Short-term changes in water chemistry in the Baccu Locci stream (Sardinia, Italy) affected by past mining

Short-term changes in water chemistry, and especially in dissolved trace element concentrations, associated with diel cycles during base-flow conditions at a specific sampling station in the Baccu Locci stream draining the homonymous old mine area in Sardinia (Italy) were investigated. Diel fluctuations in pH and alkalinity were correlated with the temperature-dependent CO2 solubility and the biologically-induced CO2 production, both of which were higher during the night. Adsorption/desorption to/from streambed material, in particular ferrihydrite, is believed to be the main in-stream mechanism causing the observed diel variations in dissolved concentrations of As and Zn. Arsenic was mainly affected by the dual action of temperature and competing carbonate ions, whereas pH seemed less important. Temperature acted in accordance with the exothermic feature of anion sorption onto hydrous metal oxide surfaces; aqueous carbonate species exerted their competitive effect in relation to alkalinity variation. Zinc was primarily affected by temperature, in accordance with the endothermic feature of metal cation sorption onto hydrous metal oxide surfaces, and secondly by pH. Co-precipitation of As and Zn with calcite is another possible mechanism, which requires further investigation involving examination of inorganic and biological materials coating the streambed. All these processes potentially controlling the diel cycles of trace elements should be carefully considered to assess the effectiveness of remediation actions currently in progress at Baccu Locci. A normalization method for data from asynchronous sampling has been developed and proposed in order to eliminate or at least attenuate the effect of sampling time and provide an additional tool to identify the processes/mechanisms involved in trace element concentration fluctuations observed along a contaminated stream during base-flow conditions.