High radium (Ra) concentrations in potable portions of the Cambrian-Ordovician (C-O) aquifer system were investigated using water-quality data and environmental tracers (³H, ³He_trit, SF₆, ¹⁴C and ⁴He_rad) of groundwater age from 80 public-supply wells (PSWs). Groundwater ages were estimated by calibration of tracers to lumped parameter models and ranged from modern (<50 yr) in upgradient, regionally unconfined areas to ancient (>1 Myr) in the most downgradient, confined portions of the potable system. More than 80 and 40 percent of mean groundwater ages were older than 1000 and 50,000 yr, respectively. Anoxic, Fe-reducing conditions and increased mineralization develop with time in the aquifer system and mobilize Ra into solution resulting in the frequent occurrence of combined Ra (Ra_c = ²²⁶Ra + ²²⁸Ra) at concentrations exceeding the USEPA MCL of 185 mBq/L (5 pCi/L). The distribution of the three Ra isotopes comprising total Ra (Ra_t = ²²⁴Ra + ²²⁶Ra + ²²⁸Ra) differed across the aquifer system. The concentrations of ²²⁴Ra and ²²⁸Ra were strongly correlated and comprised a larger proportion of the Ra_t concentration in samples from the regionally unconfined area, where arkosic sandstones provide an enhanced source for progeny from the ²³²Th decay series. ²²⁶Ra comprised a larger proportion of the Ra_tconcentration in samples from downgradient confined regions. Concentrations of Ra_t were significantly greater in samples from the regionally confined area of the aquifer system because of the increase in ²²⁶Ra concentrations there as compared to the regionally unconfined area. ²²⁶Ra distribution coefficients decreased substantially with anoxic conditions and increasing ionic strength of groundwater (mineralization), indicating that Ra is mobilized to solution from solid phases of the aquifer as adsorption capacity is diminished. The amount of ²²⁶Ra released from solid phases by alpha-recoil mechanisms and retained in solution increases relative to the amount of Ra sequestered by adsorption processes or co-precipitation with barite as adsorption capacity and the concentration of Ba decreases. Although ²²⁶Ra occurred at concentrations greater than ²²⁴Ra or ²²⁸Ra, the ingestion exposure risk was greater for ²²⁸Ra owing to its greater toxicity. In addition, ²²⁴Ra added substantial alpha-particle radioactivity to potable samples from the C-O aquifer system. Thus, monitoring for Ra isotopes and gross-alpha-activity (GAA) is important in upgradient, regionally unconfined areas as downgradient, and GAA measurements made within 72 h of sample collection would best capture alpha-particle radiation from the short-lived ²²⁴Ra.