The use of Sephadex G-10 gel chromatography with a groundwater mobile-phase to separate bound and free cobalt in concentrated groundwater samples has proven to be a relatively non-invasive technique for the investigation of groundwater chemistry. Trace amounts of cobalt as would be expected to be released from a radioactive waste repository do exhibit association with groundwater species from a test site near the Drigg low-level nuclear waste site in Cumbria.

Grundvattnets kemiska kvalitet påverkas av olika processer i dess närområde, dessa kan vara såväl mänskliga aktiviteter som klimatologiska faktorer. Hur och i vilken utsträckning de påverkar grundvattenkvaliteten kan studeras genom att undersöka utvecklingen av historiska grundvattenkvalitetsdata i relation till förändringar i klimatet. Detta kandidatarbete syftar till att studera hur grundvattnets kvalitet påverkas av klimatförändringarna. Data över ökande och minskande trender i förändringar hos olika kemiska parametrar har bearbetats utifrån material från Sveriges geologiska undersökning från stationer i grundvattenmagasin utspridda i Sverige, detta under åren 1985-2014 samt 1995-2014 i områden där risk för lokal föroreningsspridning är liten. De undersökta kemiska parametrarna är olika salter, tungmetaller, organisk halt och fysikaliska parametrar. De senaste 40 åren i Sverige har präglats av ett varmare klimat med höjda grundvattennivåer, klimatscenarier förutser en liknande utveckling men där grundvattennivåerna kommer sjunka i sydöstra Sverige. Resultatet visar på trender som mest sannolikt beror på minskade deposition av svavel, kväve och tungmetaller sedan slutet av 1970-talet. Mätvärden för sulfat, kväveföreningar, konduktivitet, tungmetaller och pH har minskat, medan dessa för alkalinitet och organisk halt har ökat. Klimatologiska faktorer som har påverkat grundvattnet är en ökad årsmedeltemperatur och förändrade grundvattennivåer, vilket främst syns genom ökande temperatur i grundvattnet samt utspädning av salter och en ökad organisk halt. / The chemical quality of groundwater is affected by different processes in its surrounding. These can be human activities as well as climatological factors. How and to what extent they influence the groundwater quality can be studied by examining the development of historical groundwater quality data in relation to changes in the climate. This Bachelor thesis aims to study how the quality of the groundwater is affected by the climate change. Data of increasing and decreasing trends in changes of different chemical parameters have been processed based on material from the Geological Survey of Sweden from stations in groundwater aquifers spread out in Sweden. The data represent the years 1985-2014 and 1995-2014 and are collected in areas where the risk of local pollution is small. The investigated chemical parameters are different salts, heavy metals, organic content and physical parameters. In the last 40 years, Sweden has been characterized by a warmer climate and higher groundwater levels, and climate scenarios predict a similar development but with a lowering of groundwater levels in south-east of Sweden. The results show trends that most likely indicate a decrease in deposition of sulfur, nitrogen and heavy metals since the end of 1970’s. Measured concentrations of sulphate, nitrogen compounds, heavy metals and also conductivity and pH have decreased, while alkalinity and organic compounds have increased. Climatological factors that have influenced the groundwater are the increased annual mean temperature and variation in groundwater levels, which is mainly evident as an increased temperature in the groundwater, dilution of salts and an increased organic content.

High concentrations of sulfate in groundwater, up to ten times the amount recommended by the EPA, in Blanco and Hays Counties, Texas, are of concern as groundwater pumping and population increase. The goals of this study are to characterize the chemistry of groundwaters in Blanco and Hays Counties within the context of Texas Groundwater Management Area-9 and to determine chemically and hydrogeologically the explanation for the spatial distribution of sulfate between the Pedernales River, the Blanco River, and Onion Creek. Insights gained by examining sulfate distribution in Blanco and Hays Counties can be applied to the other counties on the Edwards-Trinity Plateau with similarly high concentrations of sulfate in groundwater. Hydrochemical data from the Cretaceous Edwards and Trinity Groups and water level measurements were used to analyze groundwater chemistry and flow. PHREEQC was used to examine whether phase changes in aquifer minerals could explain the observed geochemical patterns. COMSOL was used to develop a simplified groundwater flow model for a cross-sectional area between the Pedernales River and Onion Creek in Hays County. Water levels indicate that groundwater generally flows southeast in the study area and most streams are gaining. The groundwater flow model indicates a zone of slow-moving groundwater beneath the topographic high between the Pedernales River, the Blanco River, and Onion Creek. Chemical analyses of well data show the presence of four groundwater chemical endmembers in Groundwater Management Area-9; a Ca-Mg-HCO3 fresh endmember, a Ca-Mg-SO4 endmember, a Ca-Mg-SO4-Na-Cl endmember, and a Na-Cl endmember. High sulfate waters generally come from the Upper and Middle Trinity aquifers while fresher waters are from the Edwards aquifer. Physical and chemical analyses indicate that the zone of high sulfate in Blanco and Hays Counties may be the result of gypsum dissolution and dedolomitization in the Upper and Middle Trinity aquifers combined with low rates of groundwater flow beneath the topographic high. Groundwater flow analyses are consistent with those for the Groundwater Availability Models published for the region. Chemical analyses, specifically SO4 distributions and Ca/Mg ratios, are consistent with those found by Nance(2010) on the Edwards Plateau, farther west of the study area. / text

