Focused recharge enhances soil carbon leakage and carbonate weathering in groundwater: Implications for subsurface carbon sinks

Soil carbon leakage into groundwater is a crucial and natural carbon sink process in the subsurface carbon cycling. However, the primary driving force for soil carbon downward leakage and the following fate of the carbon in groundwater remains elusive. Here, we investigated multi-seasonal hydrodynamics, hydrogeochemistry and environmental isotopes (delta 13C, delta 2H and delta 18O) in groundwater wells in a humid region. Frequent water-table rise (1 - 3 m) and isotopic signature fluctuation after the concentrated rainfall supported evidence for the occurrence of focused groundwater recharge. We found that focused recharge during the shorter and wetter season induced the increase of groundwater DOC (306.5 +/- 231 mu mol/L) and CO2 (2154 +/- 726.6 mu mol/L), the dilution of CH4 (1.75 +/- 1.2 mu mol/L) and DIC (4486 +/- 790.8 mu mol/L) as well as depleted delta 13C signatures (-17%0 - -18%0). These variations jointly elucidated accelerated soil carbon downward leakage and hydrodynamic mixing driven by focused recharge. Saturation index calculation and PHREEQC simulations confirmed that massive groundwater CO2 from soil carbon leakage during focused recharge exerted positive perturbations on carbonate weathering, and ultimately stored in a more stable form by transforming into HCO3- . Carbon isotope analysis further identified carbonate weathering accounted for approximately one third of DIC dynamics compared to biogenic sources. This study highlights that focused recharge has a disproportional contribution to flushing soil-derived carbon into groundwater and activating carbonate weathering in the groundwater, with important implications for temporal variability of non-negligible subsurface carbon sinks in the global carbon budget.