It was recently shown  that EMPA-WDS (Electron Probe MicroAnalysis by Wavelength Dispersive X-ray Spectroscopy) can be used to detect and to accurately quantify monolayer surface and grain boundary segregation. This paper presents the last developments of this application. It focuses on the measurement of sulphur grain boundary segregation in nickel on fractured surfaces. A special attention was paid to the quantification of the sulphur coverage, taking into account the non-normal incidence of the electron beam on a fracture surface. Sulphur grain boundary segregation kinetics was measured at 750°C in nickel to document the quantitative possibilities of the technique.