River network alteration of C-N-P dynamics in a mesoscale agricultural catchment.

The majority of freshwater ecosystems worldwide suffer from eutrophication, particularly because of agriculture-derived nutrient sources. In the European Union, a discrepancy exists between the scale of regulatory assessment and the size of research catchments. The Water Framework Directive sets water quality objectives at the mesoscale (50-500 km2), a scale at which both hillslope and in-stream processes influence carbon (C), nitrogen (N) and phosphorus (P) dynamics. Conversely, research catchments focus on headwaters to investigate hillslope processes while minimising the influence of river processes on C-N-P dynamics. Because hillslope and river processes have common hydro-climatic drivers, the relative influence of each on C-N-P dynamics is difficult to disentangle at the mesoscale. In the present study, we used repeated synoptic sampling throughout the river network of a 300 km2 intensively farmed catchment, spatial stochastic modelling and mass balance calculations to analyse this mesoscale conundrum. The main objective was to quantify how river processes altered C-N-P hydrochemical dynamics in different flow, concentration and temperature conditions. Our results show that flow was the main control of alterations of C-N-P dynamics in the river network, while temperature and source concentration had little or no influence. The influence of river processes peaked during low flow, with up to 50% of dissolved organic carbon (DOC) production, up to 100% of nitrate (NO3) retention and up to 50% of total phosphorus (TP) retention. Despite high percentages of river processes at low flow, their influence on annual loads was low for NO3 (median of -10%) and DOC (median of +25%) but too variable to draw conclusions for TP. Because of the differing river alteration rates among carbon and nutrients, stoichiometric ratios varied greatly from headwaters to the outlet, especially during the eutrophication-sensitive low-flow season.