Under de senaste decennierna har i många länder, inkluderat Sverige, långt gångna planer utvecklats för ett djupförvar av högaktivt kärnavfall. Som en del i det svenska förvarskonceptet skall avfallet inneslutas i kopparkapslar som omslutes av återfyllnadsmaterial med mycket låg genomsläpplighet av vatten. Dessutom skall kapslarna förläggas på ca 500 meters djup i granitberggrunden, vilken fungerar som en naturlig barriär för transport av radionuklider till markytan. Dessa naturliga och konstruerade barriärer väljs och utformas så att förvarets funktion kan säkras under hundra tusentals år. En viktig fråga för säkerhetsanalysen för ett sådant förvar är utvecklingen av redoxförhållandena över långa tider. Korrosionen av kopparkapslarna går fortare under oxiderande förhållanden och rörligheten hos frisläppta radionuklider ökar. I den första delen av avhandlingen studerades förmågan hos berget att upprätthålla reducerande förhållanden på förvarsdjupet över långa tider. En modellstruktur har utvecklats med målet att ta hänsyn till alla processer som bedömts viktiga för utarmning av inträngande syre från markytan över långa tider. Förenklingar introducerades så att transparenta analytiska lösningar kunde erhållas som förenklar utvärdering av resultat och tillåter identifiering av osäkra parametrar. Komplexa system löstes numeriskt för fall då analytiska lösningar ej kunde erhållas, samt för att validera förenklingar som ligger till grund för de analytiska lösningarna. Resultat redovisades för rådande förhållanden samt för förhållanden som bedömdes rimliga under smältfasen av en glaciationsperiod. Det visade sig att de hydrauliska egenskaperna har stor påverkan på inträngningsdjupet av syre längs flödesvägar i berget. Kvoten mellan den flödesvätta ytan och flödet visade sig vara en viktig parameter som bestämmer omfattningen av interaktionen mellan löst syre i grundvattnet och reducerande mineral i berget. Resultaten visar att för korta tider, beroende på mängd reducerande mineral och reaktionshastighet, kan kemisk reaktionskinetik bestämma förbrukningshastigheten av syre. För längre tider begränsas förbrukningen av intern diffusion i stora partiklar och bergmatrisen. Det visade sig att hänsyn måste tas till många osäkerheter för att kunna göra tillförlitliga kvantitativa uppskattningar av omfattningen av syreinträngningen. I den andra delen av avhandlingen undersöktes konsekvenserna av inträngande syre på korrosion av kopparkapslarna. En mekanism föreslogs också för bildande av sulfid nära kapseln. Sulfid är en annan korrodent som kan bildas mikrobiellt i reducerande miljöer från sulfat och en organisk reduktant såsom metan. Beräkningarna visar att mer än 50 kg av koppar inte är sannolikt att korrodera över en miljon år. / Advanced plans for the construction of a deep geological repository for highly radioactive wastes from nuclear power plants have evolved during the past decades in many countries including Sweden. As part of the Swedish concept, the waste is to be encapsulated in canisters surrounded by low permeability backfill material. The copper canisters will be deposited at around 500 metres depth in granitic rock, which acts as a natural barrier for the transport of radionuclides to the ground surface. These natural and engineered barriers are chosen and designed to ensure the safety of the repository over hundred of thousands of years. One issue of interest for the safety assessment of such a repository is the redox evolution over long times. An oxidising environment would enhance the corrosion of the copper canisters, and increases the mobility of any released radionuclides. In the first part of the present thesis, the ability of the host rock to ensure a reducing environment at repository depth over long times was studied. A model framework was developed with the aim to capture all processes that are deemed to be important for the scavenging of intruding oxygen from the ground surface over long times. Simplifications allowing for analytical solutions were introduced for transparency reasons so that evaluation of results is straight-forward, and so that uncertain parameter values easily can be adjusted. More complex systems were solved numerically for cases when the analytical simplifications are not applicable, and to validate the simplifications underlying the analytical solutions. Results were presented for prevailing present day conditions as well as for conditions deemed to be likely during the melting phase of a period of glaciation. It was shown that the hydraulic properties have a great influence on the oxygen intrusion length downstream along flow-paths in the rock. An important parameter that determines the extent of interaction between the dissolved oxygen and the reducing minerals in the rock was shown to be the flow-wetted surface to flow-rate ratio. The results show that for an initial period of time, depending on the amount of reducing minerals and reaction rates, chemical reaction kinetics may control the rate of the overall depletion of oxygen. For longer times, internal diffusion resistance in large particles or in the rock matrix become rate limiting for the overall process. It was found that there are many uncertainties that have to be considered in order to make reliable quantitative predictions on the extent of oxygen intrusion. In the second part of the thesis, the impact of intruding oxygen on the corrosion of the copper canisters was explored. Also, a mechanism for the production of sulphide close to the deposition holes was studied. Sulphide is another corroding agent that may be produced microbially in a reducing environment from sulphate in the presence of organic reductants such as methane. From calculation results it was found that corrosion of more than 50 kg of copper is not likely over a period of one million years / QC 20100818

