Revealing chlorinated ethene transformation hotspots in a nitrate-impacted hyporheic zone.

Hyporheic zones are increasingly thought of as natural bioreactors, capable of transforming and attenuating groundwater pollutants present in diffuse baseflow. An underappreciated scenario in the understanding of contaminant fate in hyporheic zones is the interaction between point-source trichloroethene (TCE) plumes and ubiquitous, non-point source pollutants such as nitrate. This study aims to conceptualise critical biogeochemical gradients in the hyporheic zone which govern the export potential of these redox-sensitive pollutants from carbon-poor, oxic aquifers. Within the TCE plume discharge zone, discrete vertical profiling of the upper 100 cm of sediment pore water chemistry revealed an 80% increase in dissolved organic carbon (DOC) concentrations and 20-60 cm thick hypoxic zones (<2 mg O2 L-1) within which most reactive transport was observed. A 33% reduction of nitrate concentrations coincided with elevated pore water nitrous oxide concentrations as well as the appearance of manganese and the TCE metabolite cis-1,2-dichloroethene (cDCE). Elevated groundwater nitrate concentrations (>50 mg L-1) create a large stoichiometric demand for bioavailable DOC in discharging groundwater. With the benefit of a high-resolution grid of pore water samplers investigating the shallowest 30 cm of hypoxic groundwater flow paths, we identified DOC-rich hotspots associated with submerged vegetation (Ranunculus spp.), where low-energy metabolic processes such as mineral dissolution/reduction, methanogenesis and ammonification dominate. Using a chlorine index metric, we show that enhanced TCE to cDCE transformation takes place within these biogeochemical hotspots, highlighting their relevance for natural plume attenuation.

Natural attenuation of chlorinated ethenes in hyporheic zones: A review of key biogeochemical processes and in-situ transformation potential.

Chlorinated ethenes (CEs) are legacy contaminants whose chemical footprint is expected to persist in aquifers around the world for many decades to come. These organohalides have been reported in river systems with concerning prevalence and are thought to be significant chemical stressors in urban water ecosystems. The aquifer-river interface (known as the hyporheic zone) is a critical pathway for CE discharge to surface water bodies in groundwater baseflow. This pore water system may represent a natural bioreactor where anoxic and oxic biotransformation process act in synergy to reduce or even eliminate contaminant fluxes to surface water. Here, we critically review current process understanding of anaerobic CE respiration in the competitive framework of hyporheic zone biogeochemical cycling fuelled by in-situ fermentation of natural organic matter. We conceptualise anoxic-oxic interface development for metabolic and co-metabolic mineralisation by a range of aerobic bacteria with a focus on vinyl chloride degradation pathways. The superimposition of microbial metabolic processes occurring in sediment biofilms and bulk solute transport delivering reactants produces a scale dependence in contaminant transformation rates. Process interpretation is often confounded by the natural geological heterogeneity typical of most riverbed environments. We discuss insights from recent field experience of CE plumes discharging to surface water and present a range of practical monitoring technologies which address this inherent complexity at different spatial scales. Future research must address key dynamics which link supply of limiting reactants, residence times and microbial ecophysiology to better understand the natural attenuation capacity of hyporheic systems.