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Long-term monitoring of data of ambient mercury (Hg) on a global scale to assess its emission, transport, atmospheric chemistry, and deposition processes is vital to understanding the impact of Hg pollution on the environment. The Global Mercury Observation System (GMOS) project was funded by the European Commission (http://www.gmos.eu) and started in November 2010 with the overall goal to develop a coordinated global observing system to monitor Hg on a global scale, including a large network of ground-based monitoring stations, ad hoc periodic oceanographic cruises and measurement flights in the lower and upper troposphere as well as in the lower stratosphere. To date, more than 40 ground-based monitoring sites constitute the global network covering many regions where little to no observational data were available before GMOS. This work presents atmospheric Hg concentrations recorded worldwide in the framework of the GMOS project (2010–2015), analyzing Hg measurement results in terms of temporal trends, seasonality and comparability within the network. Major findings highlighted in this paper include a clear gradient of Hg concentrations between the Northern and Southern hemispheres, confirming that the gradient observed is mostly driven by local and regional sources, which can be anthropogenic, natural or a combination of both.

Continuous measurements of atmospheric gaseous elemental mercury (GEM), particulate bound mercury (PBM) and gaseous oxidized mercury (GOM) at the high-altitude Pic du Midi Observatory (PDM Observatory, 2877 m a.s.l.) in southern France were made from November 2011 to November 2012. The mean GEM, PBM and GOM concentrations were 1.86 ng m−3, 14 pg m−3 and 27 pg m−3, respectively and we observed 44 high PBM (peak PBM values of 33–98 pg m−3) and 61 high GOM (peak GOM values of 91–295 pg m−3) events. The high PBM events occurred mainly in cold seasons (winter and spring) whereas high GOM events were mainly observed in the warm seasons (summer and autumn). In cold seasons the maximum air mass residence times (ARTs) associated with high PBM events were observed in the upper troposphere over North America. The ratios of high PBM ARTs to total ARTs over North America, Europe, the Arctic region and Atlantic Ocean were all elevated in the cold season compared to the warm season, indicating that the middle and upper free troposphere of the Northern Hemisphere may be more enriched in PBM in cold seasons. PBM concentrations and PBM ∕ GOM ratios during the high PBM events were significantly anti-correlated with atmospheric aerosol concentrations, air temperature and solar radiation, suggesting in situ formation of PBM in the middle and upper troposphere. We identified two distinct types of high GOM events with the GOM concentrations positively and negatively correlated with atmospheric ozone concentrations, respectively. High GOM events positively correlated with ozone were mainly related to air masses from the upper troposphere over the Arctic region and middle troposphere over the temperate North Atlantic Ocean, whereas high GOM events anti-correlated with ozone were mainly related to air masses from the lower free troposphere over the subtropical North Atlantic Ocean. The ARTs analysis demonstrates that the lower and middle free troposphere over the North Atlantic Ocean was the largest source region of atmospheric GOM at the PDM Observatory. The ratios of high GOM ARTs to total ARTs over the subtropical North Atlantic Ocean in summer were significantly higher than those over the temperate and sub-arctic North Atlantic Ocean as well as that over the North Atlantic Ocean in other seasons, indicating abundant in situ oxidation of GEM to GOM in the lower free troposphere over the subtropical North Atlantic Ocean in summer.

