5. Results and discussion
5.1. Groundwater chemistry
Statistical parameters, including minimum, maximum, mean,
and standard deviation, of different chemical constituents of the
analyzed groundwater samples (N = 29) from the study area were
computed, as shown in Table 1. Comparison of hydrochemical data
with the World Health Organization (WHO, 1984) drinking water
standards showed about 97% (N = 28), 76% (N = 22), 66% (N = 19),
55% (N = 16), and 7% (N = 2) of the samples exceeded the guideline
values for Total Dissolved Solids (TDS: 500 mg/l), chloride (Cl:
200 mg/l), sodium (Na+: 200 mg/l), sulfate (SO2 4 : 200 mg/l), and
nitrate (NO 3 : 45 mg/l), respectively. This indicated that water
quality has deteriorated significantly in the study area.
The degree of salinization in a well or a given area can be indi-
cated by an increase in the total dissolved solids and possibly an in-
crease in nearly all major cations and anions. Most parameters had
wide ranges and high standard deviations, as shown in Table 1. In
particular, the TDS value had a wide range between 499 and
39,100 mg/l (mean: 3635 mg/l). The ranges of Na+ and Cl ions
were from 43 to 6046 mg/l (mean: 518 mg/l), and 57 to
239
13,652 mg/l (mean: 1200 mg/l), respectively. The concentration of
SO2
4 also widely varied from 25 to 7154 mg/l (mean: 499 mg/l).
Such wide ranges of solute concentrations suggest that multiple
sources and/or complex hydrochemical processes acted in unison
to generate the chemical composition of groundwater. The very
high nitrate concentration (maximum: 87 mg/l) was a characteris-
tic of the groundwater. This reflects a considerable degradation of
groundwaters due to anthropogenic contamination/continuous un-
treated effluent discharge that was potentially maximized around
the tannery cluster. It is also true that NO3 has no known litholog-
ical source (Handa, 1988).
Sodium, magnesium, chloride, and sulfate ions were predomi-
nant in the tannery effluents (Peace Trust, 2000), while most fresh
waters were enriched in calcium and bicarbonate ions. Table 1
shows that groundwaters in the study area, compared with the aver-
age composition of worldwide groundwaters, were enriched in Na+,
Mg2+, Cl, and SO24 . Therefore, it is suggested that hydrochemistry
in this industrial area was controlled by several processes.
5.2. Spatial distribution of hydrochemical parameters
In order to determine the distribution pattern of the concentra-
tion of different elements and to demarcate higher concentration
zones, contour maps for various elements were generated with
the use of Surfer version 8.00, February 11, 2002 Surface Mapping
System, Golden Software, Inc. using a kriging method.
5.2.1. Total dissolved solids (TDS)
The TDS isoclines were constructed (see Fig. 4a) and its values
were more than the permissible limit (WHO, 1984), in and around
the tannery cluster, compared to other parts of the area. The trend
of TDS contours clearly showed that the pollutant was possibly
spreading in all directions as well as along the eastern side of the
river course. Major parts of TDS are consistent with HCO 2
3 , SO4 ;

