Oxidation of silicon surfaces at relatively low temperatures is shown to go through several activated steps, in the form of configurations inert to further uptake of oxygen. Starting from room temperature adsorption, different configurations of oxygen atoms adsorbed on and in the Si(111) and Si(001) surfaces are found, with history and/or coverage dependent energy barriers connecting them. From well below to slightly above an effective oxide coverage of a monolayer, clustering of up to three oxygen atoms around one single silicon atom has been predicted for the Si(001) surface to represent one such energy minimum; this model is confirmed here experimentally. These and other clusters are shown to agglomerate into silicon dioxide islands before coalescing into a contiguous, inert layer upon higher oxygen supplies. Another problem addressed here is the presence of molecular adsorbates in the oxidation reaction path, an issue which is still debated in the literature. For the Si(111) surface a molecular, charged oxygen species has earlier been found at temperatures up to room temperature, but not for the Si(001) surface. This is confirmed in the present experiments, and new data for this state shows that it is highly mobile until quenched at a critical oxygen coverage. It is not the initial state of oxygen on silicon, and therefore not the precursor for atomic insertion of oxygen; rather, it is found to co-exists with atomic oxygen inserted in back-bonds, at a certain, low coverage regime in which parts of the Si(111) surface are still ordered.