A large number of activities have been carried out to characterise the levels of mercury (Hg) species in ambient air and precipitation, in order to understand how they vary over time and how they ...depend on meteorological conditions. Following the discovery of atmospheric Hg depletion events (AMDEs) in Polar Regions, a significant research effort was made to assess the chemical-physical mechanisms behind the rapid conversion of atmospheric gaseous Hg (Hg0) into reactive and water-soluble forms which are potentially bioavailable. The understanding of the way in which Hg is released into the atmosphere, transformed, deposited and eventually incorporated into biota is of crucial importance not only for the polar regions but also for the marine environment in general. The oceans and seas are both sources and sinks of Hg and play a major role in the Hg cycle. In this work, the available Hg concentration datasets from a number of terrestrial sites (industrial, rural and remote) in both the Northern and Southern Hemispheres as well as over oceans and seas have been investigated. The higher Hg species concentration and variability observed in the Northern Hemisphere suggest that the majority of emissions and re-emissions occur there. The inter-hemispherical gradient with higher total gaseous mercury (TGM) concentrations in the Northern Hemisphere has remained nearly constant over the years for which data are available. The analysis of Hg concentration patterns indicates the differences in regional source/sink characteristics, with increasing variability toward areas strongly influenced by anthropogenic sources. The large increase in Hg emissions in rapidly developing countries (i.e., China, India) over the last decade, due primarily to a sharp increase in energy production from coal combustion, are not currently reflected in the long-term measurements of TGM in ambient air and precipitation at continuous monitoring sites in either Northern Europe or North America. The discrepancy between observed gaseous Hg concentrations (steady or decreasing) and global Hg emission inventories (increasing) has not yet been explained, though the potential oxidation of the atmosphere during the last decade is increasing. Currently, however, a coordinated observational network for Hg does not exist.
Although essential to fully understand the cycling of mercury at the global scale, mercury species records in the Southern Hemisphere are scarce. Under the framework of the Global Mercury Observation ...System (GMOS) project, a monitoring station has been set up on Amsterdam Island (37°48´ S, 77°34´ E) in the remote southern Indian Ocean. For the first time in the Southern Hemisphere, a 2-year record of gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and particle-bound mercury (PBM) is presented. GEM concentrations were remarkably steady (1.03 ± 0.08 ng m−3) while RGM and PBM concentrations were very low and exhibited a strong variability (mean: 0.34 pg m−3, range: < detection limit–4.07 pg m−3; and mean: 0.67 pg m−3, range: < detection limit–12.67 pg m−3, respectively). Despite the remoteness of the island, wind sector analysis, air mass back trajectories and the observation of radonic storms highlighted a long-range contribution from the southern African continent to the GEM and PBM budgets from July to September during the biomass burning season. Low concentrations of GEM were associated with southerly polar and marine air masses from the remote southern Indian Ocean. This unique data set provides new baseline GEM concentrations in the Southern Hemisphere midlatitudes while mercury speciation along with upcoming wet deposition data will help to improve our understanding of the mercury cycle in the marine boundary layer.
Our knowledge of the distribution of mercury concentrations in air of the Southern Hemisphere was until recently based mostly on intermittent measurements made during ship cruises. In the last few ...years continuous mercury monitoring has commenced at several sites in the Southern Hemisphere, providing new and more refined information. In this paper we compare mercury measurements at several remote sites in the Southern Hemisphere made over a period of at least 1 year at each location. Averages of monthly medians show similar although small seasonal variations at both Cape Point and Amsterdam Island. A pronounced seasonal variation at Troll research station in Antarctica is due to frequent mercury depletion events in the austral spring. Due to large scatter and large standard deviations of monthly average median mercury concentrations at Cape Grim, no systematic seasonal variation could be found there. Nevertheless, the annual average mercury concentrations at all sites during the 2007-2013 period varied only between 0.85 and 1.05 ng m-3. Part of this variability is likely due to systematic measurement uncertainties which we propose can be further reduced by improved calibration procedures. We conclude that mercury is much more uniformly distributed throughout the Southern Hemisphere than the distributions suggested by measurements made onboard ships. This finding implies that smaller trends can be detected in shorter time periods. We also report a change in the trend sign at Cape Point from decreasing mercury concentrations in 1996-2004 to increasing concentrations since 2007.
We perform global-scale inverse modeling to constrain present-day atmospheric mercury emissions and relevant physiochemical parameters in the GEOS-Chem chemical transport model. We use Bayesian ...inversion methods combining simulations with GEOS-Chem and ground-based Hg0 observations from regional monitoring networks and individual sites in recent years. Using optimized emissions/parameters, GEOS-Chem better reproduces these ground-based observations and also matches regional over-water Hg0 and wet deposition measurements. The optimized global mercury emission to the atmosphere is ~ 5.8 Gg yr-1. The ocean accounts for 3.2 Gg yr-1 (55 % of the total), and the terrestrial ecosystem is neither a net source nor a net sink of Hg0. The optimized Asian anthropogenic emission of Hg0 (gas elemental mercury) is 650-1770 Mg yr-1, higher than its bottom-up estimates (550-800 Mg yr-1). The ocean parameter inversions suggest that dark oxidation of aqueous elemental mercury is faster, and less mercury is removed from the mixed layer through particle sinking, when compared with current simulations. Parameter changes affect the simulated global ocean mercury budget, particularly mass exchange between the mixed layer and subsurface waters. Based on our inversion results, we re-evaluate the long-term global biogeochemical cycle of mercury, and show that legacy mercury becomes more likely to reside in the terrestrial ecosystem than in the ocean. We estimate that primary anthropogenic mercury contributes up to 23 % of present-day atmospheric deposition.
