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The sources of chemical constituents of groundwater and its associated hydrogeochemical processes in the part of Mhlathuze catchment was identified. Groundwater of the area is classified into soft to very hard and the nature is identified as acidic to alkaline. The overall electrical conductivity is < 3000 μS/cm except in three wells. The predominant water type is NaCl (69% of samples) and CaMgCl facies. Gibbs plots, mCa/Mg ratio, mNa/Cl ratio, Ca + Mg vs HCO 3 +SO 4 plot, Na + K vs HCO 3 plot, Ca/Na vs HCO 3 /Na, Chloroalkaline indices (CAI 1, CAI 2) and Ca + Mg–HCO 3 –SO 4 vs Na + K–Cl plots confirm the impact of silicate, carbonate mineral weathering and ion exchange reaction in this aquifer. However, few wells are influenced by the evaporation process. Groundwater is highly undersaturated with sulphate, chloride minerals and saturated with carbonate minerals. CA revealed that Cl and SO 4 are derived from anthropogenic sources and a significant positive correlation between HCO 3 and Cl reveals that wastewater recharge has most likely simulated the mineral weathering in the vadose zone, which could have further enhanced HCO 3 and Cl in the aquifer. PCA resulted in three factors. Factor 1 defines the influence of geogenic and anthropogenic processes while Factors 2 and 3 imply the mineral weathering and nitrification processes. Hierarchical cluster analysis defines that evaporation, anthropogenic input, silicate and carbonate weathering and nitrification process are the sources of chemical constituents of groundwater in this aquifer. [Display omitted] • Ionic ratios and bivariate plots reflect the impact of silicate & carbonate weathering and ion exchange reactions.. • Groundwater is highly undersaturated with sulphate and chloride minerals while saturated with carbonate minerals. • Wastewater recharge simulated mineral weathering in the vadose zone (HCO 3 vs Cl (r 2 >0.64)) of this aquifer. • Both PCA and HCA also reflects the influences of geogenic, anthropogenic and nitrification process. [ABSTRACT FROM AUTHOR]

• During PRM, major ion concentrations are higher than PM season due to evaporation. • GW types varied from NaCl > CaMgCl > CaHCO 3 (PRM) to CaHCO 3 = NaHCO 3 = NaCl (PM). • PRM - Mineral weathering, reverse ion exchange and evaporation dominant processes. • PM - Mineral weathering, cation exchange and dilution regulate water chemistry. • Monsoon recharge facilitated the pollutant movement from the surface to aquifer. Impact of monsoon recharge on groundwater chemistry and geochemical processes was evaluated using geochemical methods in the shallow hard-rock aquifer, southern India. Groundwater samples were collected from Salem city and its outskirts during pre-monsoon (PRM) and post-monsoon (PM) seasons and analysed for major and minor ions. Results suggest that during PRM, the average concentration of TDS, major ions and electrical conductivity (EC) in groundwater are higher than the PM season except for Na+ and HCO 3 –. The major water types also varied with seasons (PRM: NaCl > CaMgCl > CaHCO 3 ; PM: CaHCO 3 = NaHCO 3 = NaCl). Pearson correlation analysis indicates that Cl− and SO 4 2− show a strong positive correlation with EC, TDS, TH and major cations during PRM season whereas HCO 3 – and NO 3 – have a strong positive correlation with most of the ions during PM season. Before monsoon, the water chemistry is governed by the weathering of carbonate and silicate minerals, reverse ion exchange and evaporation processes, which resulted in high EC, TDS, TH and major ions in the groundwater. After the monsoon, the water chemistry is regulated by the mineral weathering, cation exchange and dilution processes. Geochemical modelling studies indicate that groundwater is saturated and oversaturated with carbonate minerals and undersaturated with sulphate and chloride minerals. During monsoon, the recharging water flushed the weathered layer and dissolved the soil CO 2 in the vadose zone, which subsequently enhanced the concentration of Na+ and HCO 3 – in the aquifer. Further, the high concentrations of Cl−, SO 4 2- and NO 3 – imply that the aquifer is polluted by surface contamination sources. After the monsoon, NO 3 – implies that monsoon recharge facilitated the pollutant movement from surface to the aquifer. Hence, a proper aquifer management plan is required to protect this aquifer and to provide clean and safe drinking water to the local community. [ABSTRACT FROM AUTHOR]