Mass-independent fractionation (MIF) of stable even mass number mercury (Hg) isotopes is observed in rainfall and gaseous elemental Hg 0 globally and is used to quantify atmospheric Hg deposition pathways. The chemical reaction and underlying even-Hg MIF mechanism are unknown however and speculated to be caused by Hg photo-oxidation on aerosols at the tropopause. Here, we investigate the Hg isotope composition of free tropospheric Hg 0 and oxidized Hg II forms at the high-altitude Pic du Midi Observatory. We find that gaseous oxidized Hg has positive Δ 199 Hg, Δ 201 Hg, and Δ 200 Hg and negative Δ 204 Hg signatures, similar to rainfall Hg, and we document rainfall Hg Δ 196 Hg to be near zero. Cloud water and rainfall Hg show an enhanced odd-Hg MIF of 0.3‰ compared to gaseous oxidized Hg II , potentially indicating the occurrence of in-cloud aqueous Hg II photoreduction. Diurnal MIF observations of free tropospheric Hg 0 show how net Hg 0 oxidation in high-altitude air masses leads to opposite even- and odd-MIF in Hg 0 and oxidized Hg II . We speculate that even-Hg MIF takes place by a molecular magnetic isotope effect during Hg II photoreduction on aerosols that involves magnetic halogen nuclei. A Δ 200 Hg mass balance suggests that global Hg deposition pathways in models are likely biased toward Hg II deposition. We propose that Hg cycling models could accommodate the Hg-isotope constraints on emission and deposition fluxes.

Atmospheric monitoring networks quantify gaseous elemental mercury (GEM) concentrations, but not isotopic compositions. Here, we present a new method for automated and quantitative stable isotope sampling of GEM (ISO-GEM) at the outlet of a commercial Hg analyzer. A programmable multivalve manifold selects Hg at the analyzer inlet and outlet based on specific criteria (location, time, GEM concentration, auxiliary threshold). Outlet Hg recovery was tested for gold traps, oxidizing acidic solution traps, and activated carbon traps. We illustrate the ISO-GEM method in an exploratory study on the effect of building walls on local GEM. We find that GEM concentrations directly at the building surface (wall inlet) are significantly enhanced (mean 3.8 ± 1.8 ng/m 3 ) compared to 3 m from the building wall (free inlet) (mean 1.5 ± 0.4 ng/m 3 ). GEM δ 202 Hg (-1.26‰ ± 0.41‰, 1 SD, n = 16) and Δ 199 Hg (-0.05‰ ± 0.10‰, 1 SD, n = 16) at the wall inlet were different from ambient GEM δ 202 Hg (0.76‰ ± 0.09‰, 1 SD, n = 16) and Δ 199 Hg (-0.21‰ ± 0.05‰, 1 SD, n = 16) at the free inlet. The isotopic fingerprint of GEM at the wall inlet suggests that GEM emission from the aluminum building surface affected local GEM concentration measurements. These results illustrate the versatility of the automated Hg isotope sampling.

Midlatitude anthropogenic mercury (Hg) emissions and discharge reach the Arctic Ocean (AO) by atmospheric and oceanic transport. Recent studies suggest that Arctic river Hg inputs have been a potentially overlooked source of Hg to the AO. Observations on Hg in Eurasian rivers, which represent 80% of freshwater inputs to the AO, are quasi-inexistent, however, putting firm understanding of the Arctic Hg cycle on hold. Here, we present comprehensive seasonal observations on dissolved Hg (DHg) and particulate Hg (PHg) concentrations and fluxes for two large Eurasian rivers, the Yenisei and the Severnaya Dvina. We find large DHg and PHg fluxes during the spring flood, followed by a second pulse during the fall flood. We observe well-defined water vs. Hg runoff relationships for Eurasian and North American Hg fluxes to the AO and for Canadian Hg fluxes into the larger Hudson Bay area. Extrapolation to pan-Arctic rivers and watersheds gives a total Hg river flux to the AO of 44 ± 4 Mg per year (1σ), in agreement with the recent model-based estimates of 16 to 46 Mg per year and Hg/dissolved organic carbon (DOC) observation-based estimate of 50 Mg per year. The river Hg budget, together with recent observations on tundra Hg uptake and AO Hg dynamics, provide a consistent view of the Arctic Hg cycle in which continental ecosystems traffic anthropogenic Hg emissions to the AO via rivers, and the AO exports Hg to the atmosphere, to the Atlantic Ocean, and to AO marine sediments., Competing Interests: The authors declare no conflict of interest.

