Routine stream monitoring data enables the unravelling of hydrological pathways and transfers of agricultural contaminants through catchments

Catchment-scale understanding of water and contaminant fluxes through all pathways is essential to address land use and climate change impacts on freshwater. However, few options exist to obtain this understanding for the many catchments worldwide for which streamflow and low-frequency water chemistry, but little other data exists. We applied the Bayesian chemistry-assisted hydrograph separation and load partitioning model (BACH) to 47 catchments with widely differing characteristics. As BACH relies on concentration differences between pathways, chemodynamic behaviour of a water constituent indicates its likely suitability as tracer. Typical tracers (e.g. silica, chloride) were unavailable, but Electrical Conductivity and a few monitored nutrients proved chemodynamic in most catchments. Using one of two tracer combinations (Total Nitrogen + Electrical Conductivity, Total Nitrogen + Total Phosphorus) allowed in 85 % of the catchments to estimate streamflow contributions by near-surface (NS), shallow groundwater (SGW), and deep groundwater (DGW) pathways and pathway-specific tracer concentrations and yields with acceptable confidence. In 46 catchments, at least two pathways contributed ≥20 % of the streamflow, and all three ≥20 % in 12 catchments, cautioning against the notion of a single ‘dominant’ pathway. In contrast to hydrometric hydrograph separation, BACH allows differentiation between ‘young’ (NS + SGW) and ‘old’ (DGW) water, which is crucial for the understanding of pollution in catchments with strong temporal gradients in land use intensity. Consistent with generally increasing land use intensity, and groundwater denitrification occurring in some catchments, Total Nitrogen (TN) concentrations were in most catchments higher in NS and SGW compared to DGW. In most catchments, the greatest fraction of the TN yield was conveyed by SGW (≈ 40–90 %). Exceptions were wet and hilly catchments under bush, where the NS transferred most of the very low yields, and three young volcanic catchments where the DGW transferred the majority of the yield due to particularly high DGW flow contributions. [Display omitted] •Chemistry-assisted hydrograph separation provided 3-component pathway understanding.•Electrical conductivity, Total Nitrogen and Total Phosphorus were promising tracers.•Tracers allowed to separate ‘young’ and ‘old’ water.•Young shallow groundwater most important flow pathway in most catchments.•Stream concentration dynamics resulting from vertical tra