Human exposure to mercury (Hg) is a cause of concern, due to the biomagnification of the neurotoxic species monomethylmercury (MMHg) in marine ecosystems. Previous research revealed that commercial fish species in the Mediterranean Sea ecosystems are particularly enriched in Hg, due to a combination of physical and ecological factors. Since the fate of Hg depends on the interactions among several biogeochemical and physical drivers, biogeochemical modeling is crucial to support the integration and interpretation of field data. Here, we develop and apply a coupled transport–biogeochemical–metal bioaccumulation numerical model (OGSTM–BFM–Hg) to simulate the biogeochemical cycling of the main Hg species (Hg^II, Hg⁰, MMHg, and DMHg) in seawater, organic detritus, and through the planktonic food web. The model is applied to a 3D domain of the Mediterranean Sea to investigate the spatial and temporal variability of methylmercury (MeHg) distribution and bioaccumulation and major uncertainties in Hg cycling. Model results reproduce the strong vertical and zonal gradients of MeHg concentrations related to primary production consistently with the observations and highlight the role of winter deep convection and summer water stratification in shaping the MeHg vertical distribution, including subsurface MeHg maximum. The modeled bioaccumulation dynamics in plankton food webs are characterized by a high spatial and temporal variability that is driven by plankton phenology and is consistent with available field data of Hg concentrations in plankton, as well as with other indicators, such as bioconcentration factors (BCFs) and trophic magnification factors (TMFs). Model results pointed out that the increment in water temperature linked to a decline of deep convection can cause an increase in water MeHg concentrations with cascading effects on plankton exposure and bioaccumulation.

Redox conditions and organic matter control marine methylmercury (MeHg) production. The Black Sea is the world's largest and deepest anoxic basin and is thus ideal to study Hg species along the extended redox gradient. Here we present new dissolved Hg and MeHg data from the 2013 GEOTRACES MEDBlack cruise (GN04_leg2) that we integrated into a numerical 1‐D model, to track the fate and dynamics of Hg and MeHg. Contrary to a previous study, our new data show highest MeHg concentrations in the permanently anoxic waters. Observed MeHg/Hg percentage (range 9–57%) in the anoxic waters is comparable to other subsurface maxima in oxic open‐ocean waters. With the modeling we tested for various Hg methylation and demethylation scenarios along the redox gradient. The results show that Hg methylation must occur in the anoxic waters. The model was then used to simulate the time evolution (1850–2050) of Hg species in the Black Sea. Our findings quantify (1) inputs and outputs of Hg_T (~31 and ~28 kmol yr⁻¹) and MeHg_T (~5 and ~4 kmol yr⁻¹) to the basin, (2) the extent of net demethylation occurring in oxic (~1 kmol yr⁻¹) and suboxic water (~6 kmol yr⁻¹), (3) and the net Hg methylation in the anoxic waters of the Black Sea (~11 kmol yr⁻¹). The model was also used to estimate the amount of anthropogenic Hg (85–93%) in the Black Sea.

In this study, a biogeochemical model of the mercury cycle is applied to the Marano–Grado Lagoon (North Adriatic Sea, Italy) to 1) integrate the ensemble of disconnected and snap shot measurements collected over the last decade into a common and coherent framework, 2) assess the concentration of mercury species (HgII, MeHg, Hg0) in water, sediment and particulates, and 3) quantify the mercury fluxes and budgets within the lagoon and among the lagoon, the atmosphere and the Adriatic Sea. As a result of long-term industrial and natural contamination, theMarano–Grado Lagoon is a hot spot of mercury contamination in the Mediterranean Region. Several monitoring activities have been undertaken to evaluate the environmental impacts and to better understand mercury cycling in this region. We used the results from these studies to build a mercury biogeochemical model and assess its ability to accurately predict mercury concentrations and fluxes. The results indicate that 1) the lagoon is a contaminated site, with water and sediment concentrations of Hg and MeHg higher than those of comparable environments; 2) there is substantial production ofMeHg favored high productivity, occurrence of seasonal anoxia, and shallow conditions; and 3) the lagoon is a source of mercury contamination for the Mediterranean Sea, contributing to about 5% of the total HgT load. Research also indicates that the most critical shortcoming of the currently available data sets is the lack of complete synoptic measurements, even for short time periods. Future research programs must also include information on the photo-transformation rates, such as of photo-reduction, photo-oxidation and photo-demethylation