Gaseous elemental mercury (GEM, Hg) emissions are transformed to divalent reactive Hg (RM) forms throughout the troposphere and stratosphere. RM is often operationally quantified as the sum of particle bound Hg (PBM) and gaseous oxidized Hg (GOM). The measurement of GOM and PBM is challenging and under mounting criticism. Here we intercompare six months of automated GOM and PBM measurements using a Tekran (TK) KCl-coated denuder and quartz regenerable particulate filter method (GOM TK , PBM TK , and RM TK ) with RM CEM collected on cation exchange membranes (CEMs) at the high altitude Pic du Midi Observatory. We find that RM TK is systematically lower by a factor of 1.3 than RM CEM . We observe a significant relationship between GOM TK (but not PBM TK ) and Tekran flush TK blanks suggesting significant loss (36%) of labile GOM TK from the denuder or inlet. Adding the flush TK blank to RM TK results in good agreement with RM CEM (slope = 1.01, r 2 = 0.90) suggesting we can correct bias in RM TK and GOM TK . We provide a bias corrected (*) Pic du Midi data set for 2012-2014 that shows GOM* and RM* levels in dry free tropospheric air of 198 ± 57 and 229 ± 58 pg m -3 which agree well with in-flight observed RM and with model based GOM and RM estimates.

Understanding the sources and transformations of mercury (Hg) in the free troposphere is a critical aspect of global Hg research. Here we present one year of observations of atmospheric Hg speciation and gaseous elemental Hg (GEM) isotopic composition at the high-altitude Pic du Midi Observatory (2860 m above sea level) in France. Biweekly integrated GEM from February 2012 to January 2013 revealed significant variations in δ(202)HgGEM (-0.04‰ to 0.52‰) but not in Δ(199)HgGEM (-0.17‰ to -0.27‰) or Δ(200)HgGEM (-0.10‰ to 0.05‰). δ(202)HgGEM was negatively correlated with CO and reflected air mass origins from Europe (high CO, low δ(202)HgGEM) and from the Atlantic Ocean (low CO, high δ(202)HgGEM). We suggest that the δ(202)HgGEM variations represent mixing of recent low δ(202)HgGEM European anthropogenic emissions with high δ(202)HgGEM northern hemispheric background GEM. In addition, Atlantic Ocean free troposphere air masses showed a positive correlation between δ(202)HgGEM and gaseous oxidized Hg (GOM) concentrations, indicative of mass-dependent Hg isotope fractionation during GEM oxidation. On the basis of atmospheric δ(202)HgGEM and speciated Hg observations, we suggest that the oceanic free troposphere is a reservoir within which GEM is readily oxidized to GOM.

Gaseous elemental mercury (GEM) is the dominant form of mercury in the atmosphere. Its conversion into oxidized gaseous and particulate forms is thought to drive atmospheric mercury wet deposition to terrestrial and aquatic ecosystems, where it can be subsequently transformed into toxic methylmercury. The contribution of mercury dry deposition is however largely unconstrained. Here we examine mercury mass balance and mercury stable isotope composition in a peat bog ecosystem. We find that isotope signatures of living sphagnum moss (Δ(199)Hg = -0.11 ± 0.09‰, Δ(200)Hg = 0.03 ± 0.02‰, 1σ) and recently accumulated peat (Δ(199)Hg = -0.22 ± 0.06‰, Δ(200)Hg = 0.00 ± 0.04‰, 1σ) are characteristic of GEM (Δ(199)Hg = -0.17 ± 0.07‰, Δ(200)Hg = -0.05 ± 0.02‰, 1σ), and differs from wet deposition (Δ(199)Hg = 0.73 ± 0.15‰, Δ(200)Hg = 0.21 ± 0.04‰, 1σ). Sphagnum covered during three years by transparent and opaque surfaces, which eliminate wet deposition, continue to accumulate Hg. Sphagnum Hg isotope signatures indicate accumulation to take place by GEM dry deposition, and indicate little photochemical re-emission. We estimate that atmospheric mercury deposition to the peat bog surface is dominated by GEM dry deposition (79%) rather than wet deposition (21%). Consequently, peat deposits are potential records of past atmospheric GEM concentrations and isotopic composition.

