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Aquatic Procedia 4 (2015) 1119 – 1125

INTERNATIONAL CONFERENCE ON WATER RESOURCES, COASTAL AND OCEAN

ENGINEERING (ICWRCOE 2015)

An Evaluation of Hydrogeochemistry of Groundwater in Upper

Vellar Sub – Basin using Mineral Stability and Solute Transport
Modelling
Saravanan Ka, Srinivasamoorthy Ka*, Prakash Ra, Gopinath Sa and Suma C.Sa
a
Department of Earth Sciences, Pondicherry University, Puducherry

ABSTACT

The absence of perennial river, semi arid climatic condition and growing neediness of water increased the usage of
groundwater. In the area proposed for the study, all the water necessities are fulfilled with groundwater. Hydrochemistry of
groundwater is influenced by geogenic and anthropogenic sources. Hence to assess the chemical characteristics of groundwater in
the study area, a total of 74 groundwater samples were collected and analyzed for physical parameters such as pH, conductivity
and Total Dissolved Solids along with major cations and anions using standard procedures. The dominant cations and anions
were, Na ˃ Ca ˃ Mg ˃ K and HCO ˃Cl> NO3 ˃ F ˃ PO4 ˃SO4 respectively. Hydro chemical facies demarcated were NaCl ,
CaNaHCO3 , CaHCO3 and CaMgCl. The facies suggests ionic exchange, dissolution, silicate weathering and anthropogenic
sources are responsible for the variation in groundwater chemistry of the study area. The silicate group minerals show over
equilibrium conditions sulphate and halide group minerals indicate under saturation condition. The saturation values trend
increases along the flow path. Identified hydro geochemical process were verified and quantified using hydro geochemical
inverse mass-balance modeling (net geochemical reactions along a flow path,PHREEQC,WATQ4F).
© 2015
2015 The
TheAuthors.
Authors.Published
Publishedbyby Elsevier
Elsevier B.V.
B.V. This is an open access article under the CC BY-NC-ND license
Peer-review under responsibility of organizing committee of ICWRCOE 2015.
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of organizing committee of ICWRCOE 2015
Keywords: Mineral stability; Inverse Geochemical modelling; Upper vellar sub-basin

*Corresponding Author
Email address: moorthy_ks@yahoo.com

1. Introduction

The utilization of groundwater has been increasing due to changes in natural and human activities, the

2214-241X © 2015 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of organizing committee of ICWRCOE 2015
doi:10.1016/j.aqpro.2015.02.142
1120 K. Saravanan et al. / Aquatic Procedia 4 (2015) 1119 – 1125

increasing water demand has triggered the alteration of water quality by various factors including geological and
anthropogenic sources. Hence, a proper appraisal of groundwater chemistry will give information regarding
changes in groundwater phases, evolution and flow directions (Rajmohan and Elango 2004). The groundwater
chemistry alters due to spatially variable recharge governed by micro topographic controls, interaction with aquifer
matrix and/or mixing of different groundwater along the flow paths in the subsurface (Domenico, 1972; Wallick
and Toth, 1976). The presence of cations and anions are mainly derived from weathering of primary and secondary
minerals (Freeze and Cherry, 1979; Barhtarya, 1993). The groundwater utilized for human utilities and its recycling
will rapidly increase the mixing of solutes by repeated circulations in addition to evaporation and
evapotranspiration (Native and Smith, 1987; Elango and Ramachandran, 1991). Hence an attempt has been made in
the upper velar sub-basin to isolate the regional hydrochemistry of groundwater using major ion chemistry and
modelling approach.

2. Study Area

The upper vellar river fall between 78°14̓ -78°58̕ E longitude and 11°24̕ -11°53̕ N latitudes covering a total
area of 1804km2 The river originate at kalrayan hills of Salem district of Tamilnadu and it runs 74 km towards East
and configures with swedha river which one of the tributary of vellar. The study area experiences tropical climate
with annual temperatures ranges between 20°c to 40°c. The annual rainfall varies between 640mm to 1100mm with
major contribution from North East monsoon followed by South West monsoon (CGWB2010).

Fig.1. Study Area Map

Regional Geology
The geology of the study area is predominantly occupies by crystalline rocks of Archean age encompassing
litho units like hornblende biotitic gneiss, Charnockites, basic rocks, Pyroxene granulites and patches of Mylonite
(GSI, 2011) the predominant rock is Gneiss characteristic rock, following charnokites. The rocks of the study area
are highly weathered, jointed, fractured and covered by recent valley fills and soil covers.

