Air samples were taken on board the RRS Bransfield (typically for 24−72 h), during an Atlantic cruise from the U.K. to Antarctica in October−December 1998, to investigate the global scale distribution of PCDD/Fs and coplanar PCBs. Highest concentrations of Cl2-8DD/Fs all occurred between 25 and 52 °N; lowest concentrations were measured around 60 °S and further south. Cl3DFs showed highest overall concentrations (up to 9800 fg/m3), followed by Cl2DFs (up to 5300 fg/m3) and OCDD (up to 1300 fg/m3). Lowest concentrations, measured in the remote Southern hemisphere, were generally 2 orders of magnitude lower than their highest concentrations over the North Atlantic. Concentrations of PCB-77 were higher in the northern hemisphere, while PCB-126 and PCB-169 exhibited highest concentrations around the equator. Evidence was obtained for substantial emissions of PCDD/Fs off west Africa and while in the port of Montevideo, Uruguay. Shifts in PCDD/F profile distribution were observed on increasing distance from source regions, such that those from the most remote locations were dominated by Cl3DF (40% of the total) and OCDD (20%). Gas-particle partition data was obtained for all samples. Cl4-6DD/Fs showed the widest range, varying between 10 and 90% of the total in the gas phase, depending on location/temperature. The study gave limited evidence for the influence of OH-radical initiated depletion reactions of gaseous PCDD/Fs. The global atmospheric burden is estimated to be on the order of 350 kg ΣCl4-8DD/Fs and 3 kg ΣTEQ.