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The composition of interstitial waters in Spain's Doñana National Park was assessed 4 years after a major pyrite slurry spill occurred from the Aznalcollar Mine. Metal and nutrient concentrations in pore waters from two of the most important watercourses traversing Doñana Park were measured: Guadiamar River (affected by the accident) and Partido Stream (unimpacted by the accident). Concentrations of dissolved constituents in interstitial waters varied according to land use in the two watersheds and to the effects of the mine spill. Levels of dissolved Co, Cu, Mo, Ti, and Zn were higher in pore waters from the Guadiamar River than in the Partido Stream, suggesting that concentrations of trace elements are still influenced by the spill. In contrast, concentrations of dissolved nutrients (NH4+, NO2-, NO3-, PO4(-3)) and some trace metals used in fertilizers (e.g. Al and Cr) were higher in the Partido Stream. Levels of dissolved As, Cs, DOC, Ge, Hg, Rb and V in the interstitial waters were equal in both watercourses. Metal concentrations in interstitial waters of the Guadiamar River floodplain were between 0.3 (As) and 16,000 (Zn) times lower than those previously reported in the river and groundwater a few weeks after the mine spill. Although metals in pore water appear to have reached levels characteristic of the area before the accident, concentrations are 60-150 times higher than those in pore waters from other regions. Metal:Al ratios in Doñana's pore waters suggest a transport of contaminants from the Iberian Pyrite Belt into Doñana Park.

Eutrophication is a major cause of wetland degradation worldwide. In recent decades, reductions in nutrient inputs have led to improvements in water quality in many rivers and lakes in central and northern Europe, but long-term trends are less clear in southern Europe. We conducted the first comprehensive study of water quality in Doñana (SW Spain), one of the most important wetland complexes in Europe and the Mediterranean region. The core area of Doñana is a large shallow, seasonal marsh (UNESCO World Heritage Site -WHS) that floods during rainy, cool winter months, then dries out during the summer. The marsh is fed by three main streams whose catchments are within a Biosphere Reserve but are impacted by greenhouses (for cultivating fruit, irrigated with groundwater), poorly treated urban wastewaters and tourism. From 2013 to 2016, we monitored nutrient (Total P, Total N, PO4 -3 , NH4 + , NO3 -, NO2 -) and phytoplankton chlorophyll-a (chla) concentrations in surface waters of the Doñana marsh and the three main streams. We quantified changes in greenhouse cover since 1995 using satellite images. Nutrient concentrations in streams were consistently higher than in the marsh, particularly in the Partido and Rocina streams that regularly reached concentrations equivalent to a "bad physico-chemical status" under the EU Water Framework Directive (WFD), and whose catchments suffered a fivefold expansion of greenhouses from 1995 to 2016. The Partido was the most polluted stream, and the most affected by wastewater effluents, and had particularly high concentrations of NH4 + (Geometric Mean = 0.3 mg L -1 ) and NO2 -(GM = 0.52 mg L -1 ) across seasons. Patterns in chla concentrations were less consistent, but streams (GM = 6.78 µg L -1 ) generally had higher concentrations than the marsh (GM = 4.27 µg L -1 ). Nutrient concentrations in spot samples within the marsh largely depended on a combination of evaporation (as revealed by higher stable isotope δ 2 H values in the water column) and spatial processes (concentrations increase close to stream entry points, where conductivity is lower). Anthropogenic nutrient pollution in entry streams is a serious problem in Doñana, with extensive stretches too toxic for fish. Reinforcement of policies aimed at reducing nutrient inputs to Doñana are urgently required to meet the biodiversity conservation and environmental objectives for the WHS and WFD, respectively. Paradoxically, the marsh is currently relied upon to purify the water entering from streams.