During the industrial period, significant amounts of mercury (Hg) were discharged into the Venice Lagoon. Here, a spatially explicit model was implemented to reconstruct the temporal evolution of the total mercury (HgT) and methylmercury (MeHgT) concentrations in lagoon water and sediments over two centuries (1900-2100), from preindustrial to postindustrial phases. The model simulates the transport and transformations of particulate and dissolved Hg species. It is forced with time-variable Hg inputs and environmental conditions, including scenarios of future atmospheric deposition, reconstructed according to local and global socioeconomic scenarios. Since 1900, ~36 Mg of HgT and ~380 kg of MeHgT were delivered to the lagoon, and stored in the sediments. The deposition of Hg from the water to the seafloor increased during a period of eutrophication (1980s); however, the reverse fluxes increased during a period of high sediment resuspension caused by the unregulated fishing of Manila clams (1990s). In the current postindustrial phase, the lagoon sediments have acted as a secondary source to the lagoon waters, delivering Hg (~38 kg y-1) and MeHg (~0.07 kg y-1). The MeHg inputs from the watershed (~0.28 kg y-1) appear to be higher than the secondary fluxes from the sediments. The estimated HgT export to the Adriatic Sea is ~56 kg y-1. Since HgT and MeHgT outputs slightly exceed inputs, the concentrations are slowly decreasing. While the decreasing trend is maintained in all scenarios, the future level of atmospheric deposition will affect Hg concentrations and sediment recovery times. Though limited by inherent simplifications, this work results show that the reconstruction of historical dynamics using a holistic approach, supported by data, can improve our understanding of the pollutants distribution and the quantification of local emissions. Downscaling from trends predicted at the global scale taking into account for regional differences seems useful to investigate the pollutants fate.

Anthropogenic activities have been releasing mercury for centuries, and despite global efforts to control emissions, concentrations in environmental media remain high. Coastal sediments can be a long-term repository for mercury, but also a secondary source, and competing processes in marine ecosystems can lead to the conversion of mercury into the toxic and bioaccumulative species methylmercury, which threatens ecosystem and human health. We investigate the fate and transport of three mercury species in a coastal lagoon affected by historical pollution using a novel high-resolution finite element model that integrates mercury biogeochemistry, sediment dynamics and hydrodynamics. The model resolves mercury dynamics in the seawater and the seabed taking into account partitioning, transport driven by water and sediment, and photochemical and microbial transformations. We simulated three years (early 2000s, 2019, and 2020) to assess the spatio-temporal distribution of mercury species concentrations and performed a sensitivity analysis to account for uncertainties. The modeled mercury species concentrations show high temporal and spatial variability, with water concentrations in some areas of the lagoon exceeding those of the open Mediterranean Sea by two orders of magnitude, consistent with available observations from the early 2000s. The results support conclusions about the importance of different processes in shaping the environmental gradients of mercury species. Due to the past accumulation of mercury in the lagoon sediments, inorganic mercury in the water is closely related to the resuspension of contaminated sediments, which is significantly reduced by the presence of benthic vegetation. The gradients of methylmercury depend on the combination of several factors, of which sediment resuspension and mercury methylation are the most relevant. The results add insights into mercury dynamics at coastal sites characterized by a combination of past pollution (i.e. sediment enrichment) and erosive processes, and suggest possible nature-based mitigation strategies such as the preservation of the integrity of benthic vegetation and morphology.