Processes controlling 234U and 238U isotope fractionation and helium in the groundwater of the St. Lawrence Lowlands,Quebec: The potential role of natural rock fracturing

The goal of this study is to explain the origin of ²³⁴U–²³⁸U fractionation in groundwater from sedimentary aquifers of the St. Lawrence Lowlands (Quebec, Canada), and its relationship with ³He/⁴He ratios, to gain insight regarding the evolution of groundwater in the region. (²³⁴U/²³⁸U) activity ratios, or (²³⁴U/²³⁸U)_act, were measured in 23 groundwater samples from shallow Quaternary unconsolidated sediments and from the deeper fractured regional aquifer of the Becancour River watershed. The lowest (²³⁴U/²³⁸U)_act, 1.14 ± 0.01, was measured in Ca–HCO₃-type freshwater from the Quaternary Shallower Aquifer, where bulk dissolution of the carbonate allows U to migrate into water with little ²³⁴U–²³⁸U isotopic fractionation. The (²³⁴U/²³⁸U)_act increases to 6.07 ± 0.14 in Na–HCO₃–Cl-type groundwater. Preferential migration of ²³⁴U into water by α-recoil is the underlying process responsible for this isotopic fractionation. An inverse relationship between (²³⁴U/²³⁸U)_act and ³He/⁴He ratios has been observed. This relationship reflects the mixing of newly recharged water, with (²³⁴U/²³⁸U)_act close to the secular equilibrium and containing atmospheric/tritiogenic helium, and mildly-mineralized older water (¹⁴C ages of 6.6 kyrs), with (²³⁴U/²³⁸U)_act of ≥6.07 and large amounts of radiogenic ⁴He, in excess of the steady-state amount produced in situ. The simultaneous fractionation of (²³⁴U/²³⁸U)_act and the addition of excess ⁴He could be locally controlled by stress-induced rock fracturing. This process increases the surface area of the aquifer matrix exposed to pore water, from which produced ⁴He and ²³⁴U can be released by α-recoil and diffusion. This process would also facilitate the release of radiogenic helium at rates greater than those supported by steady-state U–Th production in the rock. Consequently, sources internal to the aquifers could cause the radiogenic ⁴He excesses measured in groundwater.