2+ 2+ +
chloride of Ca , Mg , Na ; as well as KCl and NO3 as dissolved sol-
ids. These ions usually comprised about 90% of TDS (Davis and
DeWiest, 1966). Several hydrochemical processes, which may in-
clude the movement of groundwater through rocks containing
soluble minerals, concentration of water by evaporation, and con-
tamination of water due to industrial and municipal waste dispos-
als may cause a huge increase in dissolved solids. Based simply on
TDS values, the sampled groundwaters were classified and be-
longed to three categories; while most of it was brackish water
(TDS ranges: 1000–10,000 mg/l) of 76% samples (Freeze and Cher-
ry, 1997). Saline (TDS ranges: 10,000–100,000 mg/l), and fresh
water (TDS ranges: 0–1000 mg/l) types were about 4% and 21%
of the sampled groundwater, respectively. The water, with
TDS < 500 mg/l, was considered good for drinking purposes and
water with TDS > 1000 mg/l was considered unsafe to use (WHO,
1984). Following Davis and DeWiest (1966), more samples were
found unfit for drinking and irrigation purposes. A large variation
in TDS from 499 to 39,100 mg/l was more likely to be increased
due to different hydrochemical processes in the study area.
5.2.2. Sodium (Na+)
Among the cations, Na+ was the most dominant in groundwater
and its concentration (>50 mg/l) make the water unsuitable for
domestic use. High concentrations of Na+ and Ca2+ in the ground-
water were attributed to the cation exchange among minerals
(Tijani, 1994) and to the sewage concentration, in addition to the
filtration of pollutants from effluents. In the study area, Na+ varied
from 43 to 6046 mg/l. It was found that 66% of the samples had
more than permissible limits of potable water. High sodium con-
centration in irrigated areas could be due to the repeated use of
water. The iso-concentration map of sodium (see Fig. 4b) indicated
that the concentration of sodium was high (Na+ > 200 mg/l) in
240 N.C. Mondal, V.P. Singh / Journal of Hydrology 405 (2011) 235–247

Table 1
Minimum, maximum, mean and standard deviation of groundwater samples for the tannery belt in Southern India in comparison with tannery effluent water and those
worldwide average surface water and groundwater.

pH EC TDS Ca2+ Mg2+ Na+ K+ HCO

3 Cl SO2 NO
3 Cr(III)
4

Minimum 6.44 780 499 56 22 43 2 200 57 25 2 <50

Maximum 8.25 54,000 39,100 2490 1854 6046 62 640 13,652 7154 87 530
Mean 7.67 5263 3634.6 317 158.9 518 9.7 372.2 1200 499 11.6 –
Std. deviation 0.39 9682 6939.9 446.9 328.9 1080 11.8 115.4 2459 1299 17.2 –
Standards
For PLDW 6.5–8.5 – 500 75 30 200 100 200 200 200 45 50
For SW – – – 13.4 3.4 5.2 1.3 – 5.8 8.3 – –
For GW – – – 50 7 30 3 – 20 30 – –
For EW – – – 705 17,500 14,770 183 – 17,230 27,902 – –

All Ions in mg/l except EC in lS/cm and Cr(III) in lg/l, pH: log10 H+; collected 29 groundwater samples on February 2009; PLDW: Permissible limit for drinking water (WHO,
1984); SW: average surface water after Meybeck (1979); GW: average groundwater after Turekian (1977) and EW: effluent water after Peace Trust (2000).

