Unravelling nitrate transformation mechanisms in karst catchments through the coupling of high-frequency sensor data...

Nitrate dynamics within a catchment are critical to the earth's system process, yet the intricate details of its transport and transformation at high resolutions remain elusive. Hydrological effects on nitrate dynamics in particular have not been thoroughly assessed previously and this knowledge gap hampers our understanding and effective management of nitrogen cycling in watersheds. Here, machine learning (ML) models were employed to reconstruct the annual variation trend in nitrate dynamics and isotopes within a typical karst catchment. Random forest model demonstrates promising potential in predicting nitrate concentration and its isotopes, surpassing other ML models (including Long Short-term Memory, Convolutional Neural Network, and Support Vector Machine) in performance. The ML-modeled NO₃^--N concentrations, δ¹⁵N-NO₃^-, and δ¹⁸O-NO₃^- values were in close agreement with field data (NSE values of 0.95, 0.80, and 0.53, respectively), which are notably challenging to achieve for process models. During the transition from dry to wet period, approximately 23.0 % of the annual precipitation (∼269.1 mm) was identified as the threshold for triggering a rapid response in the wet period. The modeled nitrate isotope values were significantly supported by the field data, suggesting seasonal variations of nitrogen sources, with precipitation as the primary driving force for fertilizer sources. Mixing of multiple sources appeared to be the main control of the transport and transformation of nitrate during the rising limb in the wet period, whereas process control (denitrification) took precedence during the falling limb, and the fate of nitrate was controlled by biogeochemical processes during the dry period.