Nitrogen cycling in oxygen deficient zones : insights from [delta]¹⁵N and [delta]¹⁸O of nitrite and nitrate

Abstract

The stable isotopes, [delta]¹⁵N and [delta]¹⁸O, of nitrite and nitrate can be powerful tools used to interpret nitrogen cycling in the ocean. They are particularly useful in regions of the ocean where there are multiple sources and sinks of nitrogenous nutrients, which concentration profiles alone cannot distinguish. Examples of such regions are "oxygen deficient zones" (ODZ). They are of particular interest because they are also important hot spots of fixed N loss and production of N₂O, a potent greenhouse gas. In order to interpret these isotope profiles, the isotope systematics of each process involved must be known so that we can distinguish the isotopic signature of each process. One of the important processes to consider here is nitrification, the process by which ammonium is oxidized nitrite and then to nitrate. This thesis describes numerous experiments using both cultures of nitrifying organisms as well as natural seawater samples to determine the oxygen isotope systematics of nitrification. These experimental incubations show that the accumulation of nitrite has a large effect on the resulting [delta]¹⁸ONO3. In experiments where nitrite does not accumulate, [delta]¹⁸ONO3 produced from nitrification is between -1 to l%o. These values will be applicable for the majority of the ocean, but the nitrite isotopic exchange will be important in the regions of the ocean where nitrite accumulates, such as the base of the euphotic zone and oxygen deficient zones. [delta]¹⁸ONO2 was developed as a unique tracer in this thesis because it undergoes abiotic equilibration with water [delta]¹⁸O at a predictable rate based on pH, temperature and salinity. This rate, its dependencies, and how the [delta]¹⁸ONO2 values can be used as not only biological source indicators but also indicators of age are described. This method was applied to samples from the primary nitrite maximum in the Arabian Sea, revealing that the dominant source and sinks of nitrite are ammonia oxidation and nitrite oxidation with an average age of 37 days. Finally, using the isotope systematics of nitrification as well as the properties of nitrite oxygen isotope exchange described in this thesis, the final chapter interprets multiisotope nitrate and nitrite profiles in the Costa Rica Upwelling Dome using a simple ID model. The nitrite isotopes showed that there were multiple sources of nitrite in the primary nitrite maximum including (1) decoupling of ammonia oxidation and nitrite oxidation, (2) nitrate reduction during assimilation and leakage of nitrite by phytoplankton. In the oxygen deficient zone and secondary nitrite maximum, there were equal contributions of nitrite removal from nitrite oxidation and nitrite reduction. This recycling of nitrite to nitrate through oxidation indicates that the percentage of reduced nitrate fully consumed to N2 gas is actually smaller than previous estimates. Overall, this thesis describes new nitrogen and oxygen isotopic tracers and uses them to elucidate the complicated nitrogen biogeochemistry in oxygen deficient zones.