Mercury (Hg) is one of the primary health concerns in natural and urbanised environments due to past and present natural and anthropogenic emissions. Its environmental cycle is driven by redox reactions, microbial metabolism and organic matter (OM) interactions, which may all lead to formation of bioaccumulative organic Hg species; methylmercury (MeHg), with damaging consequences for human and ecosystem health. Hence, Hg lability and bioavailability has been the focus of many investigations and assessed with a variety of chemical proxies in order to improve understanding of the conditions that lead to enhanced bioavailability of Hg and its species. We investigated Hg labile species with Diffusive Gradient in Thin-film technique (DGT) in the water column and sediment of Zenne River (Brussels, Belgium) and Gulf of Trieste (North Adriatic). They represent two contemporary important Hg-impacted areas; the former by anthropogenic urban pollution, and the latter by historic pollution from Hg mining. Hg speciation of labile inorganic and methylmercury in these two environments was not yet investigated using DGT technique. The results show labile Hg species changing with season in the water column of Zenne River, while the sediments are the source of bioavailable MeHg to the water column that is transported further creating a halo effect in the region. Values of labile Hg species for water column and sediments in Gulf of Trieste differ from previous research, highlighting the need for more investigation into Hg bioavailability. MeHg/THg ratios were compared to other sampling methods for labile Hg species. Display omitted •Labile Hg species were measured using a Diffusive Gradient in Thin-film technique.•DGTs were used in the Zenne River Brussels and Gulf of Trieste (North Adriatic).•Winter-time THg in Zenne is highly labile and mobilized far from its source.•MeHg/THg% in Gulf showed higher labile Hg bioavailability than previously thought.•Labile MeHg in the sediment of the Gulf represents up to 75% of total labile Hg.