groundwater in Dindigul town and its surrounding areas, but was
comparatively less in the eastern side of Kodaganar River.
5.2.3. Chloride (Cl)
Abnormal concentrations of Cl (ranges: 57 to 13,652 mg/l) were
found in groundwater, and one possible source might be the tan-
nery, where common salt was used as a raw material (Peace Trust,
2000). A contour map of Cl (see Fig. 5a) showed that the Cl values
were very high in the various locations close to the residential areas
and also in places, where the density of tannery was significant. The
gradient of Na+ and Cl concentrations were not in good agreement
with the topographic pattern. In terms of magnitude and direction,
they were randomly distributed depending upon the locations of
irrigation land, residential area and tannery cluster.
5.2.4. Chromium (Cr(III))
In general, the prime cause of chromium pollution in ground-
water is chromite (Cr2O4), an ore of chromium (Thomas et al.,
2001). The background chromium value was measured below per-
missible limit of drinking water (WHO, 1984). But chromium was
used for making dyes, which are used in the tannery industries
(Ramana et al., 1992; Zhao et al., 2005). The harmful hexavalent
chromium (Cr(VI)) was obtained below the permissible limit
(0.05 mg/l). Gravity, permeability and wetness of the aquifer mate-
rial and miscibility of the pollutant in groundwater controlled the
mobility of pollutants. Fairly high incidence of rainfall (905.3 mm
annually) intercepted by consecutive drought years was character-
istic of the study area. Pollutant impregnated materials, e.g., solid
and liquid wastes, leaching through weathered granite infiltrated
into the substratum and reached the water table. The percolation
by seepage water is a slow process and likely attains greater mobil-
ity with the lapse of time in wet seasons. Since most of the efflu-
ents of tanneries were discharged into streams/tanks, chromium
was mostly washed off and the amount retained on the bottom
of streams/tanks was minimal (Singh et al., 2003). This could be
one of the reasons for its low concentration in shallow aquifers.
The other reason could be that in recent years pre-treatment of
effluent caused the Cr(III) concentration to a minimum level. Re-
sults of analysis however showed other concentrations (presented
in Table 1) harmful for drinking and irrigation purposes. Although
samples for chromium had been collected from groundwater, it
had been found that the maximum concentration of trivalent chro-
mium (Cr(III)) was 530 lg/l. A contour map was also prepared for
Cr(III) (see Fig. 5b) which indicated only the tannery cluster af-
fected by Cr(III) plume more than the permissible limit of 50 lg/l
(WHO, 1984).
5.3. Intervention of hydrochemical processes
Most of the hydrochemical parameters obtained in this study
generally exhibited log-normal density distributions. It should be
noted that Na+, Cl and, SO2 4 were major components of the tan-
nery effluent, while NO 3 was among the best indicators of anthro-
pogenic pollution (Handa, 1988). However, the occurrence of an
anomalous population as a ‘tail’ on the distribution suggested that
groundwater chemistry was controlled by several intermixing pro-
cesses. The frequency plots of Na+, Mg2+, Cl, and SO2 4 data showed
a log-normal distribution but had a tail at high concentration
ranges. This indicated that a few numbers in samples with high
Na+, Mg2+, Cl, and SO2 4 concentrations can be attributed to an
anomalous population whose chemistry was locally affected by
the effluent water mixing and others. The frequency distribution
of log NO 3 data showed a good normal distribution, except for a
few data points in samples with higher concentrations. This means
that the samples forming a tail on the distribution diagram can be
considered due to anthropogenic contamination.
Cumulative probability distributions of Na+, Mg2+, Cl, and SO2 4
are shown in Figs. 6a–d. There are two individual intersection
points in the cumulative probability plots, which can be considered
as regional threshold values and highly impacted threshold values
for differentiating the samples with the effects of geogenic, anthro-
pogenic and saline water mixing. The first approximate regional
threshold values obtained were 160 mg/l for Na+, 56 mg/l for
Mg2+, 191 mg/l for Cl, and 211 mg/l for SO2 4 (see Fig. 6). Simulta-
neously, the second estimated highly impacted threshold values
were 424, 136, 390, and 310 mg/l for Na+, Mg2+, Cl, and SO2 4 ,
respectively. Sample S-7, 8, 12, 16, and 17, located nearby down-
stream of and in the tannery cluster, fell on the third segment on
all cumulative probability curves for concentrations of Na+, Mg2+,
Cl, and SO24 in groundwaters, which were highly affected by tan-
nery effluents. In case of NO 3 , the cumulative probability curve dis-
tribution (Fig. 6e) had shown only one regional threshold value of
15 mg/l which had discriminated highly impacted groundwater
samples by agricultural activity (in well S-29), and untreated tan-
nery effluent (in well S-17).
In particular, probability distributions of Cl and NO 3 concentra-
tions were examined in order to cluster the collected samples on the
basis of saline water mixing and anthropogenic pollution, because
the approximate trends were reciprocal after the regional threshold
values. The two parameters were considered to mostly reflect the ef-
fects of saline water mixing and anthropogenic pollution, respec-
tively. The inflection points obtained were 191 mg/l for Cl and
15 mg/l for NO 3 (see Figs. 6c and e). Using these parameters, the col-
lected groundwater samples (N = 29) were grouped into two major
populations as (1) type-I waters (28%) that were relatively poor in
both Cl and NO 3 , representing natural groundwater; (2) type-II
waters (72%) which were enriched in Na+, Mg2+, SO2 
4 , and Cl , indi-
cating a considerably more influence of tannery industries, anthro-
pogenic as well/agricultural activities; among this (3) type-III
waters (17%) enriched in Cl, reflecting strong effects of nearby
the tannery disposal. This classification would be useful to discrim-
inate the source of salinization, to estimate the level of saline water
 N.C. Mondal, V.P. Singh / Journal of Hydrology 405 (2011) 235–247 241

