Abstract. Tidal estuarine channels have complex and dynamic interfaces controlled by upland groundwater discharge, waves, tides and channel velocities that also control biogeochemical processes within adjacent sediments. In an Australian subtropical estuary, discharging groundwater with elevated (> 300 mg N L−1) NH4+ and NO3- concentrations had 80 % of the N attenuated at this interface, one of the highest N removal rates (> 100 mmol m−2 day−1) measured for intertidal sediments. The remaining N was also diluted by a factor of 2 or more by mixing with surface water before being discharged to the estuary. Most of the mixing occurred in a hyporheic zone in the upper 50 cm of the channel bed. However, groundwater entering this zone was already partially mixed (12 %–60 %) with surface water via tide-induced circulation. Below the hyporheic zone (50–125 cm below the channel bed), NO3- concentrations declined slightly faster than NH4+ concentrations and δ15NNO3 and δ18ONO3 gradually increased, suggesting a co-occurrence of anammox and denitrification. In the hyporheic zone, δ15NNO3 continued to become enriched (consistent with either denitrification or anammox) but δ18ONO3 became more depleted (indicating some nitrification). A high δ15NNO3 (23 ‰–35 ‰) and a low δ18ONO3 (1.2 ‰–8.2 ‰) in all porewater samples indicated that the original synthetic nitrate pool (industrial NH4NO3; δ15N ∼ 0 ‰; δ18O ∼ 18 ‰–20 ‰) had turned over completely during transport in the aquifer before reaching the channel bed. Whilst porewater NO3- was more δ18O depleted than its synthetic source, porewater δ18OH2O (−3.2 ‰ to −1.8 ‰) was enriched by 1 ‰–4 ‰ relative to rainfall-derived groundwater mixed with seawater. Isotopic fractionation from H2O uptake during the N cycle and H2O production during synthetic NO3- reduction are the probable causes for this δ18OH2O enrichment. Whilst occurring at a smaller spatial scale than tide-induced circulation, hyporheic exchange can provide a similar magnitude of mixing and biogeochemical transformations for groundwater solutes discharging through intertidal zones.

Understanding of site-scale physical and chemical heterogeneities will inform remediation strategies for unlined rural landfills worldwide. The aim of this study was to characterize potential sources of nitrogen contamination to groundwater at an unlined landfill in rural western Victoria, Australia. Results revealed simultaneously high concentrations of both nitrate and ammonia within several wells, indicative of heterogeneous redox potentials within the unconfined aquifer. Combined isotopic analyses of δ 15 N and δ 18 O in nitrate identified a leachate-derived source and active denitrification across two sites hydraulically downgradient from the landfill cell. Groundwater at an up-gradient site, as well as nearby surface water samples from a riparian creek, reflected primarily the isotopic signature of agriculturally-derived nitrate with overprinting from atmospheric exchanges of nitrogen and oxygen. Nitrate and ammonia in the creek were interpreted to result from a mixture of leachate and agricultural sources. Results illustrate how redox gradients across a landfill leachate plume impact biogeochemical nitrogen cycling.

Abstract. Estuarine environments have a dynamic groundwater -surface water interface driven by terrestrial 15 groundwater discharge, tidal cycles, waves and other processes. This interface also corresponds to an active biogeochemical environment. An assessment of discharging groundwater with elevated (>300 mg N L -1 ) NH4 + and NO3 -concentrations at such an interface located in a subtropical estuary indicated that 80 % of the N was attenuated, one of the highest N removal rates (>100 mmol m -2 day -1 ) measured for intertidal sediments. The remaining N was also diluted by a factor of two or more by mixing before being discharged to the estuary. Most reaching the riverbed. Whilst porewater NO3 -was more  18 O depleted than its synthetic source, porewater (-3.2 to -1.8‰) was enriched by 1-4‰ relative to rainfall-derived groundwater mixed with seawater. 30Isotopic fractionation from H2O uptake during the N cycle and H2O production during synthetic NO3 -reduction are the probable causes for this enrichment.