Quantifying groundwater phosphorus flux to rivers in a typical agricultural watershed in eastern China

Increasing evidence indicates that groundwater can contain high dissolved phosphorus (P) concentrations, thereby contributing as a potential pollution source for surface waters. However, limited quantitative knowledge is available concerning groundwater P fluxes to rivers. Based on monthly hydrochemical monitoring data for rivers and groundwater in 2017-2020, this study combined baseflow separation methods and a load apportionment model (LAM) to quantify contributions from point sources, surface runoff, and groundwater/subsurface runoff to riverine P pollution in a typical agricultural watershed of eastern China. In the studied Shuanggang River, most total P (TP) and dissolved P (DP) concentrations exceeded targeted water quality standards (i.e., TP ≤ 0.2 mg P L^-1, DP ≤ 0.05 mg P L^-1), with DP (76 ± 20%) being the major riverine P form. Observed DP concentrations in groundwater were generally higher than those of river waters. There was a strong correlation between river and groundwater P concentrations, implying that groundwater might be a considerable P pollution source to rivers. The nonlinear reservoir algorithm estimated that baseflow/groundwater contributed 66-68% of monthly riverine water discharge on average, which was consistent with results estimated by an isotope-based sine-wave fitting method. The LAM incorporating point sources, surface runoff, and groundwater effectively predicted daily riverine TP [calibration: coefficient of determination (R²) = 0.76-0.82, Nash-Sutcliffe Efficiency (NSE) = 0.61-0.77; validation: R² = 0.88-0.98, NSE = 0.54-0.64] and DP loads (calibration: R² = 0.73-0.84, NSE = 0.67-0.72; validation: R² = 0.88-0.97, NSE = 0.56-0.83). The LAM estimated point source, surface runoff, and groundwater contributions to riverine loads were 15-18%, 14-35%, and 46-70% for TP loads and 7-9%, 10-32%, and 59-82% for DP loads, respectively. Groundwater was the dominant riverine P source due to long-term accumulation of P from excess fertilizer and farmyard manure applications. The developed methodology provides an alternative method for quantifying P pollution loads from point sources, surface runoff, and groundwater to rivers. This study highlights the importance of controlling groundwater P pollution from agricultural lands to address riverine water quality objectives and further implies that decreasing fertilizer P application rates and utilizing legacy soil P for crop uptake are required to reduce groundwater P loads to rivers.