The main objectives of our study were to estimate the impact of a mercury cell chlor-alkali (MCCA) complex in Rosignano Solvay (Tuscany, Italy) on the local environment and to assess mercury exposure of inhabitants living near the plant. Measurement campaigns of atmospheric Hg near the MCCA plant showed that the impact of the emitted Hg from the industry on the terrestrial environment is restricted to a close surrounding area. Total gaseous mercury concentrations in ambient air of inhabited area around the MCCA plant were in the range of 8.0-8.7 ng/m3 in summer and 2.8-4.2 ng/m3 in winter. Peaks of up to 100 ng/m3 were observed at particular meteorological conditions. Background levels of 2 ng/m3 were reached within a radius of 3 km from the plant. Reactive gaseous mercury emissions from the plant constituted around 4.2% of total gaseous mercury and total particulate mercury emission constituted around 1.0% of total gaseous mercury emitted. Analysis of local vegetables and soil samples showed relatively low concentrations of total mercury (30.1-2919 microgHg/kg DW in the soil; <0.05-111 microgHg/kg DW in vegetables) and methylmercury (0.02-3.88 microgHg/kg DW in the soil; 0.03-1.18 microgHg/kg DW in vegetables). Locally caught marine fish and fresh marine fish from the local market had concentrations of total Hg from 0.049 to 2.48 microgHg/g FW, of which 37-100% were in the form of methylmercury. 19% of analysed fish exceeded 1.0 microgHg/g FW level, which is a limit set by the European Union law on Hg concentrations in edible marine species for tuna, swordfish and shark, while 39% of analysed fish exceeded the limit of 0.5 microgHg/g FW set for all other edible marine species. Risk assessment performed by calculating ratio of probable daily intake (PDI) and provisional tolerable daily intake (PTDI) for mercury species for various exposure pathways showed no risks to human health for elemental and inorganic mercury, except for some individuals with higher number of amalgam fillings, while PDI/PTDI ratio for methylmercury and total mercury exceeded the toxicologically tolerable value due to the potential consumption of contaminated marine fish.