Vertical stratification of redox conditions, denitrification and recharge in shallow groundwater on a volcanic hillslope containing relict organic matter.

Natural denitrification in groundwater systems has been recognised as an ecosystem service that reduces the impact of agriculturally-derived nitrate inputs to surface waters. Identification of this ecosystem service within the landscape would permit spatially differentiated land management and legislation. However, spatial variation in groundwater redox conditions poses a significant challenge to such a concept. To gain understanding of the small-scale mosaic of biogeochemical and hydrological controls on denitrification, we established a well field consisting of 11 multilevel well (MLW) clusters on a hillslope containing relict organic matter buried by volcanic deposits 1.8 ka before present. Based on site-specific redox classification thresholds, vertical redox gradients and denitrification potentials were detected at 7 of the 11 sites. Palaeosols or woody debris, which had previously been identified in laboratory experiments as resident electron donors fuelling denitrification, were visually recognisable at 4 of the 7 MLW sites with vertical redox gradients. Moderately enhanced groundwater dissolved organic carbon (DOC) concentrations occurred where resident electron donors were evident. DOC concentrations were lower where anoxic and nitrate-depleted groundwater was found but with an absence of resident electron donors. In these instances, it was assumed that nitrate reduction had occurred somewhere upgradient of the sampled well screen along the lateral groundwater flow path, with the proximate electron donor (DOC) largely consumed in the process, since no evidence was found for denitrification being fuelled by inorganic electron donors. Due to high variability in the isotopic signature of nitrate in oxidised groundwater, the nitrate dual isotope method did not yield firm evidence for denitrification. However, realistic vertical patterns were obtained using the excess N method. Tritium-based age dating revealed that oxic conditions were restricted to young groundwater (mean residence time ≤ 3 y), while anoxic conditions were observed across a wider age range (3-25 y).