The Popelogan Inlier consists mainly of mafic volcanic rocks (lapilli tuffs and massive to amygdaloidal, plagioclase-phyric flows) of the Middle Ordovician Goulette Brook Formation. Pyroclastic rocks include high-MgO–Cr-Ni picritic tuffs (type I) containing, in some cases, >20% MgO, and related high-MgO andesitic tuff (type II). High-MgO rocks were generated by 30–10% partial melting of an enriched mantle source; type II is descended from type I mainly by fractionation of olivine. Mafic flows comprise basaltic andesites (type III) with low trace-element abundances and strongly fractionated, trace-element-enriched andesites (type IV). Types III and IV represent ∼20 and ∼10% partial melts, respectively, of a mantle source similar to that of the pyroclastic rocks, based on similar ratios of high field strength elements (HFSE). Unlike types I and II, petrogenesis of mafic flows involved fractionation of plagioclase and possibly amphibole. Volcanic arc signatures include negative Nb and Ti anomalies in all basalt types, along with low abundances of HFSE. Trace-element abundances are inconsistent with prior depletion in the back arc and require involvement of a mantle plume or subcontinental lithosphere. The highly magnesian composition of the picrites demands high melting temperatures and rapid transit through the crust, both of which suggest extension of the arc-bearing plate. Compositionally similar rocks in the South Pacific are associated with unusual tectono-magmatic settings involving ridge subduction, which may have established the necessary extensional environment. It is proposed that subduction of a plume-influenced ridge segment could explain the chemistry of the Goulette Brook volcanic rocks.