Circularly polarised VUV radiation from the storage ring BESSY was used to measure all three spin polarisation parameters of photoelectrons from the Hg 5d shell in the photon energy range from threshold to approximately 35 eV. The experimental results are compared with theoretical calculations in the relativistic and non-relativistic random-phase-approximation scheme (RRPA and RPAE respectively) and Dirac-Slater (DS) calculations. A discussion of the influence of relativistic and potential barrier effects on the experimental data is given.