Dr.

Siya Soummya
Assistant Professor in Civil Engineering
College of Engineering Pune-5

Groundwater chemistry is a function of recharge and the input chemistry of the rain, which gets
transformed as it moves through the soil matrix. Apart from mineral transformations, anthropogenic
activities are other external factors, which affect the groundwater chemistry. Stream – aquifer
interactions alter the chemistry of groundwater in the regions nearer to the stream. A study is carried
out to analyse the hydrogeochemical behavior under the influence of lithologic, precipitation and
anthropogenic controls in the upper Cauvery basin. This is followed by the analysis of contributions
made by the components of the hydrogeochemical cycle. A geochemical model is developed, which is
used to study the spatiotemporal variations in groundwater chemistry of a silicatic rock group in a small
experimental watershed.
Upper Cauvery river basin (~ 10000 km ) is selected for the analysis, which stretches along
2

three climatic zones – ‘semi-arid’ (500 – 800 mm/year rainfall), ‘sub-humid’ (1000 - 1200 mm/year)
and ‘humid’ (1200 – 1500 mm/year) zones. The basin is mainly formed by granitic gneissic group of
rocks with some traces of amphibolites and charnockites. Groundwater is observed to occur either in
the saprolite or in the deeper hard rock zone based on the geomorphology even at the scale of a small
watershed. Parts of this basin are under canal irrigation and are drained by Kabini and Cauvery Rivers.
Groundwater – surface water interactions play an important role in these regions. Irrigation with
different levels of intensities is practiced through groundwater in the upland areas. Observation wells
considered in these three zones are classified into four classes based on the mean annual groundwater
fluctuations. Wells in each of these four classes are further classified into ‘shallow’ and ‘deep’
categories based on the depth to groundwater.
Analysis of the groundwater chemistry in the basin (widely spread with 120 wells in the three
zones) shows a gradient in chemistry along the climatic gradient with sub-humid zone bridging
between the semi-arid and humid zones. Ca/Na and Mg/Na ratios decrease from humid zone (unimodal
rainfall) to semi-arid (bimodal rainfall) zone since both Na and Mg concentrations in groundwater
increase along this gradient. These elements are mainly controlled by weathering reactions. Apart from
the weathering of Ca, calcrete formations also play an important role in the semi-arid zone. Ion
exchange process cycles between Cl and SO and between Ca and Na. Dissolution of CaCO , silicate
4 3

weathering and evaporation are the major mineralogical reactions.

Variations in Na/Cl and Ca/Cl molar ratios indicate that shallow wells have higher molar ratios
with higher variance than the deeper wells. Semi-arid zone is more silicaceous (higher Na/Cl value)
than the humid zone, which has higher Ca/Cl ratio (~ 14). Effective seasonal patterns are identified
using ‘recharge – discharge’ concept based on the rainfall intensity. Wells under normal scenario have
low Na/Cl and Ca/Cl ratios in the ‘recharge period’ than in the corresponding ‘discharge period’
(dilution chemistry). Wells in the relatively higher pumping regions, which receive sufficient annual
recharge exhibit dilution chemistry though groundwater level fluctuations are higher. However, wells
in regions with insufficient recharge show ‘anti - dilution’ chemistry. Thus, the ‘recharge – discharge’
concept is useful in identifying the pumped wells from deeper wells and helps in characterizing the
anthropogenic effects on the basin.

Rainfall and its chemistry are to be analysed to understand the groundwater chemistry. Hence, data
from various monitoring stations in India are analyzed for assessing the influence of several major
factors such as, topographic location of the area, its distance from sea and annual rainfall. These
stations are categorized as ‘urban’, ‘suburban’ and ‘rural’. pH, HCO , NO and Mg concentrations have
3 3

not changed much from coast to inland. On the other hand, SO and Ca concentrations changes are
4

subjected to local emissions.

 Cl and Na (marine elements) originate solely from sea and a model is developed to quantify
the variation in concentration of these elements under the influence of inland distance and annual
rainfall. Non – linear regression model for the various categories shows that both rainfall amount and
precipitation chemistry follow a power law reduction with distance from sea. Cl and Na decrease
rapidly for the first 100 km distance from sea, then decrease marginally for the next 100 km and then
later stabilize. Regression parameters estimated for different cases are found to be consistent (R ~ 0.8).
2

