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Near-surface mercury and ozone depletion events occur in the lowest part of the atmosphere during Arctic spring. Mercury depletion is the first step in a process that transforms long-lived elemental mercury to more reactive forms within the Arctic that are deposited to the cryosphere, ocean, and other surfaces, which can ultimately get integrated into the Arctic food web. Depletion of both mercury and ozone occur due to the presence of reactive halogen radicals that are released from snow, ice, and aerosols. In this work, we added a detailed description of the Arctic atmospheric mercury cycle to our recently published version of the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem 4.3.3) that includes Arctic bromine and chlorine chemistry and activation/recycling on snow and aerosols. The major advantage of our modelling approach is the online calculation of bromine concentrations and emission/recycling that is required to simulate the hourly and daily variability of Arctic mercury depletion. We used this model to study coupling between reactive cycling of mercury, ozone, and bromine during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) spring season in 2020 and evaluated results compared to land-based, ship-based, and remote sensing observations. The model predicts that elemental mercury oxidation is driven largely by bromine chemistry and that particulate mercury is the major form of oxidized mercury. The model predicts that the majority (74%) of oxidized mercury deposited to land-based snow is re-emitted to the atmosphere as gaseous elemental mercury, while a minor fraction (4%) of oxidized mercury that is deposited to sea ice is re-emitted during spring. Our work demonstrates that hourly differences in bromine/ozone chemistry in the atmosphere must be considered to capture the springtime Arctic mercury cycle, including its integration into the cryosphere and ocean.

Oil sands upgrading facilities in the Athabasca Oil Sands Region (AOSR) in Alberta, Canada, have been reporting mercury (Hg) emissions to public government databases (National Pollutant Release Inventory (NPRI)) since the year 2000, yet the relative contribution of these emissions to ambient Hg deposition remains unknown. A 3D process-based global Hg model, GEM-MACH-Hg, was applied to simulate the Hg burden in and around the AOSR using NPRI reported oil sands Hg emissions from 2012 (59 kg) to 2015 (25 kg) and other regional and global Hg emissions. The impact of oil sands emissions (OSE) on Hg levels in the AOSR, relative to contributions from sources such as global anthropogenic and biomass burning emissions (BBE), was assessed. In addition, the relative importance of year-to-year changes in Hg emissions from the above sources and meteorological conditions to inter-annual variations in Hg deposition was examined. Model simulated surface air concentrations of Hg species and annually accumulated Hg in snowpacks were found comparable to independently obtained measurements in the AOSR, suggesting consistency between reported Hg emissions from oil sands activities and Hg levels in the region. As a result of global-scale transport of gaseous elemental Hg (Hg(0)), surface air concentrations of Hg(0) in the AOSR reflected the background Hg(0) levels in Canada (1.4 ng m−3, AOSR; 1.2 1.6 ng m−3, Canada) with negligible impact from OSE. Highly spatiotemporally variable wildfire Hg emission events led to episodes of high ambient Hg(0) air concentrations of up to 2.5 ng m−3 during the burning season. By comparison, average air concentrations of total oxidised Hg (gaseous plus particulate; efficiently deposited Hg species) in the AOSR were elevated by 60 % above background levels (2012–2013) within 50 km of the oil sands major upgraders as a result of OSE. Annual average Hg deposition fluxes in the AOSR were within the range of the deposition fluxes measured for the entire province of Alberta (15.6–18.3 µg m−2 y−1, AOSR (2012–2015); ~14–25 µg m−2 y−1, Alberta (2015)). Winter (November–April) and summer (June–August), respectively, accounted for 20 % and 50 % of the annual Hg deposition in the AOSR. On a broad spatial scale, imported Hg from global sources dominated the annual Hg deposition in the AOSR, with present-day global anthropogenic emissions contributing to 40 % (

