The generation of acid rock drainage (ARD) was observed after the oxidation dissolution of pyrite-rich black shales, which were excavated during the construction of a highway in León (Spain). ARDs are characterized by the presence of high concentrations of sulfate and metals (Al, Fe, Mn, Zn, Cu, Co, Ni, Th, and U) that affect the La Silva stream. Dissolved element concentrations showed values between one and four orders of magnitude higher than those of natural waters of this area. A passive treatment system was constructed; the aim of which was to improve the quality of the water of the stream. This work provides a hydrochemical characterization of the La Silva stream after its transit through the different elements that constitute the passive treatment system (open limestone channel (OLC), small ponds, and a wetland), during its first year of operation. The passive treatment system has two sections separated by a tunnel 230 m long. The first section, which stretches between the highway and the tunnel entrance, is an OLC 350 m long with a slope of 16 %. The second section, which stretches from the tunnel exit to the end wetland, has a length of 700 m and a slope of 6 %; it is in this section where six small ponds are located. In the first section of this passive treatment system, the OLC was effectively increasing the pH from 3 to 4-4.5 and eliminating all of the dissolved Fe and the partially dissolved Al. These elements, after hydrolysis at a pH 3-3.5 and 4-4.5, respectively, had precipitated as schwertmannite and hydrobasaluminite, while other dissolved metals were removed totally or partially for adsorption by the precipitates and/or by coprecipitation. The second section receives different inputs of water such as ARDs and natural waters. After exiting the treatment system, the stream is buffered by Al at a pH of 4-4.3, showing high Al concentrations (19-101 mg/L) but with a complete removal of dissolved Fe. Unfortunately, the outflow shows similar or higher acidity than the inflow into the system due to the discharge of ARDs (mainly from the tunnel) that is received and to the existence of a natural stream, which is affected by a waste-rock pile. The predictions and calculations necessary for the design of any remediation/attenuation techniques are quite difficult. Despite the fact that the selected design is the most adequate one for this valley and type of passive treatment system (including adequate slopes), we must admit that the physicochemical characteristics of the ARD were not the most appropriate according to the literature. Moreover, during the design, engineers were unaware of the existence of the inflow from two highly polluting sources, which have rendered the passive treatment system ineffective and which therefore suggest that certain improvement measures could be considered.