Variation in one of the regression parameters accounts for the effect of urbanization. Model developed
for precipitation chemistry is validated using stations from the southern peninsular region of the
country. Model predictions are found to be in good correlation with observations with a relative error
of ~ 5%.
This relationship between the three parameters – rainfall amount, coastline distance, and
concentration (in terms of Cl and Na) was validated with experiments conducted at Mule Hole SEW
and Kalekere. Monthly variations in precipitation chemistry at these stations are predicted from a
downscaled (in time) model and then compared with the observed data. Models developed at both
annual and monthly scale are found to perform well with the field observations. Hence, this model is
used for predicting the precipitation chemistry (in terms of Cl and Na) of different station points in the
upper Cauvery basin.
Comparative performance of alternate methods of recharge estimation i.e. Chloride mass
balance (CMB) and water table fluctuation (WTF) approaches, is analyzed at various stations in the
basin. Annual rainfall, Cl concentration in rain (predicted from precipitation model) and the
concentration of Cl in the groundwater are the inputs for the CMB approach. Since main source of Na
is from atmosphere, Na is taken as an alternative for Cl in the CMB approach and recharge is estimated
using sodium mass balance (SMB) approach. Na concentrations contributed from weathering are
quantified and eliminated in the analysis. Recharge estimated using SMB approach is found to be
higher than CMB estimate in the semi-arid and the sub-humid zones.
Water table fluctuation (WTF) method is used to compare the recharge obtained from both
CMB and SMB approaches. Estimates using WTF approach are found to be higher than both CMB and
SMB in the semi-arid and the sub-humid zones while SMB is found to be higher than CMB estimates.
SMB and WTF estimates match well in the humid zone. An exponential relationship between recharge
and annual rainfall is observed. Recharge coefficient estimated on an annual scale varied from 0.1 to
0.25 across the basin. Among CMB and SMB approaches, SMB is a better alternative for recharge
estimation in semi-arid zones, where WTF approach performed poorly.
Water – rock reactions are driven by the inequilibrium reactions of water with the mineral
assemblage in the rock. These reactions evolve towards equilibrium with the primary minerals while a
series of secondary minerals precipitate. Mass balance approach is adopted to quantify the rate at which
the water – rock interactions occur in order to reach the equilibrium. Field experiments in the
experimental watershed (Mule Hole SEW, ~ 4.5 km ) are carried to identify the minerals present in the
2

region and their composition. Quartz, oligoclase, sericite, epidote and chlorite are the primary minerals
while kaolinite and Fe-oxides are the secondary minerals present in this region. Percentages of oxides
of different elements in each of these minerals are determined from the field experiments.
Stoichiometric coefficients of different elements in each of these minerals are determined from these
percentages. Long – term weathering rates are determined using these stoichiometric coefficients along
with the mass fluxes of each element.
Set of minerals present at different depths are found to vary among the thirteen observation
wells of Mule Hole SEW. Hence, the mass balance calculations resulted in different weathering rates
for a particular mineral based on the spatial location and the particular depth of the occurrence of the
mineral. These weathering rates are tested for the sensitivity to carbonates with the inclusion of calcite
in the mass balance calculations. With this sensitivity analysis it is observed that the presence of
carbonates in the nodular form in the shallow wells has not changed the weathering reactions and their
rates, and hence these wells are termed to be in the ‘silicate with secondary carbonate’ system. On the
other hand, carbonates are not present in deeper wells, inclusion of which alters the equilibrium of the
mass balance calculations. Thus, these wells are said to belong to the ‘silicate’ system. Anorthite
present in some of the wells (MH2 and MH6) dissolves accompanied with the dissolution of
carbonates. These wells are observed to belong to the third group the ‘amphibolites with primary
carbonate’ system.
Weathering rates of all the minerals present in these three different systems are also
determined annually (short term rates). Mean of these short – term rates are observed to be the same as
the long – term (over a period of 4 years) weathering rates with a minor difference of 3 – 10% in
values. Thus, the weathering rates determined using mass balance approach is used to determine the
quantities of concentrations of different elements contributed from the mineralogical reactions.
Temporal variations in the concentrations of different chemical species in this small
experimental watershed are simulated using a hydrogeochemical model. The model is developed based
on a mixing cell approach, which considers the spatiotemporal variations in the recharge and the
weathering inputs. Most of the weathering reactions are observed to take place in the saturated zone,
which is termed as the ‘mixing zone’. This zone extends from few meters above the groundwater table
to few meters below the water table. Mixing zone is discretized into series of ‘cells’ and concentrations
in this zone are simulated. This group of cells is assumed to move along with the groundwater
fluctuation. Sensitivity of the model is analysed subject to the variations in the recharge and the
weathering fluxes. The developed model is used to simulate the concentrations of the groundwater in
the three systems – ‘silicate’, ‘silicate with secondary carbonate’ and ‘amphibolites with primary
carbonate’. Field data for chemical species is observed to vary in this mixing zone, boundaries of which
are defined from the model simulations. Simulations corresponding to the cell at the mid depth of this
mixing zone are observed to correlate well with the field data. Hence, the model developed is able to
simulate the temporal variations in the groundwater chemistry. In summary, the study analyses the
effects of lithological, climatic and anthropogenic factors on groundwater chemistry.