Mercury (Hg) is one of the main chemicals currently altering Mediterranean ecosystems. Red mullet (Mullus barbatus and M. surmuletus) have been widely used as quantitative bio-indicators of chemical contamination. In this study, we reassess the ability of these species to be used as efficient bio-indicators of Hg contamination by monitoring during 18 months Hg concentrations in muscle tissue of mullet sampled from 5 French Mediterranean coastal areas. Mean concentrations ranged between 0.23 and 0.78 μg g(-1) dry mass for both species. Values were consistent with expected contamination patterns of all sites except Corsica. Results confirmed that red mullets are efficient bio-indicators of Hg contamination. Nevertheless, the observed variability in Hg concentrations calls for caution regarding the period and the sample size. Attention should be paid to environmental and biologic specificities of each studied site, as they can alter the bioaccumulation of Hg, and lead to inferences about environmental Hg concentrations., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Surface snow samples were collected weekly from the 31st of December 2008 to the 21st of June 2009 from Lake Bramant in the French Alps. Total mercury (THg), total dissolved mercury (THgD), methylmercury (MeHg) and particle distributions in surface snow were analyzed. Results showed that THg concentrations, MeHg concentrations and particle load increased with snow surface temperature, which is an indicator of rising temperatures as the season progresses. Significant correlations between MeHg and snow surface temperature and MeHg and total particles greater than 10 μm were observed. This suggests that the MeHg found in the snow originates from atmospheric deposition processes rather than in situ snowpack sources. This study suggests that an important post-winter atmospheric deposition of MeHg and THg occurs on summital zones of the French Alps and it is likely that this contamination originates from the surrounding valleys., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Total mercury (THg) and methylmercury (MeHg) concentrations were measured in the muscle of Arctic charr (Salvelinus alpinus) and in the water column of 4 lakes that are located in the French Alps. Watershed characteristics were determined (6 coverage classes) for each lake in order to evaluate the influence of watershed composition on mercury and methylmercury concentrations in fish muscle and in the water column. THg and MeHg concentrations in surface water were relatively low and similar among lakes and watershed characteristics play a major role in determining water column Hg and MeHg levels. THg muscle concentrations for fish with either a standardized length of 220mm, a standardized age of 5 years or for individualuals did not exceed the 0.5mg kg(-1) fish consumption advisory limit established for Hg by the World Health Organization (WHO, 1990). These relatively low THg concentrations can be explained by watershed characteristics, which lead to short Hg residence time in the water column, and also by the short trophic chain that is characteristic of mountain lakes. Growth rate did not seem to influence THg concentrations in fish muscles of these lakes and we observed no relationship between fish Hg concentrations and altitude. This study shows that in the French Alps, high altitude lakes have relatively low THg and MeHg concentrations in both the water column and in Arctic charr populations. Therefore, Hg does not appear to present a danger for local populations and the fishermen of these lakes., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Polar regions are subject to contamination by mercury (Hg) transported from lower latitudes, severely impacting human and animal health. Atmospheric Mercury Depletion Events (AMDEs) are an episodic process by which Hg is transferred from the atmospheric reservoir to arctic snowpacks. The fate of Hg deposited during these events is the subject of numerous studies, but its speciation remains unclear, especially in terms of environmentally relevant forms such as bioavailable mercury (BioHg). Here, using a bacterial mer-lux biosensor, we report the fraction of newly deposited Hg at the surface and at the bottom of the snowpack that is bioavailable. Snow samples were collected over a two-month arctic field campaign in 2008. In surface snow, BioHg is related to atmospheric Hg deposition and snow fall events were shown to contribute to higher proportions of BioHg than AMDEs. Based on our data, AMDEs represent a potential source of 20 t.y(-1) of BioHg, while wet and dry deposition pathways may provide 135-225 t.y(-1) of BioHg to Arctic surfaces.