A hydrogeologic model, groundwater chemistry and stable isotopic analysis were used to establish recharge resources and outflows so a water balance could be developed for the Cromwell Terrace Aquifer (CTA) in Central Otago, New Zealand. Increased popularity of the Central Otago region for viticulture, orcharding and tourism, has resulted in an increased demand for water. Groundwater is a viable option to meet this demand for water. The CTA is a single unconfined aquifer contained within a thin veneer of permeable Quaternary glacial outwash gravels that range in thickness between 10 and 50m. These gravels rest unconformably on less permeable folded Tertiary sediments. The buried surface of the Tertiary sediments is irregular and provides the main hydrogeologic control in the CTA. Buried topographic highs in the Tertiary sediments impede groundwater flow, while the buried paleochannels at the southern end of the Cromwell Flat allow groundwater to flow unrestricted. The saturated thickness of the aquifer varies between 10 and 30 m. The direction of groundwater flow is in south easterly and south westerly directions toward both Lake Dunstan and the Kawarau Arm respectively. This indicates that recharge is from the Pisa Range. Annual fluctuations in groundwater levels show that there is a seasonal effect on the groundwater table. Annual fluctuations in groundwater level are in the range of 0.4 – 0.5 m, with lowest levels in winter and highest groundwater levels in late summer. The higher groundwater levels in summer correlate with when higher rainfall occurs, but could also be due to artificial recharge from irrigation during summer, and/or seepage from the Ripponvale Irrigation Scheme canals and storage ponds. Groundwater chemical analysis showed the dominant facies to be calcium bicarbonate waters. The source of the calcium bicarbonate is considered to be calcite in the Otago Schist, with concentrations of calcium bicarbonate being higher closer to the bedrock schist of the Pisa Range. Concentrations decreased toward Lake Dunstan, where calcium bicarbonate concentrations were lowest. The trend of calcium bicarbonate concentrations decreasing toward Lake Dunstan produces a similar pattern to the direction of groundwater flow. This would suggest that calcium bicarbonate concentrations are being diluted by rainwater infiltrating into the aquifer. However stable isotopic analysis showed that lake water infiltrates into the aquifer around the lake margin, and would also dilute calcium bicarbonate concentrations. Stable isotopic analysis found that groundwater was more depleted in both δ¹⁸O and δ²H than water from Lake Dunstan. The average δ¹⁸O for groundwater was -9.5‰, whereas the average δ¹⁸O for samples from Lake Dunstan was -8.1‰. The average δ¹⁸O value of Pisa Range snow, Pisa Range streams and Cromwell Flat precipitation gave values of -9.2‰ +/- 1.4‰, which is very similar to groundwater. This suggests recharge to the CTA is from a combination of snow melt and surface stream flow from the Pisa Range, and some direct rainfall infiltration on the Cromwell Flat. A water balance was calculated for the CTA groundwater system using the information from this study, and from a limited Otago Regional Council (O.R.C.) database. The main inputs to the CTA were found to be recharge precipitation and subsurface flows from the Pisa Range. The main outputs were identified as surface evaporation and discharge from the CTA to Lake Dunstan. The water balance showed that the total flow of water through the CTA is 93 Million cubic metres per year (Mm³/yr). At present the CTA has limited groundwater allocation measures in place. Using the information from the water balance, a volume of groundwater that could be abstracted sustainably was estimated. This volume was estimated using the O.R.C. method of allocating 50% of the mean annual precipitation that recharges the aquifer for groundwater abstraction. The total mean annual precipitation for the Cromwell Flat and Pisa Range is 20 Mm³/yr. Using the 50% of mean annual precipitation method, 10 Mm³/yr can be allocated for groundwater abstraction. The total volume of groundwater currently abstracted is 3 Mm³/yr, leaving 7 Mm³/yr of unallocated groundwater. Due to the small land area, types of land use, low population density of Cromwell Flat and availability of surface water (i.e. Lake Dunstan), it is unlikely that the total volume of 10 Mm³/yr will be fully allocated.

