We investigate the x-ray magnetic circular dichroism (XMCD) at the L_3,2 edges using a single crystal of Tb as a prototype system for a one-element magnet in order to ascertain the multipolar nature of the features in the dichroic spectra. The high resolution of the experimental data allows for a clear identification of the dipolar (E1: 2p→5d) and quadrupolar (E2: 2p→4f) transitions. On the basis of ab initio calculations we developed a simple procedure to extract the quadrupolar part by subtracting the derivative of the spin-averaged absorption spectra from the experimental XMCD data. The deconvolution has to be carried out before applying sum rules to determine 4f and 5d moments.