Hydrogeology of the study area

In the study area, crystalline hard rocks on the basis of its weathering condition are classified as top soil,
weathered and fractured condition. The groundwater occurs mainly in secondary porosities such as fractured,
lineation and foliations and water is extracted from dug well, tube well and deep wells for varied purposes.
 K. Saravanan et al. / Aquatic Procedia 4 (2015) 1119 – 1125 1121

3. Material and Method

Groundwater samples were collected from dug wells and bore wells during in the month of June -2014. A
total of 74 ground water samples were collected using standard sampling procedures and analyzed for pH,
Conductivity (EC) and Total Dissolved Solids (TDS) along with major ions using standard procedure. The second
stage of analysis involved geochemical modelling using PHREEQCI (Parkhurst and Appelo, 1999) package for
major element simulation for mineral Saturation Index (SI) using specific ions of interest. PHREEQCI uses the mass
balance approach to calculate the stoichiometry of chemical reactions responsible for change in water chemistry
(Plummer and Back,1980).The SI of minerals were obtained using the equation
SI = log IAP/kt
Where IAP is the ion activity product of the dissociated chemical species in solution, kt is the equilibrium solubility
product for the chemical involved at the sample temperature. SI of minerals is of prime important for evaluating the
extent to which water chemistry is controlled by equilibrium with solid phases (Appelo and Postma, 1996). If SI <0,
water is under saturated (S.Chidambaram.et, al.2012), An SI=0 means equilibrium whereas an SI > 0 means super
saturation. The stability diagram which shows the dynamic equilibrium between the solutions and coexisting solid
phases is frequently applied to interpret the geochemical behaviour of natural water in terms of water – rock
interactions (Gerrels and Christ, 1965). Stability diagrams are the basic component for evaluating equilibrium
condition of water with respect to various aquifer mineral phases.

Water Facies
Hydro chemical facies interpretation is a tool for determining the flow pattern, origin of chemical spices of
ground water masses (Srinivasamoorthy et al, 2010). The Piper diagram (Piper, 1953) is used to infer hydro
chemical facies. The hydro chemical facies identified were NaCl > mixed CaMgCl > mixed CaNaHCO3 >
CaHCO3.The faceis are mainly mixed and NaCl facies indicate prolonged water- rock interaction and matured stage
of water condition.

Fig. 2 Piper diagram

Thermodynamic Stability

One of the process of dissolution of aquifer matrix by water is controlled by thermodynamic energies hence
the study of stability condition gives the insight of dissolution process in the aquifer. Thermodynamic plotting of
[Na]/H,[K]/H,[Ca]/H,[Mg]/H are plotted for groundwater samples in the study area as a function of [H 4SiO4].In the
plot for Ca the samples fall in kaolinite field indicating impact of dilution and plot for Mg shift of stability from
kaolinite to chlorite is indicating the formation of new clay minerals due to supply of excess cations and silicates
from the aquifer matrix. The plot of K-silicates indicates incongruent dissolution of kaolinite and formation of
muscovite, due to the shift of samples from kaolinite to muscovite field and plot of Na fall in the kaolinite stability
field indicating Na- feldspar dissolving incongruently to produce kaolinite and dissolved products as dissolution of
feldspars continues the value of (SiOH) 4 and Na/ (H) increase and water chemistry moves towards montmorilinite
1122 K. Saravanan et al. / Aquatic Procedia 4 (2015) 1119 – 1125

field. The reactions by which the incongruent dissolution takes place in the presence of different feldspars along
with their end products are as follows.

Albite Kaolinite
NaAlSi3O8 +H2O +CO2 Na+ + HCO3- +H4SiO4 +AlSi2O5 (OH)4

Anorthite Kaolinite
CaAl2SiO8 +H20 +CO2 Ca2+ + HCO-3 +Al2SiO5 (OH)4

Fig: 3 Stability diagram

Silicate weathering and solute distribution

Silicate weathering is one of the key geochemical process controlling the major ions chemistry of the
groundwater especially in hard rock aquifer (Mackenzie and Garrells,1965). The mechanism of silicate weathering
can be understood by estimating the ratio between Na++K+ and total cations (TZ+). Majority of samples in the study
area plot above the trend line Na++K+ =0.5Tz+ Fig(4a) signifies the contribution of silicate weathering due to the
abundance of Na+ and K+ in groundwater (Stallard and Edmond, 1983).The ratio plot for Ca Vs Mg indicates the
clustering of sample points with reference to equiline fig(4b) signifying the dominance of both Ca 2+ and Mg2+ ions
in the groundwater samples of the study area. Further in the plot for Ca+Mg Vs HCO3+S04 the samples clusters
above the equiline fig:4(c) indicating the dominance of alkaline earth over bicarbonate, signifying the process of
silicate weathering in the study area. In the plot for Na vs. Cl fig4(d) majority of samples fall below the 1:1 equiline
 K. Saravanan et al. / Aquatic Procedia 4 (2015) 1119 – 1125 1123

line, signifying the dominance of Na+ derived from the silicate weathering from the litho units and minor inferences
along the Cl- zone might be due to the anthropogenic activities (Srinivasamoorthy.K et, al.,2009)

