Trace metal and nutrient distribution in an extremely low pH (2.5) river–estuarine system, the Ria of Huelva (South–West Spain)

Nutrient (nitrate, phosphate, silica) and dissolved metal (Al, Cu, As, Cd, Ni, Zn, Fe, U) distributions were studied in the mixing zones of the Tinto and Odiel rivers which drain the South Iberian pyrite belt. Phosphate distribution is strongly influenced by discharges from the fertiliser industry, especially in the Tinto mixing zone. The increase of silica content in this zone is related to a release of biogenic silica from diatoms. Nitrate concentrations which are influenced by urban and industrial effluents showed an important maximum in the early stages of mixing in the Tinto (as do the metals). Compared to the Odiel river, the metal concentrations in the Tinto river reached higher values in relation to more intensive mining activities. Dissolved Fe, Mn, Al, Cu, Cd and Zn concentrations were correlated in the mixing zones of both rivers. This suggests that they have the same source and are subjected to the same controlling processes in the estuary. A maximum concentration for these metals was observed in the early stage of mixing in the Tinto and reflects a decrease of redox in a low pH (<3) environment. Downstream in the Odiel system, metals showed a slight removal. Dissolved uranium, present at a low level (0.05 μmol l−1) in the rivers, is introduced by the phosphate fertiliser industry in the estuary and trapped in sedimentation areas. As a consequence, waters of the Gulf of Cadiz have a U content similar to that of the open seawater.