Enzyme-level interconversion of nitrate and nitrite in the fall mixed layer of the Antarctic Ocean

In the Southern Ocean, the nitrogen (N) isotopes of organic matter and the N and oxygen (O) isotopes of nitrate (NO3 ) have been used to investigate NO3 assimilation and N cycling in the summertime period of phytoplankton growth, both today and in the past. However, recent studies indicate the significance of processes in other seasons for producing the annual cycle of N isotope changes. This study explores the impact of fall conditions on the N/N (δN) and O/O (δO) of NO3 and nitrite (NO2 ) in the Pacific Antarctic Zone using depth profiles from late summer/fall of 2014. In the mixed layer, the δN and δO of NO3 +NO2 increase roughly equally, as expected for NO3 assimilation; however, the δN of NO3 -only (measured after NO2 removal) increases more than does NO3 -only δO. Differencing indicates that NO2 has an extremely low δN, often< 70‰ versus air. These observations are consistent with the expression of an equilibrium N isotope effect between NO3 and NO2 , likely due to enzymatic NO3 -NO2 interconversion. Specifically, we propose reversibility of the nitrite oxidoreductase (NXR) enzyme of nitrite oxidizers that, having been entrained from the subsurface during late summer mixed layer deepening, are inhibited by light. Our interpretation suggests a role for NO3 -NO2 interconversion where nitrifiers are transported into environments that discourage NO2 oxidation. This may apply to surface regions with upwelling, such as the summertime Antarctic. It may also apply to oxygen-deficient zones, where NXR-catalyzed interconversion may explain previously reported evidence of NO2 oxidation.