Hydrologic models partition flows into surface and subsurface pathways, but their calibration is typically conducted only against streamflow. Here we argue that unless model outcomes are constrained using flow pathway data, multiple partitioning schemes can lead to the same streamflow. This point becomes critical for biogeochemical modeling as individual flow paths may yield unique chemical signatures. We show how information on flow pathways can be used to constrain hydrologic flow partitioning and how improved partitioning can lead to better water quality predictions. As a case study, an agricultural basin in Ontario is used to demonstrate that using tile discharge data could increase the performance of both the hydrology and the nitrogen transport models. Watershed‐scale tile discharge was estimated based on sparse tile data collected at some tiles using a novel regression‐based approach. Through a series of calibration experiments, we show that utilizing tile flow signatures as calibration criteria improves model performance in the prediction of nitrate loads in both the calibration and validation periods. Predictability of nitrate loads is improved even with no tile flow data and by model calibration only against an approximate understanding of annual tile flow percent. However, despite high values of goodness‐of‐fit metrics in this case, temporal dynamics of predictions are inconsistent with reality. For instance, the model predicts significant tile discharge in summer with no tile flow occurrence in the field. Hence, the proposed tile flow upscaling approach and the partitioning‐constrained model calibration are vital steps toward improving the predictability of biogeochemical models in tiled landscapes.

Phosphorus (P) mobilization in agricultural landscapes is regulated by both hydrologic (transport) and biogeochemical (supply) processes interacting within soils; however, the dominance of these controls can vary spatially and temporally. In this study, we analyzed a 5-yr dataset of stormflow events across nine agricultural fields in the lower Great Lakes region of Ontario, Canada, to determine if edge-of-field surface runoff and tile drainage losses (total and dissolved reactive P) were limited by transport mechanisms or P supply. Field sites ranged from clay loam, silt loam, to sandy loam textures. Findings indicate that biogeochemical processes (P supply) were more important for tile drain P loading patterns (i.e., variable flow-weighted mean concentrations ([]) across a range of flow regimes) relative to surface runoff, which trended toward a more chemostatic or transport-limited response. At two sites with the same soil texture, higher tile [] and greater transport limitations were apparent at the site with higher soil available P (STP); however, STP did not significantly correlate with tile [] or P loading patterns across the nine sites. This may reflect that the fields were all within a narrow STP range and were not elevated in STP concentrations (Olsen-P, ≤25 mg kg). For the study sites where STP was maintained at reasonable concentrations, hydrology was less of a driving factor for tile P loadings, and thus management strategies that limit P supply may be an effective way to reduce P losses from fields (e.g., timing of fertilizer application).