Abstract. Characterizing and understanding spatial variability in water quality for a variety of chemical elements is an issue for present and future water resource management. However, most studies of spatial variability in water quality focus on a single element and rarely consider headwater catchments. Moreover, they assess few catchments and focus on annual means without considering seasonal variations. To overcome these limitations, we studied spatial variability and seasonal variation in dissolved C, N, and P concentrations at the scale of an intensively farmed region of France (Brittany). We analyzed 185 headwater catchments (from 5–179 km2) for which 10-year time series of monthly concentrations and daily stream flow were available from public databases. We calculated interannual loads, concentration percentiles, and seasonal metrics for each element to assess their spatial patterns and correlations. We then performed rank correlation analyses between water quality, human pressures, and soil and climate features. Results show that nitrate (NO3) concentrations increased with increasing agricultural pressures and base flow contribution; dissolved organic carbon (DOC) concentrations decreased with increasing rainfall, base flow contribution, and topography; and soluble reactive phosphorus (SRP) concentrations showed weaker positive correlations with diffuse and point sources, rainfall and topography. An opposite pattern was found between DOC and NO3: spatially, between their median concentrations, and temporally, according to their seasonal cycles. The annual maximum NO3 concentration was in-phase with maximum flow when the base flow index was low, but this synchrony disappeared when flow flashiness was lower. The annual maximum SRP concentration occurred during the low-flow period in nearly all catchments. The approach shows that despite the relatively low frequency of public water quality data, such databases can provide consistent pictures of the spatio-temporal variability of water quality and of its drivers as soon as they contain a large number of catchments to compare and a sufficient length of concentration time series.

Variability of hydro-chemical response to storm events captured using high-frequency river monitoring in subtropical catchments, southern Brazil.

<p>The effects of climate change on the quality of freshwaters remains poorly investigated while these effects are likely to be ambiguous. Indeed, such effects are partly direct such as temperature control on reaction rates, and partly indirect such as decrease of dilution processes with drier low flows. How the fate of a given pollutant responds to climate change can differ depending on its sources, reactivity and mobilization processes. Therefore, investigating the hydrochemical response of streams to climate change requires considering several elements that differ in their sources and pathways, and in their sensitivity to local and global forcings.</p><p>A cross-analysis of hydro-climatic variables and the dynamics of three solutes - carbon (C), nitrogen (N) and phosphorus (P) - was conducted at multiple temporal scales using the long-term data sets from a Critical Zone Observatory in Western France (AgrHyS). We identified trends on climatic variables (air temperature increased, winters became wetter and summers drier) and stream concentrations (NO<sub>3</sub> concentrations decreased, DOC concentrations increased). However, no effect of air temperature and radiation was observed on stream-water concentrations for the three solutes and there was no clear response of seasonal water-quality signals to increased contrast among hydrological seasons. Therefore, despite observed inter and intra-annual effects of climate on water quality, long-term changes of stream-water concentrations seemed to be more related to agricultural changes than to climate variations.  </p><p>In such a temperate and humid region, the seasonal amplitude of climatic variables is higher than the magnitude of their long-term changes. In addition, agricultural catchments of Western Europe have received high inputs of nutrients since the 1960s that led to create legacy storages in particular N and P in the soil, the vadose zone and/or the groundwater. The damped response of water quality may then be related to legacy storage, leading to lower sensitivity to climatic than to agricultural drivers. Disentangling the respective effects of climate and human activities on stream water quality is particularly challenging, even more in such contexts dealing with legacy storages. As a perspective, we show how using ratios of elements with contrasted properties or origin can help addressing this challenge.  </p>

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