This thesis deals with the evaluation of hydrochemical characteristics of groundwater (dripping water) in The Chýnov Cave and the subsequent statistical processing of the results. There were followed three sampling points, which were irregularly distributed in the cave system. Bicarbonates occured as the dominant anions in the dripping water. The dominant cation was calcium. Water can therefore be classified as bicarbonate - calcium. This corresponds with the expectations for The Chýnov cave location. There were also detected enhanced concentrations of nitrates and sulphates at sampling site Štola - this has long-term character and influences the quality of the underground stream of The Chýnov cave, which is directly connected to spring "Rutický" (source of drinking water for the town of Chýnov). Although a protective zone is declared over the whole territory of Rutice water resources, there is increased amount of nitrates and sulphates which probably has anthropogenic character and it comes from applied fertilizer and mineralization processes in arable land in the close surrounding of the National Natural Monument: The Chýnov cave.

Groundwater is potentially a useful source for storing and providing thermal energy to the built environment. In a nordic context, aquifer thermal energy storage, (ATES) has not been subject to a wider extent of research concerning environmental impact. This thesis intends to study the impact on groundwater chemistry from an ATES that has been operational since 2016 and is located in the northern part of Stockholm, on a glaciofluvial deposit called the Stockholm esker. Analysis of groundwater sampling included a period of 9 months prior to ATES operation as well as a 7 month period after operation and sampling was conducted in a group of wells in vicinity of the installation and within the system as ATES operation began. Means of evaluation constituted a statistical approach which included Kruskal-Wallis test by ranks, to compare the ATES wells with the wells in the surroundings and principal component analysis, (PCA), to study the chemical parameters that could be related to ATES. In addition, a geophysical survey comprising 2D-resistivity and induced polarization, (IP) was done to elucidate whether the origin of high salinity could be traced to nearby possible sources. The analysis was based on foremost the cycle of cold energy storage. The results showed large variations in redox potential, particularly at the cold wells which likely was due to the mixing of groundwater considering the different depths of groundwater being abstracted/injected from different redox zones. Arsenic, which has shown to be sensitive to high temperatures in other research showed a decrease in concentration compared to surrounding wells. There were found to be a lower specific conductivity and total hardness at the ATES well compared to their vicinity. That indicates that they are less subject to salinization and that no accumulation has occurred to date.  It is evident that the environmental impact from ATES is governed by the pre-conditions in  soil- and groundwater. / Grundvatten har förutsättningen att utgöra en värdefull resurs för att lagra och förse byggnader med termisk energi. I en nordisk kontext har termisk energilagring i akviferer, (ATES)  inte varit föremål för någon bredare forskning angående miljöpåverkan. Denna uppsats syftar till att studera kemisk grundvattenpåverkan från ett ATES som togs i drift 2016 i norra Stockholm, i en isälvsavlagring vid namn Stockholmsåsen. Analysen omfattar grundvattenprovtagning 9 månader före ATES driften samt 7 månader efter driftstart och provtagningen genomfördes i ett antal brunnar i närheten av installationen samt i ATES systemet då driften startade. Utvärderingsmetoden bestod av ett statistiskt tillvägagångssätt och omfattade Kruskal-Wallis test by ranks, för att jämföra ATES brunnarna med omgivande brunnar och principal component analysis, (PCA), för att studera kemiska parametrar som kan kopplas till ATES. I tillägg genomfördes en geofysisk undersökning som omfattar 2D-resistivitet samt inducerad polarisation, (IP) för att klarlägga huruvida källan till den höga saliniteten kunde spåras. Analysen baseras på främst på cykeln då kyld energi lagras. Resultaten visar stor variation i redoxpotential, i synnerhet vid de kalla brunnarna vilket sannolikt beror på omblandning av grundvatten med tanke på en differens i djup som grundvattnet infiltrerar/pumpas från med tillhörande skillnad i redox zon. Arsenik vilket har visat sig känsligt för höga temperaturer i annan forskning visade minskade koncentrationer jämfört med omgivande brunnar. ATES brunnarna uppvisade även lägre specifik konduktivitet och totalhårdhet i jämförelse. Det pekar mot att brunnarna är mindre utsatta för salinitet och att ingen ackumulering har skett till dags dato. Det framgår tydligt att miljömässig påverkan från ATES styrs av grundförutsättningarna i mark och grundvatten.

