Detailed full-scale groundwater monitoring was carried out over a period of nine years, sampling at selected points along the groundwater flow direction in its final stretch. This established the hydrogeochemical evolution along the flow of a natural system formed by a calcareous aquifer which discharges and then passes through a quaternary aquifer of lake origin which is rich in organic matter. This evolution is highly conditioned by the oxidation of pyrites that are abundant in both aquifers. In the first aquifer, one kilometre before the discharge location, oxidizing groundwater crosses a pyrite mineralization zone whose oxidation produces an important increase in sulphates and water denitrification over a short period of time. In the quaternary aquifer with peat sediments and pyrites, water experiences, over a small 500 m passage and residence time of between three and nine years, a complete reduction by way of pyrite oxidation, and a consequent increase in sulphates and the generation of hydrogen sulphuric acid. This is an example of an exceptional natural hydrogeological environment which provides guidance on hydrogeochemical processes such as denitrification.

As a preliminary phase in the conservation and sustainable management of a karst system in Fuentetoba, Soria, Spain, an interdisciplinary study was carried out to determine its hydrogeological evolution. The hydrogeological history of this aquifer system began during the late Miocene, where discharges were driven by paleo-emergences in the moor, and associated conduits were developed under phreatic (or vadose) conditions—for example, the upper syngenetic galleries in the main known karst cave (Majada del Cura cave). Later on, the nearby karstic massifs, a general flattening of the relief, occurred during the Quaternary Period, during which the karstic base level had been in decline. The aquifer flow was then derived and modified towards the Fuentetoba spring from the earliest stages through the galleries of the aforementioned cave. The observations made in this cave indicate the existence of a unique type of hydrogeological organization. The hypogean network is the result of the excavation of the same water flow that has been entrenching and abandoning the vadose regimen toward the free regimen. The dating of the tuffaceous buildings, associated with the emergences, indicates that since almost the Middle Pleistocene, flow lines have converged in the Fuentetoba spring, inducing a high grade of karstification in the saturated zone of the syncline basin. Moreover, a major drainage conduit was developed by dissolution. During the late Upper Pleistocene, an essential component of the groundwater flow had been derived towards the source of the Mazos River spring. Tufa and paleogour datings in caves indicate that the aquifer has undergone different climatic stages during the latest Quaternary and, therefore, different feeding and recharge processes. These tufas and paleogours are interrelated as well, as they are associated with the warm stages during the most recent Quaternary, according to the regional context, when there was less natural recharge. The simulation of the springs’ flow enabled an approximate quantification of the variation in the aquifer’s hydraulic balance during the different climatic stages. For example, during the last glaciation, the natural recharge was impacted by snowmelt and increased by 160%.