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Groundwater is the most important water resource, on which depends human geo-economic development and survival. Recent environmental changes and anthropogenic activities render groundwater severely vulnerable. Groundwater in Central Sindh, Pakistan, is facing a similar situation. Hydrogeochemical characteristics of the groundwater in the said region were investigated by analyzing 59 groundwater samples via agricultural and drinking indices, using various statistical methods and graphical approaches to identify factors affecting groundwater. Major reactions occurring in the groundwater system were quantified by hydrogeochemical modeling. A statistical summary reveals the abundance of cations is Na+ > Ca2+ > Mg2+ > K+, while the abundance of anions is HCO3- > Cl- > SO42. Groundwater chemistry is mainly of rock dominance. Correlation analysis and graphical relationships between ions reveal that ion exchange and rock weathering such as the dissolution of halite, albite, and dissolution of carbonate minerals are important rock-water interactions, governing the evolution of groundwater chemistry. Hydrochemical facies are predominantly of mixed CaMgCl and Na-Cl type, with few samples of Ca-HCO3 type, which constitutes fresh recharged water. Based on the Water Quality Index (WQI), 28.82% samples were found to be unsuitable for drinking. A United States Salinity Laboratory (USSL) diagram, Wilcox diagram, and other agricultural indices indicate that majority of the groundwater samples fall within the acceptable range for irrigation purposes.