Cores taken during exploration for Mississippi Valley-type lead and zinc ores in the Mascot-Jefferson City zinc district of eastern Tennessee commonly contain hydrocarbon residues in carbonate rocks of the Knox Group immediately below the Lower Ordovician Knox unconformity. The location and number of these residue-bearing strata reveal information about the Paleozoic history of hydrocarbon emplacement in the region. Contour maps, generated from nearly 800 holes covering more than 20 km², indicate that zones with elevated organic content in the uppermost 30 m of the Lower Ordovician Mascot Dolomite show a strong spatial correlation with Middle Ordovician paleotopographic highs. These same zones show no spatial association with present-day structural highs, which were formed during Pennsylvanian-Permian Alleghenian tectonism. This suggests that the physical entrapment of hydrocarbons migrating through the upper permeable units of the Mascot must have occurred prior to the principal tectonism of the Alleghenian orogeny.