Study of Groundwater Flow Properties in a Karst System by Coupled Analysis of Diverse Environmental Tracers and Discharge Dynamics

Monitoring of various naturally present substances or physical properties of the water, commonly called environmental tracers, can provide valuable insight in characteristics of groundwater flow systems and intrinsic processes. Analysis of individual tracer data most often gives an ambiguous interpretation, but employment of multiple diverse tracers can greatly increase interpretation reliability. We monitored multiple natural tracers including spring water electrical conductivity, temperature, loads of major anions and cations, stable isotopes of water, and total organic carbon together with discharge dynamics on Krbavica springs located in the Croatian part of Dinaric Karst region. We also monitored dissolved oxygen concentration as an indicator of “excess air” dynamics in the spring water, which is a very rarely recognized and not properly understood phenomenon in the karst groundwater studies. Analysis of the monitoring data revealed main characteristics of the karst system, among which following can be emphasized: (1) oxygen concentration together with conductivity and temperature (parameters monitored with high temporal resolution) were strongly related to discharge dynamics, while seasonal patterns were absent; (2) supersaturation with oxygen confirmed presence of “excess air”, most pronounced in high water conditions following the hydrograph peaks, indicating prevalence of closed flow conditions within the system; (3) electrical conductivity showed “anomalous” gradual decrease during the hydrograph recessions, attributed both to CO2 dynamics and mobilization of water from tiny fissures during high recharge conditions; and (4) stable isotope measurements confirmed good mixing of water within the system with mean residence time of a few years. Simultaneous monitoring of diverse tracer dynamics enabled detailed characterization of the karst system without excessive ambiguity.