Shifting nitrous oxide source/sink behaviour in a subtropical estuary revealed by automated time series observations

Abstract

The oceans are a major source of the potent greenhouse gas nitrous oxide (N2O) to the atmosphere. However, little information is available on how estuaries and the coastal ocean may contribute to N2O budgets, and on the drivers of N2O in aquatic environments. This study utilised five time series stations along the freshwater to marine continuum in a sub-tropical estuary in Australia (Coffs Creek, Australia). Each time series station captured N2O, radon (222Rn, a natural submarine groundwater discharge tracer), dissolved nitrogen, and dissolved organic carbon (DOC) concentrations for a minimum of 25 h. The use of automated time series observations enabled spatial and tidal-scale variability of N2O to be captured. Groundwater was highly enriched in N2O (up to 306 nM) compared to the receiving surface water. Dissolved N2O supersaturation as high as 386% (27.4 nM) was observed in the upstream freshwater and brackish water areas which represented only a small (∼13%) proportion of the total estuary area. A large area of N2O undersaturation (as low as 53% or 3.9 nM) was observed in the mangrove-dominated lower estuary. This undersaturated area likely resulted from N2O consumption due to nitrate/nitrite (NOx) limitation in mangrove sediments subject to shallow porewater exchange. Overall, the estuary was a minor source of N2O to the atmosphere as the lower mangrove-dominated estuary sink of N2O counteracted groundwater-dominated source of N2O in the upper estuary. Average area-weighted N2O fluxes at the water-air interface approached zero (0.2–0.7 μmol m−2 d−1, depending on piston velocity model used), and were much lower than nitrogen-rich Northern Hemisphere estuaries that are considered large sources of N2O to the atmosphere. This study revealed a temporally and spatially diverse estuary, with areas of N2O production and consumption related to oxygen and total dissolved nitrogen availability, submarine groundwater discharge, and uptake within mangroves.