Passive air samplers (PASs), which provide time-averaged concentrations of gaseous mercury over the timescale of weeks to months, are promising for filling a gap in the monitoring of atmospheric mercury worldwide. Their usefulness will depend on their ease of use and robustness under field conditions, their availability and affordability, and most notably, their ability to provide results of acceptable precision and accuracy. Here we describe a comparative evaluation of three PASs with respect to their ability to precisely and accurately record atmospheric background mercury concentrations at sites in both southern Italy and southern Ontario, Canada. The study includes the CNR-PAS with gold nanoparticles as a sorbent, developed by the Italian National Research Council, the IVL-PAS using an activated carbon-coated disk, developed by the Swedish Environmental Research Institute, and the MerPAS® using a sulfur-impregnated activated carbon sorbent, developed at the University of Toronto and commercialized by Tekran. Detection limits are deduced from the variability in the amount of mercury quantified in more than 20 field blank samples for each PAS. Analytical and sampling precision is quantified through 22 triplicate deployments for each PAS, ranging in duration from 2 to 12 weeks. Accuracy and bias are assessed through comparison with gaseous elemental mercury concentrations recorded by Tekran 2537 automated mercury analyzers operating alongside the PASs at both locations. The performance of the PASs was significantly better in Italy, with all of them providing concentrations that are not significantly different from the average concentrations of the Tekran 2537 instruments. In Canada, where weather conditions were much harsher and more variable during the February through April deployment period, there are differences amongst the PASs. At both sites, the MerPAS® is currently the most sensitive, precise, and accurate among the three PASs. A key reason for this is the larger size and the radial configuration of the MerPAS®, which results in lower blank levels relative to the sequestered amounts of mercury when compared to the other two PASs, which rely on axial diffusion geometries. Since blank correction becomes relatively smaller with longer deployments, performance tends to be closer amongst the PASs during deployments of 8 and 12 weeks.

Wildfire impacts on air quality and climate are expected to be exacerbated by climate change with the most pronounced impacts in the boreal biome. Despite the large geographic coverage, there is a lack of information on boreal forest wildfire emissions, particularly for organic compounds, which are critical inputs for air quality model predictions of downwind impacts. In this study, airborne measurements of 250 compounds from 15 instruments, including 228 non-methane organics compounds (NMOG), were used to provide the most detailed characterization, to date, of boreal forest wildfire emissions. Highly speciated measurements showed a large diversity of chemical classes highlighting the complexity of emissions. Using measurements of the total NMOG carbon (NMOGT), the ΣNMOG was found to be 46.2 % of NMOGT, of which, the intermediate- and semi-volatile organic compounds (I/SVOCs) were estimated to account for 7.4 %. These estimates of I/SVOC emission factors expand the volatility range of NMOG typically reported. Despite extensive speciation, a substantial portion of NMOGT remained unidentified (46.4 %), with expected contributions from more highly-functionalized VOCs and I/SVOCs. The emission factors derived in this study improve wildfire chemical speciation profiles and are especially relevant for air quality modelling of boreal forest wildfires. These aircraft-derived emission estimates were further linked with those derived from satellite observations demonstrating their combined value in assessing variability in modelled emissions. These results contribute to the verification and improvement of models that are essential for reliable predictions of near-source and downwind pollution resulting from boreal forest wildfires.

The Arctic region forms a unique environment with specific physical, chemical, and biological processes affecting mercury (Hg) cycles and limited anthropogenic Hg sources. However, historic global emissions and long range atmospheric transport has led to elevated Hg in Arctic wildlife and waterways. Continuous atmospheric Hg measurements, spanning 20 years, and increased monitoring sites has allowed a more comprehensive understanding of how Arctic atmospheric mercury is changing over time. Time-series trend analysis of TGM (Total Gaseous Mercury) in air was performed from 10 circumpolar air monitoring stations, comprising of high-Arctic, and sub-Arctic sites. GOM (gaseous oxidised mercury) and PHg (particulate bound mercury) measurements were also available at 2 high-Arctic sites. Seasonal mean TGM for sub-Arctic sites were lowest during fall ranging from 1.1 ng m−3 Hyytiälä to 1.3 ng m−3, Little Fox Lake. Mean TGM concentrations at high-Arctic sites showed the greatest variability, with highest daily means in spring ranging between 4.2 ng m−3 at Amderma and 2.4 ng m−3 at Zeppelin, largely driven by local chemistry. Annual TGM trend analysis was negative for 8 of the 10 sites. High-Arctic seasonal TGM trends saw smallest decline during summer. Fall trends ranged from −0.8% to −2.6% yr−1. Across the sub-Arctic sites spring showed the largest significant decreases, ranging between −7.7% to −0.36% yr−1, while fall generally had no significant trends. High-Arctic speciation of GOM and PHg at Alert and Zeppelin showed that the timing and composition of atmospheric mercury deposition events are shifting. Alert GOM trends are increasing throughout the year, while PHg trends decreased or not significant. Zeppelin saw the opposite, moving towards increasing PHg and decreasing GOM. Atmospheric mercury trends over the last 20 years indicate that Hg concentrations are decreasing across the Arctic, though not uniformly. This is potentially driven by environmental change, such as plant productivity and sea ice dynamics.

