Integrating thermodynamics and mathematical modelling to investigate the stoichiometry and kinetics of sulphide oxidation-nitrate reduction with a special focus on partial autotrophic denitrification

In the present study, the stoichiometry of the Sulphur Oxidizing-Nitrate Reducing (SO-NR) process, with a focus on Partial Autotrophic Denitrification (PAD), has been evaluated through a thermodynamic-based study whereas a model-based approach has been adopted to assess process kinetics. Experimental data on process performance and biomass yields were available from a previous work achieving efficient PAD, where a biomass yield of 0.113 gVSS/gS was estimated. First, the free Gibbs energy dissipation method has been implemented, in order to provide a theoretical framework exploring the boundaries for sulphur oxidizing biomass yields. Second, a screening of available mathematical models describing SO-NR process was conducted and five published models were selected, in order to assess the most suitable model structure for describing the observed PAD kinetics. To the best of our knowledge, none of reported biomass yields are estimated in systems operating PAD as the main process and, analogously, none of the proposed models have been applied to case studies aiming at partial denitrification only. The work showed that the very low biomass yield of 0.117 ± 0.007 gVSS/gS, observed in a PAD system in our previous work, suggests that the conditions applied to achieve partial denitrification resulted in a high energy-dissipating metabolism compared to complete denitrification applications. Models’ analysis revealed that nitrite accumulation can be described by a classical Monod kinetics if different μ_max are adopted for each intermediate reaction, with Theil Inequality Coefficient values lower than 0.21 for both NO₃⁻ and NO₂⁻. Nonetheless, adopting Haldane-type kinetics for nitrite uptake inferred higher identifiability to the model structure, resulting in confidence intervals below ±10% for all the parametric estimations. The thermodynamic and modelling outcomes support the experimental results obtained in the reference study and the critical comparison of model suitability to represent PAD process is believed pivotal to pave the way to its real-scale implementation.