Mediterranean Mercury Assessment 2022: An Updated Budget, Health Consequences, and Research Perspectives.

Mercury (Hg) and especially its methylated species (MeHg) are toxic chemicals that contaminate humans via the consumption of seafood. The most recent UNEP Global Mercury Assessment stressed that Mediterranean populations have higher Hg levels than people elsewhere in Europe. The present Critical Review updates current knowledge on the sources, biogeochemical cycling, and mass balance of Hg in the Mediterranean and identifies perspectives for future research especially in the context of global change. Concentrations of Hg in the Western Mediterranean average 0.86 ± 0.27 pmol L-1 in the upper water layer and 1.02 ± 0.12 pmol L-1 in intermediate and deep waters. In the Eastern Mediterranean, Hg measurements are in the same range but are too few to determine any consistent oceanographical pattern. The Mediterranean waters have a high methylation capacity, with MeHg representing up to 86% of the total Hg, and constitute a source of MeHg for the adjacent North Atlantic Ocean. The highest MeHg concentrations are associated with low oxygen water masses, suggesting a microbiological control on Hg methylation, consistent with the identification of hgcA-like genes in Mediterranean waters. MeHg concentrations are twice as high in the waters of the Western Basin compared to the ultra-oligotrophic Eastern Basin waters. This difference appears to be transferred through the food webs and the Hg content in predators to be ultimately controlled by MeHg concentrations of the waters of their foraging zones. Many Mediterranean top-predatory fish still exceed European Union regulatory Hg thresholds. This emphasizes the necessity of monitoring the exposure of Mediterranean populations, to formulate adequate mitigation strategies and recommendations, without advising against seafood consumption. This review also points out other insufficiencies of knowledge of Hg cycling in the Mediterranean Sea, including temporal variations in air-sea exchange, hydrothermal and cold seep inputs, point sources, submarine groundwater discharge, and exchanges between margins and the open sea. Future assessment of global change impacts under the Minamata Convention Hg policy requires long-term observations and dedicated high-resolution Earth System Models for the Mediterranean region.

Particulate-phase mercury emissions from biomass burning and impact on resulting deposition: a modelling assessment.

Mercury (Hg) emissions from biomass burning (BB) are an important source of atmospheric Hg and a major factor driving the interannual variation of Hg concentrations in the troposphere. The greatest fraction of Hg from BB is released in the form of elemental Hg(Hg(g)0) . However, little is known about the fraction of Hg bound to particulate matter (HgP) released from BB, and the factors controlling this fraction are also uncertain. In light of the aims of the Minamata Convention to reduce intentional Hg use and emissions from anthropogenic activities, the relative importance of Hg emissions from BB will have an increasing impact on Hg deposition fluxes. Hg speciation is one of the most important factors determining the redistribution of Hg in the atmosphere and the geographical distribution of Hg deposition. Using the latest version of the Global Fire Emissions Database (GFEDv4.1s) and the global Hg chemistry transport model, ECHMERIT, the impact of Hg speciation in BB emissions, and the factors which influence speciation, on Hg deposition have been investigated for the year 2013. The role of other uncertainties related to physical and chemical atmospheric processes involving Hg and the influence of model parametrisations were also investigated, since their interactions with Hg speciation are complex. The comparison with atmospheric HgP concentrations observed at two remote sites, Amsterdam Island (AMD) and Manaus (MAN), in the Amazon showed a significant improvement when considering a fraction of HgP from BB. The set of sensitivity runs also showed how the quantity and geographical distribution of HgP emitted from BB has a limited impact on a global scale, although the inclusion of increasing fractions HgP does limit Hg(g)0 availability to the global atmospheric pool. This reduces the fraction of Hg from BB which deposits to the world's oceans from 71 to 62 %. The impact locally is, however, significant on northern boreal and tropical forests, where fires are frequent, uncontrolled and lead to notable Hg inputs to local ecosystems. In the light of ongoing climatic changes this effect could be potentially be exacerbated in the future.

A Modeling Comparison of Mercury Deposition from Current Anthropogenic Mercury Emission Inventories.

Human activities have altered the biogeochemical cycle of mercury (Hg) since precolonial times, and anthropogenic activities will continue to perturb the natural cycle of Hg. Current estimates suggest the atmospheric burden is three to five times greater than precolonial times. Hg in the upper ocean is estimated to have doubled over the same period. The Minamata convention seeks to reduce the impact human activities have on Hg releases to the environment. A number of the Articles in the Convention concern the development of detailed inventories for Hg emissions and releases. Using the global Hg chemical transport model, ECHMERIT, the influence of the anthropogenic emission inventory (AMAP/UNEP, EDGAR, STREETS) on global Hg deposition patterns has been investigated. The results suggest that anthropogenic Hg emissions contribute 20-25% to present-day Hg deposition, and roughly two-thirds of primary anthropogenic Hg is deposited to the world's oceans. Anthropogenic Hg deposition is significant in the North Pacific, Mediterranean and Arctic. The results indicate immediate reductions in Hg emissions would produce benefits in the short term, as well as in the long term. The most impacted regions would be suitable to assess changes in Hg deposition resulting from implementation of the Minamata convention.

