Bursting Oscillations in the Revised Mechanism of the Hemin – Hydrogen Peroxide – Sulfite Oscillator

Abstract

The reaction mechanism for the hemin-mediated oxidation of sulfite by hydrogen peroxide was reinvestigated. This has become necessary due to an erroneous stoichiometric factor used during a previous numerical analysis. A simple correction of the previous model failed to reproduce the experimentally observed bursting oscillations of the pH value. Therefore, we propose an extended mechanism which includes not only the autocatalytic production of H⁺ and pH-dependent equilibria of hemin species, but also the decomposition of hemin in media of high H₂O₂ concentration. The dynamic properties of this 7-variable reaction mechanism are in good agreement with previous experimental and numerical observations. A closer analysis reveals that the pH-dependent dimerisation equilibrium of hemin provides only a minor contribution to the onset of oscillations. Therefore, this equilibrium can be neglected yielding a 6-variable version of the revised 7-variable model, while maintaining the local bifurcation structure. The revised mechanisms are considered realistic models that describe the observed dynamical features of the hemin-containing pH oscillator.