Assessment of phosphogypsum impact on the salt-marshes of the Tinto river (SW Spain): role of natural attenuation processes.

About 120 Mton of phosphogypsum from the fertiliser industry were stack-piled on the salt-marshes of the Tinto river (Spain). This paper investigates the capacity of salt-marshes to attenuate contamination due to downward leaching from phosphogypsum. Solids and pore-waters were characterized at different depths of the pile to reach the marsh-ground. In superficial zones, metals were highly mobile, and no reduced sulphur was found. However, pollutant concentration decreased in the pore-water in deeper oxygen-restricted zones. Metal removal occurred by precipitation of newly formed sulphides, being this process main responsible for the contamination attenuation. Pyrite-S was the main sulphide component (up to 2528 mg/kg) and occurred as framboids, leading to high degrees of pyritization (up to 97%). The sulphidization reaction is Fe-limited; however, excess of acid-volatile sulphide over other metals cause precipitation of other sulphides, mainly of Cu and As. This decrease in metal mobility significantly minimises the impact of phosphogypsums on the salt-marshes.