Spatial Distribution of Nitrous Oxide (N2O) in the Reloncav\xed Estuary\u2013Sound and Adjacent Sea (41\xb0\u201343\xb0 S), Chilean Patagonia

Abstract

Fjords and estuaries exchange large amounts of solutes, gases, and particulates between fluvial and marine systems. These exchanges and their relative distributions of compounds/particles are partially controlled by stratification and water circulation. The spatial and vertical distributions of N2O, an important greenhouse gas, along with other oceanographic variables, are analyzed from the Reloncaví estuary (RE) (~41° 30′ S) to the gulf of Corcovado in the interior sea of Chiloé (43° 45′ S) during the austral winter. Freshwater runoff into the estuary regulated salinity and stratification of the water column, clearly demarking the surface (<5 m depth) and subsurface layer (>5 m depth) and also separating estuarine and marine influenced areas. N2O levels varied between 8.3 and 21 nM (corresponding to 80 and 170 % saturation, respectively), being significantly lower (11.8 ± 1.70) at the surface than in subsurface waters in the Reloncaví estuary (14.5 ± 1.73). Low salinity and NO3−, NO2−, and PO43− levels, as well as high Si(OH)4 values were associated with low surface N2O levels. Remarkably, an accumulation of N2O was observed in the subsurface waters of the Reloncaví sound, associated with a relatively high consumption of O2. The sound is exposed to increasing anthropogenic impacts from aquaculture and urban discharge, occurring simultaneously with an internal recirculation, which leads to potential signals of early eutrophication. In contrast, within the interior sea of Chiloé (ISC), most of water column was quasi homohaline and occupied by modified subantarctic water (MSAAW), which was relatively rich in N2O (12.6 ± 2.36 nM) and NO3− (18.3 ± 1.63 μM). The relationship between salinity, nutrients, and N2O revealed that water from the open ocean, entering into ISC (the Gulf of Corcovado) through the Guafo mouth, was the main source of N2O (up to 21 nM), as it gradually mixed with estuarine water. In addition, significant relationships between N2O excess vs. AOU and N2O excess vs. NO3− suggest that part of N2O is also produced by nitrification. Our results show that the estuarine and marine waters can act as light source or sink of N2O to the atmosphere (air–sea N2O fluxes ranged from −1.57 to 5.75 μmol m−2 day−1), respectively; influxes seem to be associated to brackish water depleted in N2O that also caused a strong stratification, creating a barrier to gas exchange.