During atmospheric mercury and ozone depletion events in the springtime in polar regions gaseous elemental mercury and ozone undergo rapid declines. Mercury is quickly transformed into oxidation ...products, which are subsequently removed by deposition. Here we show that such events also occur during Antarctic winter over sea ice areas, leading to additional deposition of mercury. Over four months in the Weddell Sea we measured gaseous elemental, oxidized, and particulate-bound mercury, as well as ozone in the troposphere and total and elemental mercury concentrations in snow, demonstrating a series of depletion and deposition events between July and September.
The winter depletions in July were characterized by stronger correlations between mercury and ozone and larger formation of particulate-bound mercury in air compared to later spring events. It appears that light at large solar zenith angles is sufficient to initiate the photolytic formation of halogen radicals. We also propose a dark mechanism that could explain observed events in air masses coming from dark regions. Br2 that could be the main actor in dark conditions was possibly formed in high concentrations in the marine boundary layer in the dark. These high concentrations may also have caused the formation of high concentrations of CHBr3 and CH2I2 in the top layers of the Antarctic sea ice observed during winter.
These new findings show that the extent of depletion events is larger than previously believed and that winter depletions result in additional deposition of mercury that could be transferred to marine and terrestrial ecosystems.
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•Atmospheric mercury and ozone depletions were detected during Antarctic winter.•Winter depletion events were detected exclusively over sea ice areas.•Higher formation of particulate mercury during winter depletions.
Mercury (Hg) is a worldwide contaminant that can cause adverse health effects to wildlife and humans. While atmospheric modeling traces the link from emissions to deposition of Hg onto environmental ...surfaces, large uncertainties arise from our incomplete understanding of atmospheric processes (oxidation pathways, deposition, and re-emission). Atmospheric Hg reactivity is exacerbated in high latitudes and there is still much to be learned from polar regions in terms of atmospheric processes. This paper provides a synthesis of the atmospheric Hg monitoring data available in recent years (2011–2015) in the Arctic and in Antarctica along with a comparison of these observations with numerical simulations using four cutting-edge global models. The cycle of atmospheric Hg in the Arctic and in Antarctica presents both similarities and differences. Coastal sites in the two regions are both influenced by springtime atmospheric Hg depletion events and by summertime snowpack re-emission and oceanic evasion of Hg. The cycle of atmospheric Hg differs between the two regions primarily because of their different geography. While Arctic sites are significantly influenced by northern hemispheric Hg emissions especially in winter, coastal Antarctic sites are significantly influenced by the reactivity observed on the East Antarctic ice sheet due to katabatic winds. Based on the comparison of multi-model simulations with observations, this paper discusses whether the processes that affect atmospheric Hg seasonality and interannual variability are appropriately represented in the models and identifies research gaps in our understanding of the atmospheric Hg cycling in high latitudes.
Sunlit snow is highly photochemically active and plays a key role in the
exchange of gas phase species between the cryosphere and the atmosphere.
Here, we investigate the behaviour of two selected ...species in surface snow:
mercury (Hg) and iodine (I). Hg can deposit year-round and accumulate in the
snowpack. However, photo-induced re-emission of gas phase Hg from the
surface has been widely reported. Iodine is active in atmospheric new
particle formation, especially in the marine boundary layer, and in the
destruction of atmospheric ozone. It can also undergo photochemical
re-emission. Although previous studies indicate possible post-depositional
processes, little is known about the diurnal behaviour of these two species
and their interaction in surface snow. The mechanisms are still poorly
constrained, and no field experiments have been performed in different
seasons to investigate the magnitude of re-emission processes Three sampling
campaigns conducted at an hourly resolution for 3 d each were carried out
near Ny-Ålesund (Svalbard) to study the behaviour of mercury and iodine
in surface snow under different sunlight and environmental conditions
(24 h darkness, 24 h sunlight and day–night cycles). Our results indicate a
different behaviour of mercury and iodine in surface snow during the
different campaigns. The day–night experiments demonstrate the existence of a
diurnal cycle in surface snow for Hg and iodine, indicating that these
species are indeed influenced by the daily solar radiation cycle.
Differently, bromine did not show any diurnal cycle. The diurnal cycle also
disappeared for Hg and iodine during the 24 h sunlight period and during
24 h darkness experiments supporting the idea of the occurrence (absence) of
a continuous recycling or exchange at the snow–air interface. These results
demonstrate that this surface snow recycling is seasonally dependent,
through sunlight. They also highlight the non-negligible role that snowpack
emissions have on ambient air concentrations and potentially on
iodine-induced atmospheric nucleation processes.
This study presents measurements of gaseous elemental mercury (GEM) concentrations in the 80 m of firn air at the international drilling site of NEEM in Greenland (2452 m, 77°25.8 N, 51°06.4 W). ...Using inverse modeling, we were able to reconstruct the atmospheric GEM trend at this Arctic site over the last 60 years. We show discrepancies between this record and the previous firn record of Summit. This could be attributed to experimental biases and/or differences in air mass transport. A multisite inverse model was used to derive an atmospheric scenario reconciling the two firn records. We show that GEM seasonal variations are very limited at these high altitude sites and thus probably unaffected by spring/summer photochemistry. The firn reconstructions suggest an increase of GEM concentrations since the 1950s peaking in the late 1960s and early 1970s. A decrease is then observed with minimum GEM concentrations around 1995–2000. The reconstruction compares well with historical mercury (Hg) releases and recent simulations of atmospheric Hg. Our optimal GEM scenario does not allow to categorically conclude on recent trends for GEM concentrations over the 2000–2010 decade.
•Reconstruction of atmospheric gaseous mercury trend in the Arctic over 60 years.•The absence of strong seasonal variations for atmospheric GEM.•The optimal scenario is consistent with historical releases and model simulations.
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