Fig. 4. Contours map (a) TDS (mg/l) and (b) Na + for February 2009.

mixing and anthropogenic pollution, and ultimately to properly
manage groundwater resources in the study area.
5.4. Computation of saline water mixing
The first threshold (T) values were calculated for the tannery
belt as 160 mg/l for Na+, 56 mg/l for Mg2+, 191 mg/l for Cl, and
211 mg/l for SO24 (see Fig. 6). The relative concentration propor-
tions of Na+(=a), Mg2+(=b), Cl(=c), and SO24 ð¼ dÞ between average
world groundwater and tannery effluent were estimated and these
values are a = 0.20, b = 0.04, c = 0.12 and d = 0.10 for Na+, Mg2+, Cl,
and SO24 , respectively. Using these relative concentration and T
values with the aid of Eq. (1) the SWMI values of individual wells
were calculated. It was found that almost all of the type-I waters
242 N.C. Mondal, V.P. Singh / Journal of Hydrology 405 (2011) 235–247

Fig. 5. Contours map (a) Cl (mg/l) and Cr(III)(lg/l) for February 2009.

(at well S-5, 9, 21, 23, 24, 27, and 28) had SWMI values <0.50, ex-
cept for sample S-14 (SWMI value = 0.53), while type-II and type-
III waters had >0.50. Among them, five groundwater samples (their
TDS values ranged from 4782 to 39,100 mg/l) belonged to type-III
waters, corresponding to about 17% of the analyzed samples, and
could be considered to be significantly affected by the tannery
effluents. Fig. 7a shows the spatial distribution of the SWMI values
calculated based on the first threshold values for the study area.
Groundwater was affected with salination by the tannery effluent
having more than SWMI = 2.50 (according to the first threshold
values).
The second calculated threshold (T) values were 424 mg/l for
Na+, 136 mg/l for Mg2+, 390 mg/l for Cl, and 310 mg/l for SO2 4
(see Fig. 6). Using these T-values, results of the calculated SWMI
 N.C. Mondal, V.P. Singh / Journal of Hydrology 405 (2011) 235–247
(a)
(c)
(e)
Fig. 6. Cumulative probability distribution for (a) Na+, (b) Mg2+, (c) Cl, (d) SO2
values showed that almost all of type-I waters had SWMI
values 60.24 with TDS values of 499–1270 mg/l, while type-II
and type-III waters had SWMI > 0.24. In this case five groundwa-
ter samples (i.e., S-7, 8, 12, 16, and 17) had SWMI values >1.00
which tend to be preferentially located within the tannery clus-
ters (see Fig. 7b). Based on the SWMI, there are three types of
groundwater, i.e., type-I dominated by rock water interaction,
type-II for water polluted by anthropogenic and agricultural
activities, and type-III highly contaminated by the untreated tan-
nery effluents.
5.5. Mechanisms controlling groundwater chemistry
The Gibbs diagrams, representing the ratios of Na+:
(Na+ + Ca2+) and Cl: (Cl + HCO 3 ), as a function of TDS are widely
employed to assess the functional sources of dissolved chemical
constituents, such as precipitation, rock, and evaporation domi-
nance (Gibbs, 1970). Chemical data of groundwater samples were
plotted on the Gibbs diagram (see Fig. 8). Eight groundwater sam-
ples (i.e., S-5, 9, 14, 21, 23, 24, 27, and 28) suggested that the
chemical weathering of rock-forming minerals were influencing
the groundwater quality, whereas about 17% samples (i.e., S-7,
8, 12, 16, and 17) represented the evaporation dominance (see
Fig. 8). These groundwaters falling in the evaporation dominance
were collected from open wells located in the tannery cluster.
Evaporation increased salinity by increasing Na+ and Cl in rela-
tion to the increase of TDS. This was also supported by significant
positive correlation coefficients amongst TDS, Na+ and Cl (see
Table 2). It was observed that the remaining data were laid be-
tween rock-evaporation dominance boomerangs. However, no
data plotted in the lower-right side of the boomerang, meaning
243
(b)
(d)

