Abstract:Nitrate concentrations in streamwater of agricultural catchments often exhibit interannual variations, which are supposed to result from land-use changes, as well as seasonal variations mainly explained by the effect of hydrological and biogeochemical cycles. In catchments on impervious bedrock, seasonal variations of nitrate concentrations in streamwater are usually characterized by higher nitrate concentrations in winter than in summer. However, intermediate or inverse cycles with higher concentrations in summer are sometimes observed. An experimental study was carried out to assess the mechanisms that determine the seasonal cycles of streamwater nitrate concentrations in intensive agricultural catchments. Temporal and spatial patterns of groundwater concentrations were investigated in two adjacent catchments located in south-western Brittany (France), characterized by different seasonal variations of streamwater nitrate concentrations. Wells were drilled across the hillslope at depths ranging from 1Ð5 to 20 m. Dynamics of the water table were monitored and the groundwater nitrate and chloride concentrations were measured weekly over 2 years. Results highlighted that groundwater was partitioned into downslope domains, where denitrification induced lower nitrate concentrations than into mid-slope and upslope domains. For one catchment, high subsurface flow with high nitrate concentrations during high water periods and active denitrification during low water periods explained the higher streamwater nitrate concentrations in winter than in summer. For the other catchment, the high contribution of groundwater with high nitrate concentrations smoothed or inverted this trend. Increasing bromide/chloride ratio and nitrate concentrations with depth argued for an effect of past agricultural pressure on this catchment. The relative contribution of flows in time and correlatively the spatial origin of waters, function of the depth and the location on the hillslope, and their chemical characteristics control seasonal cycles of streamwater nitrate concentrations and can influence their interannual trends.

Abstract. High-frequency, long-term and multisolute measurements are required to assess the impact of human pressures on water quality due to (i) the high temporal and spatial variability of climate and human activity and (ii) the fact that chemical solutes combine short-and long-term dynamics. Such data series are scarce. This study, based on an original and unpublished time series from the Kervidy-Naizin headwater catchment (Brittany, France), aims to determine solute transfer processes and dynamics that characterise this strongly human-impacted catchment.The Kervidy-Naizin catchment is a temperate, intensive agricultural catchment, hydrologically controlled by shallow groundwater. Over 10 yr, five solutes (nitrate, sulphate, chloride, and dissolved organic and inorganic carbon) were monitored daily at the catchment outlet and roughly every four months in the shallow groundwater.The concentrations of all five solutes showed seasonal variations but the patterns of the variations differed from one solute to another. Nitrate and chloride exhibit rather smooth variations. In contrast, sulphate as well as organic and inorganic carbon is dominated by flood flushes. The observed nitrate and chloride patterns are typical of an intensive agricultural catchment hydrologically controlled by shallow groundwater. Nitrate and chloride originating mainly from organic fertilisers accumulated over several years in the shallow groundwater. They are seasonally exported when upland groundwater connects with the stream during the wet season. Conversely, sulphate as well as organic and inorganic carbon patterns are not specific to agricultural catchments. These solutes do not come from fertilisers and do not accumulate in soil or shallow groundwater; instead, they are biogeochemically produced in the catchment. The results allowed development of a generic classification system based on the specific temporal patterns and source locations of each solute. It also considers the stocking period and the dominant process that limits transport to the stream, i.e. the connectivity of the stocking compartment. This mechanistic classification can be applied to any chemical solute to help assess its origin, storage or production location and transfer mechanism in similar catchments.

The French critical zone initiative, called OZCAR (Observatoires de la Zone Critique-Application et Recherche or Critical Zone Observatories-Application and Research) is a National Research Infrastructure (RI). OZCAR-RI is a network of instrumented sites, bringing together 21 pre-existing research observatories monitoring different compartments of the zone situated between "the rock and the sky," the Earth's skin or critical zone (CZ), over the long term. These observatories are regionally based and have specific initial scientific questions, monitoring strategies, databases, and modeling activities. The diversity of OZCAR-RI observatories and sites is well representative of the heterogeneity of the CZ and of the scientific communities studying it. Despite this diversity, all OZCAR-RI sites share a main overarching mandate, which is to monitor, understand, and predict ("earthcast") the fluxes of water and matter of the Earth's near surface and how they will change in response to the "new climatic regime." The vision for OZCAR strategic development aims at designing an open infrastructure, building a national CZ community able to share a systemic representation of the CZ , and educating a new generation of scientists more apt to tackle the wicked problem of the Anthropocene. OZCAR articulates around: (i) a set of common scientific questions and cross-cutting scientific activities using the wealth of OZCAR-RI observatories, (ii) an ambitious instrumental development program, and (iii) a better interaction between data and models to integrate the different time and spatial scales. Internationally, OZCAR-RI aims at strengthening the CZ community by providing a model of organization for pre-existing observatories and by offering CZ instrumented sites. OZCAR is one of two French mirrors of the European Strategy Forum on Research Infrastructure (eLTER-ESFRI) project.