An understanding of the size of petroleum secondary migration systems is vital for successful exploration for petroleum reserves. Geochemists have suggested that compositional fractionation of petroleum accompanying the migration process (geochromatography) can potentially be used to infer distances petroleum may have travelled and the ratio of oil in the reservoir to that lost in the carrier. To date, this has been attempted by measuring concentrations and distributions of specific steranes, and aromatic oxygen and nitrogen compounds in reservoired oils which have been proposed to respond to migration rather than to source maturity or other effects. We report here an experiment involving oil migration through an initially water wet siltstone under realistic subsurface carrier bed or reservoir conditions (48 MPa, 70 °C) where source facies and maturity effects are eliminated. We show that geochromatography does indeed occur even for initially water saturated rocks and that the migration fractionations observed for alkylcarbazoles, benzocarbazoles and alkylphenols are very similar to those seen in field data sets. In contrast, sterane based migration parameters show no compositional fractionation under these conditions. © The Royal Society of Chemistry and the Division of Geochemistry of the American Chemical Society 2000.