We report first-principle based studies of the adsorption interaction of astatine species on a gold surface. These studies are aimed primarily at the support and interpretation of gas chromatographic experiments with superheavy elements, tennessine (Ts, Z = 117), a heavier homologue of At, and possibly its pseudo-homologue nihonium (Nh, Z = 113). We use gold clusters with up to 69 atoms to simulate the adsorption sites and estimate the desorption energies of At & AtOH from a stable gold (111) surface. To describe the electronic structure of At - Au-n and AtOH - Aun complexes, we combine accurate shape-consistent relativistic pseudopotentials and non-collinear two-component relativistic density functional theory. The predicted desorption energies of At and AtOH on gold are 130 +/- 10 kJ/mol and 90 +/- 10 kJ/mol, respectively. These results confirm the validity of the estimates derived from chromatographic data (147 +/- 15 kJ/mol for At, and 100(-10)(+20) kJ/mol for AtOH). (C) 2017 Elsevier B.V. All rights reserved.