Fuel reburning usually serves in mitigating NOx formation in stationary combustion sources. However, the use of biomass as reburning fuel could facilitate the production of relatively more nitrogen-containing aromatic products of incomplete combustion. This study investigates the heterogeneous reaction between biomass and mixtures of NO/O2 gases, employing isothermal high-temperature experiments in a vertically-entrained reactor, and in situ diffuse reflective infrared Fourier transform spectroscopy (DRIFTS) under a non-isothermal heating condition ranging from ambient temperature to 700 °C. The method enables sensitive evaluation of the surface species ensuing during the thermal reaction. Results from this study elucidate the formation of nitrated structures as active intermediate species of the heterogeneous reaction. The nitrogenated signatures persist on the surface of the residual ash, suggesting the production of N-aromatics such as nitro-PAH. Considering the severe toxicity and bioaccumulative properties of these by-products, further research should focus on the relative contribution of various reburning fuels, while favouring sustainable fuels such as non-charring plastics.