Carbon Isotopic Signatures of Aquifer Organic Molecules along Anthropogenic Recharge Gradients

The property of groundwater dissolved organic matter (DOM) subjected to anthropogenic groundwater recharge (AGR) might be affected by the water quality disparity between surface water and natural groundwater. However, the diverse molecular scenarios of groundwater DOM under uneven recharging levels remain largely unexplored. We combined molecular characteristics, carbon isotopic signatures of organic molecules, and end-member mixing analysis to explore the sensitivity and potential tracking capabilities of DOM to AGR along with recharging gradients. Our findings suggested that AGR enriched groundwater with diverse, saturated, labile, and sulfur-rich molecules, amplifying DOM abundance and intensity, which intensified with recharge gradients. Additionally, S-containing molecules and their indicators like CHOS% (with threshold values of 7.82%) exhibited high sensitivity and predictive power for AGR recognition. The major signatures (diversity, saturated degree, and stability) indicated by ¹³C-containing molecules were similar to the whole molecular pool. Notably, specific molecules (C₁₂H₁₀O₅S and C₁₅H₁₆O₁₂), although not detected in all groundwater samples, exhibit robust stability or favorable solubility, rendering them potential candidates as AGR-sensitive molecules. The R_13C/12C ratio of ¹³C-containing C₁₉H₂₄O₅ emerged as the most robust tracer, exhibiting a strong correlation with the recharge ratio and the smallest deviation from the theoretical mixing line, signifying its optimal suitability for precise groundwater DOM source apportionment. This study offers novel insights into AGR impacts and contributes to fostering a harmonious balance between human activities and water resource sustainability.