Reduction capacity in the transmissive zones fueled by the embedded low-permeability lenses: Implications for contaminant transformation in heterogeneous aquifers.

Redox conditions play a decisive role in regulating contaminant and nutrient transformation in groundwater. Here we quantitatively described and interpreted the temporal and spatial variations of aquifer reduction capacity formation in lens-embedded heterogeneous aquifers in 1-D columns. Experimental results indicated that the aquifer reduction capacity exported from the low-permeability lens permeated into the downstream sandy zones, where it subsequently accumulated and extended. Reactive transport modeling suggested that reduction capacity within the lens preferentially diffused to the transmissive zones around the lens-sand interface, and was then transported via convection to downstream transmissive zones. A low-permeability lens of the same volume, but more elongated in the flow direction, led to less concentrated reduction capacity but extended further downgradient from the lens. The increased flow velocity attenuated the maintenance of aquifer reduction capacity by enhancing mixing and diluting processes in the transmissive zones. The reduction zones formed downstream from the low-permeability lens were hotpots for resisting the oxidative perturbation by O2. This study highlights the important role of low-permeability lenses as large and long-term electron pools for the transmissive zones, and thus providing aquifer reduction capacity for contaminant transformation and remediation in heterogeneous aquifers.

Water Table Fluctuations Regulate Hydrogen Peroxide Production and Distribution in Unconfined Aquifers.

Significance of reactive oxygen species (ROS) in subsurface has been increasingly documented in recent years, whereas the mechanisms controlling ROS production and distribution in subsurface remain poorly understood. Here we show that water table fluctuations regulate the dynamics of hydrogen peroxide (H2O2) production and distribution in unconfined aquifers. In one hydrological year, we measured the dynamics of H2O2 distribution in an unconfined aquifer impacted by a 14 m water level fluctuation in the adjacent Yangtze River. H2O2 concentrations in groundwater attained up to 123 nM at rising water table stage in summer, but were low or even below the detection limit at the other stages of stable and falling water table. Lab experiments and kinetic models revealed that abiotic reactions between dissolved O2 and reduced species (i.e., Fe(II) and organic matter) were responsible for H2O2 production in the aquifers. Both field observations and reactive transport models unveiled that a rising water table developed a thermodynamically unstable banded zone in the unconfined aquifer in which elevated coexisting dissolved O2 and reduced species favored abiotic H2O2 production. Our findings provide fundamentals for understanding and predicting ROS distribution in unconfined aquifers, and constrain the significance of ROS in aquifers to specific temporal and spatial domains.