The microstructure of heavy section nodular graphite cast irons often presents a bimodal distribution of nodule size associated with so-called primary and secondary graphite nucleation. It has been found that the nuclei in both types of nodules consist mainly in magnesium sulphide. However, nuclei in primary nodules contain some traces of calcium and are thus related with the inoculation treatment. On the contrary, nuclei in secondary nodules do not contain any element that could be associated to inoculation. It is suggested they form in the late stage of the eutectic reaction as a result of microsegregation build-up in magnesium and sulphur.