4 , and (e) NO3 .
that atmospheric precipitation was not an important process in
determining the chemical composition of these waters. Anthropo-
genic activities (i.e., agricultural activity and irrigation-return
flows) also influenced evaporation by increasing Na+ and Cl,
and thus TDS.
5.6. Cross plots and correlation matrix
In general, fresh water was dominated by calcium, whereas sal-
ine water was affected by common salts in the tannery effluent
(Mondal et al., 2005, 2008). The Ca2+/Na+ and HCO 
3 /Cl molar ra-
tios provided an indicator for demarcating groundwater types. To
evaluate the effect of saline water mixing, the TDS versus inter-io-
nic ratios (i.e., Ca2+/Na+ and HCO 
3 /Cl ) diagrams were examined.
There was a specific trend in a TDS vs. Ca2+/Na+ diagram (see
Fig. 9a), suggesting that Ca2+/Na+ ratios were controlled by several
processes in addition to saline water mixing. In the TDS vs. HCO 3/
Cl diagram (see Fig. 9b), on the other hand, a strong negative cor-
relation between the two variables was visible. For type-I (TDS
ranges: 499–1270 mg/l) molar ratios of Ca+/Na+ and HCO 
3 /Cl var-
ied from 0.41 to 4.30 and 0.97 to 3.16, respectively, whereas from
0.33 to 1.30 and 0.009 to 0.26 for type-III (TDS ranges: 4782–
39,100 mg/l). This suggested that high TDS groundwaters were
typically enriched in chloride ion, mainly due to saline water mix-
ing (generated by the tannery industries).
Correlations of TDS with different chemical constituents of 29
groundwater samples were also calculated, as presented in Table
2. It had shown that the highest correlation had been found be-
tween Na+, Mg2+ and Cl with TDS, which were on the order of
0.99 (see Fig. 10a and b). The correlation coefficients for other con-
stituents, such as SO2 2+ + 
4 , Ca , K , and NO3 , declined progressively
244 N.C. Mondal, V.P. Singh / Journal of Hydrology 405 (2011) 235–247

Fig. 7. Spatial distribution of calculated (a) 1st SWM Index and (b) 2nd SWM Index in the tannery belt, Southern India.

with values of 0.98, 0.97, 0.85, and 0.83, respectively. This indicates were 0.99, 0.98, 0.98, and 0.85, respectively (see Fig. 10c and d).
proportionately diminishing contributions of these constituents to The discussion shows that groundwater was extensively damaged
groundwater pollution. Strong correlations were also found be- due to the anthropogenic pollution and excessive use of salts in the
tween Mg2+ vs. Cl, Na+ vs. Cl, Ca2+ vs. Cl, and K+ vs. Cl which tannery belt.
 N.C. Mondal, V.P. Singh / Journal of Hydrology 405 (2011) 235–247 245

Fig. 8. Gibb’s diagram of collected groundwater samples from the tannery belt.

Table 2
Correlation matrix among different chemical constituents of groundwater samples collected from the tannery belt, Southern India.

pH EC TDS TH Ca2+ Mg2+ Na+ K+ HCO

3 Cl SO2 NO
3
4

pH 1.00 – – – – – – – – – – –
EC 0.65 1.00 – – – – – – – – – –
TDS 0.67 1.00 1.00 – – – – – – – – –
TH 0.67 0.99 0.99 1.00 – – – – – – – –
Ca2+ 0.68 0.97 0.97 0.99 1.00 – – – – – – –
Mg2+ 0.65 0.99 0.99 0.99 0.96 1.00 – – – – – –
Na+ 0.62 0.99 0.99 0.97 0.94 0.97 1.00 – – – – –
K+ 0.63 0.86 0.85 0.84 0.81 0.85 0.86 1.00 – – – –
HCO 3 0.06 0.24 0.24 0.31 0.33 0.28 0.18 0.07 1.00 – – –
Cl 0.65 0.99 0.99 0.99 0.98 0.99 0.98 0.85 0.28 1.00 –
SO2 0.64 0.99 0.98 0.98 0.95 0.98 0.98 0.86 0.23 0.98 1.00 –
4
NO3 0.72 0.83 0.83 0.83 0.80 0.83 0.83 0.94 0.08 0.82 0.85 1.00

Total 29 samples collected on February 2009.

