The Ajuricaba Basin Creek is located west of the Parana State, it is part of the Parana 3 Hydrographic Basin and it is located at southwest of the Marechal Candido Rondon county. Its area of around 18 km2 is manly used for agricultural purposes. The basin is part of the Serra Geral Aquifer System (SGAS), which comprises basic volcanic rocks of the Serra Geral Group. The main objectives of this study are the characterization of the hydrogeochemical environments and the understanding of the dissolved elements sources, both geological and human, in order to create a water circulation model of the basin. Two field campaigns, in August and November 2019, were done to collect water samples from surface waters (SW), phreatic aquifer (PA) and fractured aquifer (FA). During the 2019 field campaigns, the temperature, pH, total dissolved solids (TDS) and electrical conductivity (EC) were measured on site. Physicochemical parameters (SiO2, HCO3−, CO3−2, Cl−, F−, PO4−3, SO4−2, NO3−, NO2−, Ca+2, Mg+2, Na+, K+, Fe total, Mn+2, Nb, S, V, Zn, Al, Sr, Ba, P, Ti) of the collected samples were analysed. Preexisting data from December 2010 was also used to observe historical changes in water quality through time. Based on this data, statistical (univariate and correlation) and hydrochemical analysis were conducted in order to characterize the hydrogeochemical environments and surface and groundwater flows in the basin. Historical analysis revealed that SW and PA samples have the most significant impacts on water quality with double the median concentration of NO3− and three to nine times the concentration of Cl−. Hydrochemical analysis showed that SW have higher concentrations of HCO3−, Cl−, NO3−, Ca+2, Mg+2, Al, Sr, Ba and Fe, high TDS and neutral to acid pH. PA has the lowest TDS and acid pH and its main ions are HCO3−, NO3−, Ca+2 and Mg+2. In addition, FA was divided in: FA (Ca+2) with HCO3−, Ca+2 and Mg+2 as main ions, neutral pH and low TDS and FA (Na+) with CO3−2, HCO3−, SO4−2, Na+, V, Nb and P as main ions, basic pH and high TDS. SW has a similar pattern to PA and FA (Ca+2) indicating that the rivers are discharge zones for both aquifers. FA (Ca+2) has a similar hydrochemical signature to SGAS, confirming it origins. In opposition, the FA (Na+) aquifer hydrochemical signature differs from the SGAS and, in fact, is more similar to the one of the confined Guarani Aquifer System (GAS), suggesting a higher residence time. Fa (Na+) waters have higher TDS and basic pH, indicating a higher residence time and depth associated with the ascension of even deeper flows from GAS towards the basin. In addition to the hydrochemical model, this research also highlights the potential of the multielement-hydrochemistry to understand the relations between surface and groundwater resources contributing for the management of water resources in watersheds.