The role of gypsum and/or dolomite dissolution in tufa precipitation: lessons from the hydrochemistry of a carbonate-sulphate karst system

Abstract

The precipitation of freshwater carbonates (tufa) along karstic rivers is enhanced by degassing of carbon dioxide (CO2) downstream of karstic springs. However, in most karstic springs CO2 degassing is not enough to force the precipitation of tufa sediments. Little is known about the role of dissolution of gypsum or dolomite in the hydrochemistry of these systems and how this affects the formation of tufa deposits. Here we present a monitoring study conducted over a year in Trabaque River (Spain). The river has typical karst hydrological dynamics with water sinking upstream and re-emerging downstream of the canyon. Mixing of calcium–magnesium bicarbonate and calcium sulphate waters downstream of the sink enhances the dissolution of carbonates and potentially plays a positive role in the formation of tufa sediments. However, due to the common-ion effect, dissolution of dolomite and/or gypsum causes precipitation of underground calcite cements as part of the incongruent dissolution of dolomite/dedolomitization process, which limits the precipitation of tufa sediments. Current precipitation of tufa is scant compared to previous Holocene tufa deposits, which likely precipitated from solutions with higher saturation indexes of calcite (SIcc values) than nowadays. Limited incongruent dissolution of dolomite/dedolomitization favours higher SIcc values. This circumstance occurs when waters with relatively high supersaturation of dolomite and low SO 4 2 composition sink in the upper sector of the canyon. In such a scenario, the process of mixing waters enhances the exclusive dissolution of limestones, preventing the precipitation of calcite within the aquifer and favouring the increase of SIcc values downstream of the springs. Such conditions were recorded during periods of high water level of the aquifers and during floods. This research shows that the common-ion effect caused by the dissolution of gypsum and/or dolomite rocks can limit [or favour] the precipitation of tufa sediments depending on the occurrence [or not] of incongruent dissolution of dolomite/dedolomitization.