Mercury speciation in the Valdeazogues River–La Serena Reservoir system: Influence of Almadén (Spain) historic mining activities

Mercury (Hg) speciation and partitioning have been investigated in a river-reservoir system impacted by the Almadén mining activities, the world''s largest Hg district. This study is the first to simultaneously investigate Hg dynamics from above the mining district and into the La Serena Reservoir (3219 Hm3), being the third largest reservoir in Europe and the largest in Spain. Water, sediment and biota were sampled at different seasons during a 2-year study from the Valdeazogues River, which flows east–west from the mining District, to La Serena Reservoir. Simultaneously, a comprehensive study was undertaken to determine the influence of some major physico-chemical parameters that potentially influence the fate of Hg within the watershed. Concentrations of dissolved Hg in water were below 0.14 µg/L, whereas particulate Hg ranged from 0.1 to 87 µg/g, with significant seasonal variation. Total Hg concentrations varied from 7 to 74 µg/g in sediment from the Valdeazogues River, while in sediments from La Serena Reservoir were below 2 µg/g. On the other hand, methyl-Hg reached concentrations up to 0.3 ng/L in water and 6 ng/g in sediment from La Serena Reservoir, whereas maximum concentrations in Valdeazogues River were 5 ng/L and 880 ng/g in water and sediment, respectively. The distribution of Hg species in the Valdeazogues River–La Serena Reservoir system indicated a source of Hg from the mine waste distributed along the river. Total Hg in water was strongly correlated with total dissolved solids and chlorophyll a concentrations, whereas organic carbon and Fe concentrations seem to play a role in methylation of inorganic Hg in sediment. Total Hg concentrations were low in fish from Valdeazogues River (0.8–8.6 ng/g, wet weight) and bivalves from La Serena Reservoir (10–110 ng/g, wet weight), but most was present as methyl-Hg. [Copyright &y& Elsevier]