Hypothesis: Silanol groups at the silica-water interface determine not only the surface charge, but also have an important role in the binding of ions and biomoiecules. As the pH is increased above pH 2, the silica surface develops a net negative charge primarily due to deprotonation of the silanol group. An improved understanding of the energetics and mechanisms of this fundamentally important process would further understanding of the relevant dynamics. Simulations: Density Functional Theory ab initio molecular dynamics and geometry optimisations were used to investigate the mechanisms of surface neutralisation and charging in the presence of OH- and H3O+ respectively. This charging mechanism has received little attention in the literature. Findings: The protonation or deprotonation of isolated silanols in the presence of H3O+ or OH-, respectively, was shown to be a highly rapid, exothermic reaction with no significant activation energy. This process occurred via a concerted motion of the protons through 'water wires'. Geometry optimisations of large water clusters at the silica surface demonstrated proton transfer to the surface occurring via the rarely discussed 'proton holes' mechanism. This indicates that surface protonation is possible even when the hydronium ion is distant (at least 4 water molecules separation) from the surface. (C) 2015 The Authors. Published by Elsevier Inc.