In this study, the vertical distribution of mercury (Hg) in estuarine and marine sediment porewaters and solid phases was assessed by conventional and passive sampling techniques in the historically polluted Scheldt Estuary and Belgian Coastal Zone (BCZ). The Diffusive Gradients in Thin-films (DGT) measured labile Hg concentrations (Hg_LA) were mostly lower than the porewater Hg concentrations (Hg_PW), and they also presented different vertical distribution patterns. Still high Hg concentrations in the sediment solid phases, comparable to the historical ones, were observed. Even though pH, redox potential and dissolved sulfide concentration could influence the Hg biogeochemical behaviour, organic matter (OM) played a key role in governing Hg mobilization from sediment solid phase to porewater and in its partitioning between porewater and solid phase over depth. In the marine sediments, where OM had a marine signature, higher labile Hg concentrations in the porewater and faster resupply from the solid phase were observed. The DGT technique showed significant potential not only for the measurement of bioavailable Hg fractions in porewater, but also for the assessment of kinetic parameters governing the release of labile Hg species from the solid phase with the assistance of the DGT Induced Fluxes in Sediments (DIFS) model.