Laminated and massive sulfide (pyrite, sphalerite, galena) mineralization and massive barite – fluorite–galena lenses occur in Upper Silurian – Lower Devonian Road River Formation shales of the Vulcan property along the eastern flank of the Selwyn Basin, Northwest Territories, Canada. The 5 km thick stratigraphic section, ranging in age from Hadrynian through Mississippian, offers insight into the nature of the Mackenzie Platform – Selwyn Basin transition. Abrupt facies changes, synsedimentary faults, debris flows, local unconformities, and the presence of high-potassium mafic flows indicate extensional tectonics during deposition of the Road River Formation. Mineralization resulted from heated, metal-rich basinal brines that vented on the sea floor up normal faults.Sulfur-isotope studies indicate that both sulfate and sulfide were derived from the exhaling metalliferous brine. Sulfur-isotope data also suggest that reduction of sulfate in the brine occurred as a result of organic decomposition, possibly during thermal maturation of hydrocarbons at temperatures greater than 80 °C. Fluid inclusion observations indicate that the brine salinity reached 26 wt.% NaCl for at least a portion of the evolution of the hydrothermal system.Cooling of the brine during venting into bottom waters caused initial rapid precipitation of fine-grained barite, resulting in a baritic buildup above vent areas. Continued percolation of the brine through the baritic mound caused recrystallization of the barite and then the deposition of interstitial fluorite and galena. In other areas the dense ore fluid collected in topographic depressions, or brine pools, in which sulfide minerals accumulated under anoxic conditions. Location of hydrothermal vents, paleotopography, and intensity of hydrothermal activity were the main controls on the thickness, distribution, and grade of Vulcan mineralization.