High-fluoride (F−) groundwater is a widespread environmental problem that poses significant risks to human health in many regions worldwide. Understanding the origin, circulation, and evolution of fluoride-rich groundwater is therefore essential for effective groundwater management and mitigation strategies. In recent years, stable isotope techniques have helped to address key gaps in understanding the hydrogeochemical processes governing F− enrichment, particularly regarding the source identification and water-rock interaction mechanisms that remain poorly constrained. This study reviews the applications of hydrogen–oxygen, strontium–calcium, and lithium–boron isotopes in research on high-F− groundwater systems. Hydrogen and oxygen isotopes (δ2H and δ18O) are widely used to identify groundwater recharge sources, mixing processes, and evaporative effects, thereby providing key constraints on the origin of fluoride-rich groundwater. Strontium and calcium isotopes (87Sr/86Sr and δ44/40Ca) serve as effective tracers of water-rock interactions and associated hydrogeochemical processes, including mineral weathering and dissolution, cation exchange, and secondary mineral precipitation, which play critical roles in fluoride mobilization and enrichment. In addition, lithium, and boron isotopes (δ7Li and δ11B) provide valuable insights into the influence of geothermal fluids and deep hydrothermal processes on fluoride accumulation in groundwater systems. Overall, the integrated application of these stable isotope systems offers a robust framework for elucidating the formation mechanisms and evolutionary pathways of high-F− groundwater. Moving beyond qualitative source identification, future research should prioritize the development of Bayesian isotope mixing models that explicitly quantify uncertainty in fluoride source apportionment and utilize sensitivity analysis to test competing hydrogeochemical mechanisms.
Zhang et al. (2026) studied this question.