Understanding how water and solutes enter and propagate through freshwater landscapes in the Anthropocene is critical to protecting and restoring aquatic ecosystems and ensuring human water security. However, high hydrochemical variability in headwater streams, where most carbon and nutrients enter river networks, has hindered effective modelling and management. We developed an analytical framework informed by landscape ecology and catchment hydrology to quantify spatiotemporal variability across scales, which we tested in 56 headwater catchments, sampled periodically over 12 years in western France. Unexpectedly, temporal variability in dissolved carbon, nutrients and major ions was preserved moving downstream and spatial patterns of water chemistry were stable on annual to decadal timescales, partly because of synchronous variation in solute concentrations. These findings suggest that while concentration and flux cannot be extrapolated among subcatchments, periodic sampling of headwaters provides valuable information about solute sources and subcatchment resilience to disturbance.

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of the mechanisms and processes associated with the identification of critical source areas, P mobilization, delivery and biogeochemical processing, as otherwise even highintensity and high-resolution research efforts will only reveal an incomplete picture of the full global impact of the terrestrial derived P on downstream aquatic and marine ecosystems.

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Quantifying nutrient attenuation at watershed scales requires long-term water chemistry data, water discharge, and detailed nutrient input chronicles. Consequently, nutrient attenuation estimates are largely limited to long-term research areas or modeling studies, constraining understanding of the ecological characteristics controlling nutrient attenuation and complicating efforts to protect or restore water quality in developed and developing regions. Here, we combined long-term data and a broad suite of biogeochemical parameters from 49 watersheds in northwestern France to test how well instantaneous measurements can predict nitrogen (N) and phosphorus (P) attenuation at watershed scales. We evaluated 13 biogeochemical and 12 hydrological proxies of hydrological flowpaths, residence time, and biogeochemical transformation. Across the 49 watersheds, nutrient attenuation ranged from 88 to −2% for N and 99-96% for P. The strongest biogeochemical proxies of N attenuation were NO − 3 isotopes, rare earth elements (REEs), radon, and turbidity, together explaining 75% of observed variation. For P attenuation, REEs, NO − 3 isotopes, molecular weight of dissolved organic matter, and radon were the strongest proxies, but only explained 27% of observed variation. However, a single hydrological parameter-annual runoff-explained 91% of N attenuation and the relative abundance of schist bedrock explained 56% of P attenuation. We discuss how runoff both controls and reflects watershed hydrology, biogeochemistry, and nutrient attenuation. For example, runoff was correlated with long-term decreases in nutrient concentration, demonstrating how leakier watersheds recover more quickly from nutrient saturation. Given the immense fertilization capacity of modern society, we propose that eutrophication can only be solved by reducing nutrient inputs, though hydrochemical proxies can provide valuable information on where to carry out essential food production activities.

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