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Dr. Siya Soummya
Assistant Professor in Civil EngineeringCollege of Engineering Pune-5Groundwater chemistry is a function of recharge and the input chemistry of the rain, which getstransformed as it moves through the soil matrix. Apart from mineral transformations, anthropogenicactivities are other external factors, which affect the groundwater chemistry. Stream aquife
interactions alter the chemistry of groundwater in the regions nearer to the stream. A study is carriedout to analyse the hydrogeochemical behavior under the influence of lithologic, precipitation andanthropogenic 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 isused to study the spatiotemporal variations in groundwater chemistry of a silicatic rock group in a smallexperimental watershed. 
Upper Cauvery river basin (~ 10000 km
) is selected for the analysis, which stretches alongthree 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 inthe saprolite or in the deeper hard rock zone based on the geomorphology even at the scale of a smallwatershed. 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 withdifferent levels of intensities is practiced through groundwater in the upland areas. Observation wellsconsidered 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 threezones) 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 (unimodalrainfall) 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 fromthe weathering of Ca, calcrete formations also play an important role in the semi-arid zone. Ionexchange process cycles between Cl and SO
and between Ca and Na. Dissolution of CaCO
, silicateweathering and evaporation are the major mineralogical reactions.Variations in Na/Cl and Ca/Cl molar ratios indicate that shallow wells have higher molar ratioswith 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 identifiedusing ‘recharge – discharge’ concept based on the rainfall intensity. Wells under normal scenario havelow 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 annualrecharge exhibit dilution chemistry though groundwater level fluctuations are higher. However, wellsin 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 theanthropogenic effects on the basin.Rainfall and its chemistry are to be analysed to understand the groundwater chemistry. Hence, datafrom 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. Thesestations are categorized as ‘urban’, ‘suburban’ and ‘rural’. pH, HCO
, NO
and Mg concentrations havenot changed much from coast to inland. On the other hand, SO
and Ca concentrations changes are
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 annualrainfall. 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 thenlater stabilize. Regression parameters estimated for different cases are found to be consistent (R 
~ 0.8).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 thecountry. 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, andconcentration (in terms of Cl and Na) was validated with experiments conducted at Mule Hole SEWand Kalekere. Monthly variations in precipitation chemistry at these stations are predicted from adownscaled
(in time) model and then compared with the observed data. Models developed at bothannual and monthly scale are found to perform well with the field observations. Hence, this model isused 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 theconcentration of Cl in the groundwater are the inputs for the CMB approach. Since main source of Nais from atmosphere, Na is taken as an alternative for Cl in the CMB approach and recharge is estimatedusing sodium mass balance (SMB) approach. Na concentrations contributed from weathering arequantified and eliminated in the analysis. Recharge estimated using SMB approach is found to behigher 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 bothCMB and SMB approaches. Estimates using WTF approach are found to be higher than both CMB andSMB 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 rechargeand annual rainfall is observed. Recharge coefficient estimated on an annual scale varied from 0.1 to0.25 across the basin. Among CMB and SMB approaches, SMB is a better alternative for rechargeestimation in semi-arid zones, where WTF approach performed poorly.Water – rock reactions are driven by the inequilibrium reactions of water with the mineralassemblage in the rock. These reactions evolve towards equilibrium with the primary minerals while aseries of secondary minerals precipitate. Mass balance approach is adopted to quantify the rate at whichthe water rock interactions occur in order to reach the equilibrium. Field experiments in theexperimental watershed (Mule Hole SEW, ~ 4.5 km
) are carried to identify the minerals present in theregion and their composition. Quartz, oligoclase, sericite, epidote and chlorite are the primary mineralswhile kaolinite and Fe-oxides are the secondary minerals present in this region. Percentages of oxidesof 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 alongwith the mass fluxes of each element.Set of minerals present at different depths are found to vary among the thirteen observationwells 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 themineral. These weathering rates are tested for the sensitivity to carbonates with the inclusion of calcitein 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 

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