Tritium/helium-3 (³H/³He) and chlorofluorocarbon (CFCs, CFC–11, CFC–12, CFC–113) data are used to date the young fraction in groundwater mixtures from a karstic limestone aquifer near Valdosta, Georgia, where regional paleowater in the Upper Floridan aquifer receives recharge from two young sources—the flow of Withlacoochee River water through sinkholes in the river bed, and leakage of infiltration water through post-Eocene semi-confining beds above the Upper Floridan aquifer. In dating the young fraction of mixtures using CFCs, it is necessary to reconstruct the CFC concentration that was in the young fraction prior to mixing. The ³H/³He age is independent of the extent of dilution with older (³H-free and ³He_trit-free) water. The groundwater mixtures are designated as Type-1 for mixtures of regional paleowater and regional infiltration water and Type-2 for mixtures containing more than approximately 4% of river water. The fractions of regional paleowater, regional infiltration water, and Withlacoochee River water in the groundwater mixtures were determined from Cl⁻ and δ¹⁸O data for water from the Upper Floridan aquifer at Valdosta, Georgia.

The chlorofluorocarbons CFC–11 and CFC–113 are removed by microbial degradation and/or sorption processes in most anaerobic (Type-2) groundwater at Valdosta, but are present in some aerobic Type-1 water. CFC–12 persists in both SO₄-reducing and methanogenic water. The very low detection limits for CFCs (approximately 0.3 pg kg⁻¹) permitted CFC–11 and CFC–12 dating of the fraction of regional infiltration water in Type-1 mixtures, and CFC-12 dating of the river-water fraction in Type-2 mixtures. Overall, approximately 50% of the 85 water samples obtained from the Upper Floridan aquifer have CFC–12-based ages of the young fraction that are consistent with the ³H concentration of the groundwater. Because of uncertainties associated with very low ³H and ³He content in dilute mixtures, ³H/³He dating is limited to the river-water fraction in Type-2 mixtures containing more than about 10% river water. Of the 41 water samples measured for ³H/³He dating, dilution of ³H and low ³He concentration limited ³H/³He dating to 16 mixtures in which ³H/³He ages are defined with errors ranging from ±2 to ±7.5 a (1 σ). After correction for dilution with (assumed) CFC-free regional infiltration water and regional paleowater in the Upper Floridan aquifer, adjusted CFC–12 ages agree with ³H/³He ages within 5 a or less in 7 of the 9 co-dated Type-2 mixtures.

Tritium data and dating based on both CFC–11 and CFC–12 in Type-1 mixtures indicate that travel times of infiltration water through the overlying Post-Eocene semi-confining beds exceed 35 a. The CFC and ³H/³He dating indicate that the river fraction in most groundwater entered the groundwater reservoir in the past 20 to 30 a. Few domestic and municipal supply wells sampled intercept water younger than 5 a. Calculated velocities of river water in the Upper Floridan aquifer downgradient of the sinkhole area range from 0.4 to 8.2 m/d. Radiocarbon data indicate that ages of the regional paleowater are on the 10 000-a time scale. An average lag time of approximately 10 to 25 a is determined for discharge of groundwater from the surficial and intermediate aquifers above the Upper Floridan aquifer to the Withlacoochee River.