(a) (b)

Fig. 9. Relationship between TDS and molar ratios of (a) Ca2+/Na+and (b) HCO 
3 /Cl .
246 N.C. Mondal, V.P. Singh / Journal of Hydrology 405 (2011) 235–247
(a)
(c)
Fig. 10. Cross plots of (a) Na+ & Mg2+ with TDS, (b) Cl & SO2
4 with TDS, (c) Mg
6. Conclusions
The hydrochemical study for a tannery belt in Southern India
indicates that various processes, including mixing of tannery efflu-
ents, anthropogenic contamination, and water–rock interaction,
influence groundwater pollution. The concentrations of total dis-
solved solids (TDS), chloride, and sodium exceed drinking water
standards (WHO, 1984) in about 97%, 76%, and 66% of the collected
samples (N = 29), respectively. This indicates that groundwaters
are significantly degraded and suffer from extensive salinization.
Spatial distributions of TDS, Na+, Cl, and Cr(III) show that their
magnitudes are comparatively high in and around the tannery
clusters located between Dindigul town and Kodaganar River.
The harmful hexavalent chromium (Cr(VI)) is within permissible
limits, but Cr(III) plume exits in the tannery cluster.
The cumulative probability distributions of Na+, Mg2+, Cl, and
SO2
4 show two individual intersection points with three different
segments, which indicate three different types of groundwater.
The first segment represents the background groundwater concen-
tration of the study area, whereas second and third segments for
anthropogenic and saline water mixing from the tannery effluents,
respectively. These classifications are confirmed by the proposed
parameter called saline water mixing index (SWMI).
Two threshold values are obtained in three different significant
stages. The first threshold values obtained are 160 mg/l for Na+,
56 mg/l for Mg2+, 191 mg/l for Cl, and 211 mg/l for SO24 . Consec-
utively, second calculated highly impacted threshold values are ob-
tained as 424, 136, 390, and 310 mg/l for Na+, Mg2+, Cl, and SO24 ,
respectively. The calculated SWMI values based on 1st and 2nd
threshold values are >2.50 and 1.00, respectively, for the ground-
water samples (i.e., S-7, 8, 12, 16, and 17) having TDS ranges from
4782 to 39,100 mg/l, but SWMI values for the samples (i.e., S-5, 9,
21, 23, 24, 27, and 28) are <0.5 and 60.24 with TDS ranges of 499 to
1270 mg/l. This indicates that there are three types of groundwa-
ter, i.e., type-I dominated by rock–water interaction, type-II for
water polluted by anthropogenic activities, and type-III highly pol-
luted by the untreated tannery disposal. This is also indicated on
the Gibbs diagrams as well as cross plots of molar ratios of Ca2+/
Na+ and HCO 
3 /Cl with total dissolved solids.
(b)
(d)
2+
& Na+ with Cl, and (d) Ca2+ & K+ with Cl.
Thus, the saline water mixing index of the tannery belt quanti-
tatively indicates the degree of salinization influenced by several
processes and could be used for any tannery belt. The information
obtained represents a base for future hydrochemical work that will
help in the planning, protection, decision-making regarding
groundwater management especially for the better control of both
saline water mixing from the tannery industries and other saliniza-
tion or contamination sources.
Acknowledgments
This work was performed, in part, under the BOYSCAST Fellow-
ship of the first author funded by Department of Science and Tech-
nology (Government of India), New Delhi (Ref. No. SR/BY/A-05/
2008, Date: 16–19th January, 2009) and also partially funded by
the Council of Scientific and Industrial Research (CSIR), New Delhi,
India on Groundwater Programme. Professor Gultekin Tarcan, Do-
kuz Eylül University, Turkey, had critically reviewed the article.
The authors are thankful to them.
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