Bromine atoms play a central role in atmospheric reactive halogen chemistry, depleting ozone and elemental mercury, thereby enhancing deposition of toxic mercury, particularly in the Arctic near-surface troposphere. However, direct bromine atom measurements have been missing to date, due to the lack of analytical capability with sufficient sensitivity for ambient measurements. Here we present direct atmospheric bromine atom measurements, conducted in the springtime Arctic. Measured bromine atom levels reached 14 parts per trillion (ppt, pmol mol −1 ; 4.2 × 10 8 atoms per cm −3 ) and were up to 3–10 times higher than estimates using previous indirect measurements not considering the critical role of molecular bromine. Observed ozone and elemental mercury depletion rates are quantitatively explained by the measured bromine atoms, providing field validation of highly uncertain mercury chemistry. Following complete ozone depletion, elevated bromine concentrations are sustained by photochemical snowpack emissions of molecular bromine and nitrogen oxides, resulting in continued atmospheric mercury depletion. This study provides a breakthrough in quantitatively constraining bromine chemistry in the polar atmosphere, where this chemistry connects the rapidly changing surface to pollutant fate.

Thin solid films 735, 138862 (2021). doi:10.1016/j.tsf.2021.138862, Published by Elsevier, Amsterdam [u.a.]

Ferromagnetic insulator thin films can convey information by spin waves, avoiding charge displacement and Eddy current losses. The sparsity of high-temperature insulating ferromagnetic materials hinders the development of spin wave based devices. Stoichiometric magnesium titanate, MgTiO$_3$, has an electronic-energy-band structure in which all bands are either full or empty, being a paramagnetic insulator. The MgTiO$_3$ ilmenite consists of ordered octahedra and cation network in which one third of the octahedra are vacant, one third host magnesium and one third titanium. By giving up these characteristics, a rich variety of different magnetic structures can be formed. Our experiments and electronic-energy-band-structure computations show that the magnetic and electric properties of Mg-Ti-O films can drastically be changed and controlled by Mg- and Ti-cation arrangement and abundancy in the octahedra. Insulating titanium- and semiconducting magnesium-rich films were ferromagnetic up to elevated temperatures. The presence and origin of ferromagnetic insulating phase in the films is not apparent - the expectation, based on the well-established rules set by Goodenough and Kanamori, is paramagnetic or antiferromagnetic ordering. We show that ferro- and paramagnetic phases, possessing the same stoichiometry, can be obtained by merely rearranging the cations, thus allowing defect-free interfaces in multilayer structures.

