Hydroxylamine Diffusion Can Enhance N₂O Emissions in Nitrifying Biofilms: A Modeling Study

Wastewater treatment plants can be significant sources of nitrous oxide (N₂O), a potent greenhouse gas. However, little is known about N₂O emissions from biofilm processes. We adapted an existing suspended-growth mathematical model to explore N₂O emissions from nitrifying biofilms. The model included N₂O formation by ammonia-oxidizing bacteria (AOB) via the hydroxylamine and the nitrifier denitrification pathways. Our model suggested that N₂O emissions from nitrifying biofilms could be significantly greater than from suspended growth systems under similar conditions. The main cause was the formation and diffusion of hydroxylamine, an AOB nitrification intermediate, from the aerobic to the anoxic regions of the biofilm. In the anoxic regions, hydroxylamine oxidation by AOB provided reducing equivalents used solely for nitrite reduction to N₂O, since there was no competition with oxygen. For a continuous system, very high and very low dissolved oxygen (DO) concentrations resulted in lower emissions, while intermediate values led to higher emissions. Higher bulk ammonia concentrations and greater biofilm thicknesses increased emissions. The model effectively predicted N₂O emissions from an actual pilot-scale granular sludge reactor for sidestream nitritation, but significantly underestimated the emissions when the NH₂OH diffusion coefficient was assumed to be minimal. This numerical study suggests an unexpected and important role of hydroxylamine in N₂O emission in biofilms