Petrochemical industries normally use storage tanks containing large amounts of flammable and hazardous substances. Therefore, the occurrence of a tank fire, such as the large industrial accident on 11th December 2005 at Buncefield Oil Storage Depots, is possible and usually leads to fire and explosions. Experience has shown that the continuous production of black smoke from these fires due to the toxic gases from the combustion process, presents a potential environmental and health problem that is difficult to assess. The goals of the present effort are to estimate the height of the smoke plume, the ground-level concentrations of the toxic pollutants (smoke, SO2, CO, PAHs, VOCs) and to characterize risk zones by comparing the ground-level concentrations with existing safety limits. For the application of the numerical procedure developed, an external floating-roof tank has been selected with dimensions of 85 m diameter and 20 m height. Results are presented and discussed. It is concluded that for all scenarios considered, the ground-level concentrations of smoke, SO2, CO, PAHs and VOCs do not exceed the safety limit of IDLH and there are no “death zones” due to the pollutant concentrations.