Lagrangian statistics of mesoscale turbulence in a natural environment: The Agulhas return current.

The properties of mesoscale geophysical turbulence in an oceanic environment have been investigated through the Lagrangian statistics of sea surface temperature measured by a drifting buoy within the Agulhas return current, where strong temperature mixing produces locally sharp temperature gradients. By disentangling the large-scale forcing which affects the small-scale statistics, we found that the statistical properties of intermittency are identical to those obtained from the multifractal prediction in the Lagrangian frame for the velocity trajectory. The results suggest a possible universality of turbulence scaling.

Observational and modeling constraints on global anthropogenic enrichment of mercury.

Centuries of anthropogenic releases have resulted in a global legacy of mercury (Hg) contamination. Here we use a global model to quantify the impact of uncertainty in Hg atmospheric emissions and cycling on anthropogenic enrichment and discuss implications for future Hg levels. The plausibility of sensitivity simulations is evaluated against multiple independent lines of observation, including natural archives and direct measurements of present-day environmental Hg concentrations. It has been previously reported that pre-industrial enrichment recorded in sediment and peat disagree by more than a factor of 10. We find this difference is largely erroneous and caused by comparing peat and sediment against different reference time periods. After correcting this inconsistency, median enrichment in Hg accumulation since pre-industrial 1760 to 1880 is a factor of 4.3 for peat and 3.0 for sediment. Pre-industrial accumulation in peat and sediment is a factor of ∼ 5 greater than the precolonial era (3000 BC to 1550 AD). Model scenarios that omit atmospheric emissions of Hg from early mining are inconsistent with observational constraints on the present-day atmospheric, oceanic, and soil Hg reservoirs, as well as the magnitude of enrichment in archives. Future reductions in anthropogenic emissions will initiate a decline in atmospheric concentrations within 1 year, but stabilization of subsurface and deep ocean Hg levels requires aggressive controls. These findings are robust to the ranges of uncertainty in past emissions and Hg cycling.

Mercury in the Mediterranean. Part 2: processes and mass balance.

Mass balance of contaminants can provide useful information on the processes that influence their concentrations in various environmental compartments. The most important sources, sinks and the equilibrium or non-equilibrium state of the contaminant in individual environmental compartments can also be identified. Using the latest mercury speciation data, the results of numerical models and the results of recent studies on mercury transport and transformation processes in the marine environment, we have re-evaluated the total mercury (HgT) mass balance in the Mediterranean Sea. New calculations have been performed employing three distinct marine layers: the surface layer, the thermocline and the deep sea. New transport mechanisms, deep water formation and density-driven sinking and upwelling, were included in the mass balance calculations. The most recent data have even enabled the calculation of an approximate methylmercury (MeHg) mass balance. HgT is well balanced in the entire Mediterranean, and the discrepancies between inputs and outputs in individual layers do not exceed 20 %. The MeHg balance shows larger discrepancies between gains and losses due to measurement uncertainties and gaps in our knowledge of Hg species transformation processes. Nonetheless, the main sources and sinks of HgT (deposition and evasion) and MeHg (fluxes from sediment, outflow through the Gibraltar Strait) are in accordance with previous studies on mercury in the Mediterranean Basin. Mercury in the Mediterranean fish harvest is the second largest MeHg sink; about 300 kg of this toxic substance is consumed annually with sea food.

Chasing quicksilver: modeling the atmospheric lifetime of Hg(0)(g) in the marine boundary layer at various latitudes.

The lifetime of elemental mercury in the marine boundary layer(MBL) has been studied using AMCOTS (Atmospheric Mercury Chemistry Over The Sea), a box model of MBL photochemistry including aerosols and detailed mercury chemistry. Recently measured Hg(0)(g) oxidation reactions have been included, and the studies were performed as a function of latitude, time of year, boundary layer liquid water content (LWC) and cloud optical depth. The results show that Hg has the shortest lifetime when air temperatures are low and sunlight and deliquescent aerosol particles are plentiful. Thus the modeled lifetime for clear-sky conditions is actually shorter at mid-latitudes and high latitudes than near the equator, and for a given latitude and time of year, cooler temperatures enhance the rate of Hg oxidation. Under typical summer conditions (for a given latitude) of temperature and cloudiness, the lifetime (tau) of Hg(0)(g) in the MBL is calculated to be around 10 days at all latitudes between the equator and 60 degrees N. This is much shorter than the generally accepted atmospheric residence time for Hg(0)(g) of a year or more. Given the relatively stable background concentrations of Hg(0)(g) which have been measured, continual replenishment of Hg(0)(g) must take place, suggesting a "multihop" mechanism for the distribution of Hg, rather than solely aeolian transport with little or no chemical transformation between source and receptor. Inclusion of an empirical Hg(0)(g) emission factor related to insolation was used to stabilize the Hg(0)(g) concentration in the model, and the emission rates necessarily agree well with estimated emission fluxes for the open ocean.