Groundwater is potentially a useful source for storing and providing thermal energy to the built environment. In a nordic context, aquifer thermal energy storage, (ATES) has not been subject to a wider extent of research concerning environmental impact. This thesis intends to study the impact on groundwater chemistry from an ATES that has been operational since 2016 and is located in the northern part of Stockholm, on a glaciofluvial deposit called the Stockholm esker. Analysis of groundwater sampling included a period of 9 months prior to ATES operation as well as a 7 month period after operation and sampling was conducted in a group of wells in vicinity of the installation and within the system as ATES operation began. Means of evaluation constituted a statistical approach which included Kruskal-Wallis test by ranks, to compare the ATES wells with the wells in the surroundings and principal component analysis, (PCA), to study the chemical parameters that could be related to ATES. In addition, a geophysical survey comprising 2D-resistivity and induced polarization, (IP) was done to elucidate whether the origin of high salinity could be traced to nearby possible sources. The analysis was based on foremost the cycle of cold energy storage. The results showed large variations in redox potential, particularly at the cold wells which likely was due to the mixing of groundwater considering the different depths of groundwater being abstracted/injected from different redox zones. Arsenic, which has shown to be sensitive to high temperatures in other research showed a decrease in concentration compared to surrounding wells. There were found to be a lower specific conductivity and total hardness at the ATES well compared to their vicinity. That indicates that they are less subject to salinization and that no accumulation has occurred to date. It is evident that the environmental impact from ATES is governed by the pre-conditions in soil- and groundwater.

This study aims to integrate groundwater geochemistry and mathematical modeling to determine the dominant geochemical processes and groundwater residence time within the Wilcox aquifer in the northern Gulf Coastal Plain. Groundwater samples were collected and analyzed for major ion chemistry, stable isotopes (18O, 2H, and 13C), and radioisotope 36Cl content. Geochemical modeling enabled the identification of major sources and sinks of solutes in the aquifer. A two-dimensional, finite-difference, numerical model was used to determine the deep groundwater flow rate and transport of 36Cl in the aquifer. Major ion chemistry shows a chromatographic pattern along the flow path in which a gradual increase of Na+ and decrease of Ca2+ and Mg2+ is evident. The most plausible inverse models in the downgradient section of the aquifer indicate that oxidation of organic matter (OM), which may be associated with discontinuous lenses of lignite, and consequent release of CO2 sustain the reduction of Fe(III) (oxyhydr)oxides and sulfate and the dissolution of carbonate minerals (calcite and, in some instances, siderite). These processes, in turn, result in pyrite precipitation and exchange of Ca2+ for Na+ on clay-mineral surfaces. Models constrained with 13C are consistent with mole transfers between pairs of wells in close proximity, but not for the entire flow path. The observed range of δ13C of dissolved inorganic carbon (-7.3‰ to -12.4‰) is interpreted as a result of both oxidation of OM and dissolution of carbonates. Calculated values of 36Cl/Cl show an abrupt discontinuity between the upgradient and downgradient sections that was also observed in δ18O and δ2H data. The gradual enrichment of 18O and 2H along the flow path could be the result of diffusion. The distinct differences in δ18O and δ2H between the upgradient and downgradient Wilcox aquifer suggest that the latter preserves a paleoclimatic signal.

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. In order to study the effects of precipitation control on the groundwater chemistry the Upper Cauvery river basin (~ 10000 km2) is selected for the analysis, which stretches along 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 SO4 and between Ca and Na. Dissolution of CaCO3, silicate 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, HCO3, NO3 and Mg concentrations have not changed much from coast to inland. On the other hand, SO4 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 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 (R2 ~ 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 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 km2) are carried to identify the minerals present in the 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. The transformations in the rainwater chemistry as it reaches groundwater are analysed along different stages. A hydrogeochemical model is developed to simulate the groundwater concentrations in three different mineralogical settings over a period of three years.