Atmospheric noble gases as tracers of biogenic gas dynamics in a shallow unconfined aquifer

Atmospheric noble gases (NGs) were used to investigate biogenic gas dynamics in a shallow unconfined aquifer impacted by a crude oil spill, near Bemidji, MN. Concentrations of He-3,He-4, Ne-20,Ne-22, Ar-36,Ar-40, Kr, and Xe were determined for gas-and aqueous-phase samples collected from the vadose and saturated zones, respectively. Systematic elemental fractionation of Ne, Ar, Kr, and Xe with respect to air was observed in both of these hydrogeologic zones. Within the vadose zone, relative ratios of Ne and Ar to Kr and Xe revealed distinct process-related trends when compared to corresponding ratios for air. The degree of NG deviation from atmospheric concentrations generally increased with greater atomic mass (i.e., Delta Xe > Delta Kr > Delta Ar > Delta Ne), indicating that Kr and Xe are the most sensitive NG tracers in the vadose zone. Reactive transport modeling of the gas data confirms that elemental fractionation can be explained by mass-dependent variations in diffusive fluxes of NGs opposite to a total pressure gradient established between different biogeochemical process zones. Depletion of atmospheric NGs was also observed within a methanogenic zone of petroleum hydrocarbon degradation located below the water table. Solubility normalized NG abundances followed the order Xe > Kr > Ar > Ne, which is indicative of dissolved NG partitioning into the gas phase in response to bubble formation and possibly ebullition. Observed elemental NG ratios of Ne/Kr, Ne/Xe, Ar/Xe, and Kr/Xe and a modeling analysis provide strong evidence that CH4 generation below the water table caused gas exsolution and possibly ebullition and carbon transfer from groundwater to the vadose zone. These results suggest that noble gases provide sensitive tracers in biologically active unconfined aquifers and can assist in identifying carbon cycling and transfer within the vadose zone, the capillary fringe, and below the water table. (C) 2013 Elsevier Ltd. All rights reserved.