Effects of nitrate contamination and seasonal variation on the denitrification and greenhouse gas production in La Rocina Stream (Doñana National Park, SW Spain)

Climatic influence (global warming and decreased rainfall) could lead to an increase in the ecological and toxicological effects of the pollution in aquatic ecosystems, especially contamination from agricultural nitrate (NO₃⁻) fertilizers. Physicochemical properties of the surface waters and sediments of four selected sites varying in NO₃⁻ concentration along La Rocina Stream, which feeds Marisma del Rocio in Doñana National Park (South West, Spain), were studied. Electrical conductivity, pH, content in macro and microelements, total organic carbon and nitrogen, and dissolved carbon and nitrogen were affected by each sampling site and sampling time. Contaminant NO₃⁻ in surface water at the site with the highest NO₃⁻ concentration (ranged in 61.6-106.6 mg L⁻¹) was of inorganic origin, most probably from chemical fertilizers, as determined chemically (90% of the total dissolved nitrogen from NO₃⁻) and by isotopic analysis of δ¹⁵N-NO₃⁻. Changes in seasonal weather conditions and hydrological effects at the sampling sites were also responsible for variations in some biological activities (dehydrogenase, β-glucosidase, arylsulphatase, acid phosphatase and urease) in sediments, as well as in the production of the greenhouse gases CO₂, CH₄ and N₂O. Both organic matter and NO₃⁻ contents influenced rates of gas production. Increased NO₃⁻ concentration also resulted in enhanced levels of potential denitrification measured as N₂O production. The denitrification process was affected by NO₃⁻ contamination and the rainfall regimen, increasing the greenhouse gases emissions (CO₂, CH₄ and especially N₂O) during the driest season in all sampling sites studied.