The aim of the study was to assess the groundwater quality in a rural area affected by the abandoned pyrite ash waste dumps. The abundance of major ions in groundwater depends largely on the nature of the rocks, climatic conditions, and mobility. To evaluate geochemical processes, 30 groundwater samples collected from Valea Calugareasca, Prahova County, Romania, were analyzed for the major anions (NO3−, SO42−, Cl−, HCO3−, and F−) and cations (Ca2+, Mg2+, Na+, and K+), which are naturally highly variable due to climatic and geographical location conditions. Ca2+, Na+, Mg2+, and K+ varied between 118 and 275 mg/L, 32 and 160 mg/L, 12.2 and 78.4 mg/L, and 0.21 and 4.48 mg/L, respectively. NO3− levels exceeding the World Health Organization (WHO) limit of 50 mg/L were identified in 17% of the groundwater samples, mainly as result of fertilizers applied to agricultural activities. The hydrogeochemical study identified dolomite dissolution and halite precipitation as natural sources of ions as well as the presence of pyrite as a source of SO42− ions in 60% of the samples. The sulfate content varied between 125 and 262 mg/L. Bicarbonate and chloride concentrations varied between 202 and 530 mg/L and 21 and 212 mg/L. The saturation index indicates the contribution of Ca2+ ions in the groundwater samples came from some processes of dissolving rocks such as aragonites (values between 1.27 and 2.69) and calcites (values between 1.43 and 2.82). Negative halite values indicated that salt accumulation results from precipitation processes. Only 10% of the analyzed groundwater samples were suitable for human consumption, the samples being situated on the hill, far away from the pyrite ash waste dumps and agricultural land.