Determining nitrogen fate by hydrological pathways and impact on carbonate weathering in an agricultural karst watershed

Identifying the nitrogen (N) fate is complicated and a great challenge in karst watersheds because of the co-existence of natural pools and anthropogenic sources. The objective of the study was to use stable isotopic composition of dual-isotope (δ¹⁵N_Nitrate and δ¹⁸O_Nitrate) and LOADEST model approaches to trace N sources, pathways in karst watershed. The study was conducted in the Houzhai watershed, which is a typical agricultural karst watershed from July 2016 to August 2018, to reveal the N fate and the coupled carbon(C)–N processes occurring in the riverine-watershed with agricultural activities. We found that the wet deposition of total nitrogen (TN) flux was 33.50 kg hm⁻²·a⁻¹ and dissolved nitrogen (DN) flux was 21.66 kg hm⁻²·a⁻¹. The DN runoff loss was 2.10 × 10⁵ kg·a⁻¹ and the loss of DN during the wet season accounted for 95.4% over a year. In the wet season, NO₃⁻-N daily efflux was 977.62 ± 516.66 kg ha⁻¹·day⁻¹and 248.77 ± 57.83 kg ha⁻¹·day⁻¹ in the dry season. The NH₄⁺-N efflux was 29.17 ± 10.50 kg ha⁻¹·day⁻¹ and 4.42 ± 3.07 kg ha⁻¹·day⁻¹ in the wet and dry seasons, respectively. The main form output load of N was NO₃⁻-N which was more than 30 times as much as NH₄⁺-N output loss. The NO₃⁻-N caused by rainfall contributed 11.82%–53.61% to the export load. Nitrate from soil contributed over 94% of the N to Houzhai river caused by N leaching. In addition, manure and farmland soil were the main sources of groundwater in the Houzhai watersheds, the contribution rates were 25.9% and 22.5%. The chemical N fertilizers affected carbonate weathering strongly, and the HCO₃⁻ flux caused by nitrification due to N fertilizers application in soil accounted for 23.5% of the entire watershed. This study suggested that carbonate weathering may be influenced by nitrogen nitrification in the karst watershed.