Fig: 4 Ratio plots

4. Geochemical Modelling

Geochemical modelling is handy tool for understanding the flow direction trend of groundwater. Same
chemical composition of two water samples is not a proof of hydrodynamic connection. However a hydraulic
connection is assumed from the point of groundwater recharge to discharge (L.Andre and M.Franceschi, 2004). In
this study PREEQCI (Parkhurst and Appelo, 1999) has been used to study the speciation and saturation index of
minerals dissolved in ground water environment using available geochemical data sets to isolate the groundwater
flow direction. In complex crystalline terrain like the present study area, the water flow is influenced by factors like
elevation, secondary porosity like lineation, foliation and fractures (Balaji and Ramasamy, 2005). Four sample
points were located considering all significant parameters such as geology, elevation and slope of the study area.
The saturation values are noted in the (Tab: 1) found to be increasing along the groundwater flow path.
1124 K. Saravanan et al. / Aquatic Procedia 4 (2015) 1119 – 1125

Table:1 Saturation index values

S.NO MINERAL SATURATION LOCATION (SI) LOCATION(SI)

INDEX(SI) 7 AND 69 4 AND 22

1 Quartz 2.14 , 2.22 2.52, 2.43

2 Chrysotile -5.34 ,5.39 -7.31, 7.71

3 Chalcedony 1.71, 1.79 2.09, 2

4 SIO2- (Amorphous) 0.87, .95 1.25, 1.65

5 Aragonite 1.87, 3.07 1.13, 3.4

6 Calcite 2.02, 3.22 1.27, 3.55

7 Dolomite 3.23, 6.39 1.79, 7.09

8 Gypsum -1.8 , -2.04 -2.11,-1.53

9 Hydroxy apatite 4.19, 13.27 0.82, 10.16

10 Anhydrite 4.91, 13.27 -2.32, -1.74

11 Fluorite 2.84, 2.41 1.68, 1.5

12 Talc 1.8, 12.68 0.58, 15.4

13 Sepiolite -.92, 6.36 -1.61, 8.25

14 Sepiolite(d) -3.82, 3.46 -4.51, 5.35

15 Halite -3.64, -3.32 -3.76, -3.64

5. Discussions

The groundwater in the area is generally of Na-Cl type fig (2) with concentration of Na 2+ and Cl- as (112 -
382mg/l) and (53 -390mg/l) respectively. The major processes controlling the groundwater chemistry were
identified mainly due to water rock reaction and associated geochemical process like adsorption, dissolution and
ionic exchanges. In the recharge area silicate weathering from feldspars of the litho units were found to be
influencing the water chemistry contributing ions like Na2+,Ca2+ and K+. The presence of HCO3 in groundwater is
mainly due to the interaction of groundwater with vegetation, action of atmospheric CO2 and soil micro organisms.
The presence of Cl- might be due to the anthropogenic activities. The existence of NO3- and SO4- are mainly due to
the practice of agricultural activities in study area. The saturation index of the silicate, carbonate, Fluoride and PO4
phases show over saturation with under saturation of halide and sulphate group of mineral phases. The groundwater
flow direction assumed from sample locations (4, 7, 22, and 69) shows the significant increase of mineral phases
 K. Saravanan et al. / Aquatic Procedia 4 (2015) 1119 – 1125 1125

from recharge area to discharge area indicating the continued interaction between the groundwater and aquifer
matrix.

6. Conclusion

The dominance of cations like Na, Ca, Mg and lower K indicates the significance of silicate weathering and
the resistance of potassium minerals to weathering and the concentrations of PO4 and SO4 might have been derived
from sources like agricultural influences since no dominant litho units for the contribution of the same have been
identified in the study area. The source for HCO3 might have been attributed from sources like atmospheric CO2
and soil organic materials. The sources for ions like Cl- and NO3- might have been derived from anthropogenic
activities like agricultural influences. The water facies identified were NaCl, Ca-Na-HCO3, Ca-HCO3 and Ca-Mg-
Cl. The water stability mainly fall in kaolinite field indicating the effective dissolution of silicates from feldspar
group of minerals. The ionic ratio plots suggest silicate weathering, carbonate dissolution and ionic exchange
processes to be activated in the study area. Increase in SI of minerals along the groundwater flow path signifies the
influence of litho logical sources for the alteration in the water chemistry.

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