N₂O production and consumption from stable isotopic and concentration data in the Peruvian coastal upwelling system

The ocean is an important source of nitrous oxide (N 2 O) to the atmosphere, yet the factors controlling N 2 O production and consumption in oceanic environments are still not understood nor constrained. We measured N 2 O concentrations and isotopomer ratios, as well as O 2 , nutrient and biogenic N 2 concentrations, and the isotopic compositions of nitrate and nitrite at several coastal stations during two cruises off the Peru coast (~5–16°S, 75–81°W) in December 2012 and January 2013. N 2 O concentrations varied from below equilibrium values in the oxygen deficient zone (ODZ) to up to 190 nmol L −1 in surface waters. We used a 3‐D‐reaction‐advection‐diffusion model to evaluate the rates and modes of N 2 O production in oxic waters and rates of N 2 O consumption versus production by denitrification in the ODZ. Intramolecular site preference in N 2 O isotopomer was relatively low in surface waters (generally −3 to 14‰) and together with modeling results, confirmed the dominance of nitrifier‐denitrification or incomplete denitrifier‐denitrification, corresponding to an efflux of up to 0.6 Tg N yr −1 off the Peru coast. Other evidence, e.g., the absence of a relationship between ΔN 2 O and apparent O 2 utilization and significant relationships between nitrate, a substrate during denitrification, and N 2 O isotopes, suggest that N 2 O production by incomplete denitrification or nitrifier‐denitrification decoupled from aerobic organic matter remineralization are likely pathways for extreme N 2 O accumulation in newly upwelled surface waters. We observed imbalances between N 2 O production and consumption in the ODZ, with the modeled proportion of N 2 O consumption relative to production generally increasing with biogenic N 2 . However, N 2 O production appeared to occur even where there was high N loss at the shallowest stations.