The Seine River estuary (France) is the receptacle of a drainage basin characterised by high population density, heavy industrial activity and intensive agriculture. Whereas nitrate concentrations are high due to diffuse sources in the upstream drainage basin, ammonium mainly originates from the effluents of the Ache`res wastewater treatment plant (WWTP) downstream from Paris and its suburbs (6.5 million equivalent-inhabitants). Ammonium is mostly nitrified in the tidal freshwater estuary and nitrification causes a strong summer oxygen deficit. Average longitudinal summer profiles of oxygen and nitrogen concentrations for two periods, between 1993-1997 and 1998-2003 in dry hydrological conditions (excluding the wet years 2000 and 2001) clearly reflect the changes due to the improved treatment of wastewater from Paris and its suburbs. On the basis of daily water flux data and twice monthly nitrogen measurements at the boundaries of the upstream freshwater estuarine section (108 km), we calculated nitrification and denitrification fluxes, whose annual averages were 43 and 71 · 10 3 kg N d À1 respectively from 1993 to 2003, with summer values (July-September) representing 73 and 57% of the annual fluxes, respectively. The degree of denitrification in the upper estuary appears to be closely related to the nitrification, itself more loosely related to the amount of reduced nitrogen (Kjeldahl) brought by the treated effluents from the Ache`res WWTP. We estimated the total N 2 O emissions to about 40 kg N d À1 (25-60 kg N d À1 ) in the same sector.
We used various approaches to establish a comprehensive budget of methane (CH4) emissions from the Seine basin, including direct emissions from livestock and soils as well as emissions from the drainage network. For the direct emissions from livestock, we used official livestock census numbers and emission factors (CH4 emitted by each animal species per head per year) available in the literature. For the emissions from soils, we based our estimates on experimental measurements in closed chambers installed on different agricultural plots, forest, and grasslands in 2008 and 2009. The results were extrapolated to the whole Seine basin, including grassland, cropland, and forest soil distributions in the Seine basin. The CH4 emissions from the Seine drainage network were also based on measurements of sampled waters in various rivers and streams (from headwaters to estuary) during different seasons in 2007, 2008, and 2010. After chemical analysis of CH4 concentrations in the water samples using a gas chromatographic technique and calculation of the CH4 supersaturation by stream order in rivers of the Seine basin (from 1 to 8) and by season we could estimate the CH4 emissions for the whole water surface area of the Seine drainage network. The livestock of the Seine basin produce CH4 emissions amounting to 166 × 106 kg C year−1, among which cattle are responsible for 85 %. The total CH4 emission from the Seine drainage network was estimated at 0.3 × 106 kg C year−1, large rivers being responsible for the largest proportion. Ebullition could account for an additional 0.2 × 106 kg C year−1. Soils of the Seine basin are a net sink for CH4 (9.4 × 106 kg C year−1). The water and soils fluxes are low with regard to emissions by livestock, but domestic waste, through landfills, could contribute an additional 40 × 106 kg C year−1
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