Mine drainage impacts from a coal waste pile at Smolnica, Poland have been monitored. Groundwater in an unconfined aquifer downgradient from the pile has near-neutral pH, but high concentrations of sulfate (up to 3,827 mg/l), chloride (up to 903 mg/l), and sodium (up to 2,606 mg/l). Concentrations of iron and manganese are elevated only locally, and concentrations of other metals are low. The behavior of sulfate seems to be conservative in the downgradient aquifer, and gypsum may only be precipitating locally. Concentrations of iron and manganese seem to be controlled by the precipitation of ferric oxide and hydroxides and rhodochrosite, respectively. Complete neutralization of mine drainage by carbonates is consistent with high concentrations of calcium (up to 470 mg/l) and magnesium (up to 563 mg/l) and also with high strontium concentrations of up to 3.08 mg/l, observed in groundwater downgradient from the pile. Hydraulic head profiles at two sites within the river bottom sediments indicate upward flow toward the river with large local differences in groundwater recharge. Water chemistry profiles in the river bottom sediments and geochemical modeling suggest conservative behavior of Na, Cl, and SO4 and precipitation of Fe and Mn at the groundwater/river water interface. Mine drainage enters the Bierawka River and causes increasing sulfate concentrations. In contrast, concentrations of sodium and chloride in the Bierawka River decrease downgradient from the pile because water in the river upgradient from the pile is already highly contaminated by these species from the discharge of mining waters. Concentrations of Fe and Mn in the river water are low, as a consequence of the precipitation of Fe and Mn oxide and hydroxides. Direct geochemical modeling was able to reproduce measured concentrations of conservative species (e.g., Na, Cl, and SO4), but errors for metals and Ba were relatively large. In addition, calculated P-CO2 values in the river water are very high, suggesting that equilibrium with atmospheric P-CO2 and P-O2 has not been reached, and at least some reactions should be modeled as kinetic processes. High concentrations of Na, Cl, and SO4 contribute to the contamination of the Odra River, which is joined by the Bierawka River farther downgradient, thus limiting the use of river water for recreation and other purposes.