Identify nitrogen transport paths and sources contribution in karst valley depression area using isotopic approach.

Karst groundwater provides drinking water for a quarter of Earth's population. However, in intensive agricultural regions worldwide, karst water is commonly polluted by nitrate (NO ₃ ^- ), particularly in the valley depression areas with well hydrological connectivity. The valley depression aquifers are particularly vulnerable to anthropogenic pollution because their pipes and sinkholes respond quickly to rainfall events and anthropogenic inputs. Identifying nitrate sources and transport paths in the valley depression areas is key to understanding the nitrogen cycle and effectively preventing and controlling NO ₃ ^- pollution. This study collected high-resolution samples at four sites including one surface stream-SS, two sinkholes-SH and reservoir-Re, during the wet season in the headwater sub-catchment. The chemical component concentrations and stable isotopes (δ ¹⁵ N-NO ₃ ^- and δ ¹⁸ O-NO ₃ ^- ) were analyzed. The stable isotope analysis model in R language (SIAR) was used to quantitatively analyze the contribution rate of NO ₃ ^- sources. The results showed that the down section site (Re) has the highest [NO ₃ ^- -N], followed by SH and the lowest SS. The sources calculation of SIAR demonstrated that, during the non-rainfall period, soil organic nitrogen was the primary source of the down section site, followed by fertilizer and the upper reaches sinkholes. During the rainfall period, fertilizer was the primary source of the down section site, followed by soil organic nitrogen and from upper reaches sinkholes. Rainfall events accelerated fertilizer-leaching into the groundwater. Slight denitrification may have occurred at the sampling sites but the assimilation of Re and SH could not occur. In conclusion, agricultural activities were still the primary influencing factor of [NO ₃ ^- -N] in the study area. Therefore, the focus of NO ₃ ^- prevention and control in the valley depression areas should consider the methods and timing of fertilization and the spatial distribution of sinkholes. To reduce nitrogen flux in the valley depression area, effective management policy should consider, e.g., prolongation of water residence time by wetland, and blocking nitrogen loss paths by sinkholes.
Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
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