Christian N. Gencarelli

Global atmospheric cycle of mercury: a model study on the impact of oxidation mechanisms

Mercury (Hg) is a global pollutant since its predominant atmospheric form, elemental Hg, reacts relatively slowly with the more abundant atmospheric oxidants. Comprehensive knowledge on the details of the atmospheric Hg cycle is still lacking, and in particular, there is some uncertainty regarding the atmospherically relevant reduction-oxidation reactions of mercury and its compounds. ECHMERIT is a global online chemical transport model, based on the ECHAM5 global circulation model, with a highly customisable chemistry mechanism designed to facilitate the investigation of both aqueous- and gas-phase atmospheric mercury chemistry. An improved version of the model which includes a new oceanic emission routine has been developed. Results of multiyear model simulations with full atmospheric chemistry have been used to examine the how changes to chemical mechanisms influence the model’s ability to reproduce measured Hg concentrations and deposition flux patterns. The results have also been compared to simple fixed-lifetime tracer simulations to constrain the possible range of atmospheric mercury redox rates. The model provides a new and unique picture of the global cycle of mercury, in that it is online and includes a full atmospheric chemistry module.

Development and application of a regional-scale atmospheric mercury model based on WRF/Chem: a Mediterranean area investigation

The emission, transport, deposition and eventual fate of mercury (Hg) in the Mediterranean area has been studied using a modified version of the Weather Research and Forecasting model coupled with Chemistry (WRF/Chem). This model version has been developed specifically with the aim to simulate the atmospheric processes determining atmospheric Hg emissions, concentrations and deposition online at high spatial resolution. For this purpose, the gas phase chemistry of Hg and a parametrised representation of atmospheric Hg aqueous chemistry have been added to the regional acid deposition model version 2 chemical mechanism in WRF/Chem. Anthropogenic mercury emissions from the Arctic Monitoring and Assessment Programme included in the emissions preprocessor, mercury evasion from the sea surface and Hg released from biomass burning have also been included. Dry and wet deposition processes for Hg have been implemented. The model has been tested for the whole of 2009 using measurements of total gaseous mercury from the European Monitoring and Evaluation Programme monitoring network. Speciated measurement data of atmospheric elemental Hg, gaseous oxidised Hg and Hg associated with particulate matter, from a Mediterranean oceanographic campaign (June 2009), has permitted the model’s ability to simulate the atmospheric redox chemistry of Hg to be assessed. The model results highlight the importance of both the boundary conditions employed and the accuracy of the mercury speciation in the emission database. The model has permitted the reevaluation of the deposition to, and the emission from, the Mediterranean Sea. In light of the well-known high concentrations of methylmercury in a number of Mediterranean fish species, this information is important in establishing the mass balance of Hg for the Mediterranean Sea. The model results support the idea that the Mediterranean Sea is a net source of Hg to the atmosphere and suggest that the net flux is ≈30 Mg year−1 of elemental Hg.

Model study of global mercury deposition from biomass burning

Mercury emissions from biomass burning are not well characterized and can differ significantly from year to year. This study utilizes three recent biomass burning inventories (FINNv1.0, GFEDv3.1, and GFASv1.0) and the global Hg chemistry model, ECHMERIT, to investigate the annual variation of Hg emissions, and the geographical distribution and magnitude of the resulting Hg deposition fluxes. The roles of the Hg/CO enhancement ratio, the emission plume injection height, the Hg(g)0 oxidation mechanism and lifetime, the inventory chosen, and the uncertainties with each were considered. The greatest uncertainties in the total Hg deposition were found to be associated with the Hg/CO enhancement ratio and the emission inventory employed. Deposition flux distributions proved to be more sensitive to the emission inventory and the oxidation mechanism chosen, than all the other model parametrizations. Over 75% of Hg emitted from biomass burning is deposited to the world’s oceans, with the highest fluxes predicted i...

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 worlds 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.

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.

Sea surface temperature variation linked to elemental mercury concentrations measured on Mauna Loa

The Hg0 time series recorded at the Mauna Loa Observatory (MLO) in Hawaii between 2002 and 2009 has been analyzed using Empirical Mode Decomposition. This technique has been used in numerous contexts in order to identify periodical variations in time series data. The periodicities observed in the tropical Pacific sea surface temperature (SST), through the data collected from five buoys, are also observed in Hg0 concentrations and the relative humidity measured at the MLO. The lag times in the observed periodicities are related to the position of the buoys with respect to the measurement site. This demonstrates a direct link between climatological phenomena, in this case SST, and measured Hg0 and reflects the influence of ocean SST on Hg0 evasion. This is the first long-term experimental evidence of such a direct effect on Hg0 evasion from the oceanic surface driven by temperature.

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.

Mercury in the Black Sea: new insights from measurements and numerical modeling

Abstract Redox conditions and organic matter control marine methylmercury (MeHg) production. The Black Sea is the worlds 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 HgT (~31 and ~28 kmol yr−1) and MeHgT (~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.

Regional modelling of polycyclic aromatic hydrocarbons : WRF/Chem-PAH model development and East Asia case studies

Polycyclic aromatic hydrocarbons (PAHs) are hazardous pollutants, with increasing emissions in pace with economic development in East Asia, but their distribution and fate in the atmosphere are not yet well understood. We extended the regional atmospheric chemistry model WRFChem (Weather Research Forecast model with Chemistry module) to comprehensively study the atmospheric distribution and the fate of low-concentration, slowly degrading semivolatile compounds. The WRF-Chem-PAH model reflects the state-of-the-art understanding of current PAHs studies with several new or updated features. It was applied for PAHs covering a wide range of volatility and hydrophobicity, i.e. phenanthrene, chrysene and benzo[a]pyrene, in East Asia. Temporally highly resolved PAH concentrations and particulate mass fractions were evaluated against observations. The WRF-Chem-PAH model is able to reasonably well simulate the concentration levels and particulate mass fractions of PAHs near the sources and at a remote outflow region of East Asia, in high spatial and temporal resolutions. Sensitivity study shows that the heterogeneous reaction with ozone and the homogeneous reaction with the nitrate radical significantly influence the fate and distributions of PAHs. The methods to implement new species and to correct the transport problems can be applied to other newly implemented species in WRF-Chem.

The Superstatistical Nature and Interoccurrence Time of Atmospheric Mercury Concentration Fluctuations

The probability density function (PDF) of the time intervals between subsequent extreme events in atmospheric Hg0 concentration data series from different latitudes has been investigated. The Hg0 dynamic possesses a long-term memory autocorrelation function. Above a fixed threshold Q in the data, the PDFs of the interoccurrence time of the Hg0 data are well described by a Tsallis q-Exponential function. This PDF behavior has been explained in the framework of superstatistics, where the competition between multiple mesoscopic processes affects the macroscopic dynamics. An extensive parameter μ, encompassing all possible fluctuations related to mesoscopic phenomena, has been identified. It follows a χ 2-distribution, indicative of the superstatistical nature of the overall process. Shuffling the data series destroys the long-term memory, the distributions become independent of Q, and the PDFs collapse on to the same exponential distribution. The possible central role of atmospheric turbulence on extreme events in the Hg0 data is highlighted.