Passive air samplers (PASs) for gaseous mercury (Hg) were deployed for time periods between 1 month and 1 year at 20 sites across the globe with continuous atmospheric Hg monitoring using active Tekran instruments. The purpose was to evaluate the accuracy of the PAS vis-à-vis the industry standard active instruments and to determine a sampling rate (SR; the volume of air stripped of gaseous Hg per unit of time) that is applicable across a wide range of conditions. The sites spanned a wide range of latitudes, altitudes, meteorological conditions, and gaseous Hg concentrations. Precision, based on 378 replicated deployments performed by numerous personnel at multiple sites, is 3.6 ± 3.0 %1, confirming the PAS's excellent reproducibility and ease of use. Using a SR previously determined at a single site, gaseous Hg concentrations derived from the globally distributed PASs deviate from Tekran-based concentrations by 14.2 ± 10 %. A recalibration using the entire new data set yields a slightly higher SR of 0.1354 ± 0.016 m3 day−1. When concentrations are derived from the PAS using this revised SR the difference between concentrations from active and passive sampling is reduced to 8.8 ± 7.5 %. At the mean gaseous Hg concentration across the study sites of 1.54 ng m−3, this represents an ability to resolve concentrations to within 0.13 ng m−3. Adjusting the sampling rate to deployment specific temperatures and wind speeds does not decrease the difference in active–passive concentration further (8.7 ± 5.7 %), but reduces its variability by leading to better agreement in Hg concentrations measured at sites with very high and very low temperatures and very high wind speeds. This value (8.7 ± 5.7 %) represents a conservative assessment of the overall uncertainty of the PAS due to inherent uncertainties of the Tekran instruments. Going forward, the recalibrated SR adjusted for temperature and wind speed should be used, especially if conditions are highly variable or deviate considerably from the average of the deployments in this study (9.89 °C, 3.41 m s−1). Overall, the study demonstrates that the sampler is capable of recording background gaseous Hg concentrations across a wide range of environmental conditions with accuracy similar to that of industry standard active sampling instruments. Results at sites with active speciation units were inconclusive on whether the PASs take up total gaseous Hg or solely gaseous elemental Hg primarily because gaseous oxidized Hg concentrations were in a similar range as the uncertainty of the PAS. 1Subscripted numbers are not significant, but are reported to reduce rounding errors in subsequent studies (see Sect. 2.3 for details).

Passive air samplers (PASs) provide an opportunity to improve the spatial range and resolution of gaseous mercury (Hg) measurements. Here, we propose a sampler design that combines a sulfur-impregnated activated carbon sorbent, a Radiello diffusive barrier, and a protective shield for outdoor deployments. The amount of gaseous Hg taken up by the sampler increased linearly with time for both an 11-week indoor (r2 = 0.990) and 12-month outdoor (r2 = 0.996) deployment, yielding sampling rates of 0.158 ± 0.008 m3 day–1 indoors and 0.121 ± 0.005 m3 day–1 outdoors. These sampling rates are close to modeled estimates of 0.166 m3 day–1 indoors and 0.129 m3 day–1 outdoors. Replicate precision is better than for all previous PASs for gaseous Hg, especially during outdoor deployments (2 ± 1.3%). Such precision is essential for discriminating the relatively small concentration variations occurring at background sites. Deployment times for obtaining reliable time-averaged atmospheric gaseous Hg concentrations range fr...

Long-range atmospheric transport and deposition are important sources of mercury (Hg) to Arctic aquatic and terrestrial ecosystems. We review here recent progress made in the study of the transport, transformation, deposition and reemission of atmospheric Hg in the Canadian Arctic, focusing on field measurements (see Dastoor et al., this issue for a review of modeling studies on the same topics). Redox processes control the speciation of atmospheric Hg, and thus impart an important influence on Hg deposition, particularly during atmospheric mercury depletion events (AMDEs). Bromine radicals were identified as the primary oxidant of atmospheric Hg during AMDEs. Since the start of monitoring at Alert (NU) in 1995, the timing of peak AMDE occurrence has shifted to earlier times in the spring (from May to April) in recent years, and while AMDE frequency and GEM concentrations are correlated with local meteorological conditions, the reasons for this timing-shift are not understood. Mercury is subject to various post-depositional processes in snowpacks and a large portion of deposited oxidized Hg can be reemitted following photoreduction; how much Hg is deposited and reemitted depends on geographical location, meteorological, vegetative and sea-ice conditions, as well as snow chemistry. Halide anions in the snow can stabilize Hg, therefore it is expected that a smaller fraction of deposited Hg will be reemitted from coastal snowpacks. Atmospheric gaseous Hg concentrations have decreased in some parts of the Arctic (e.g., Alert) from 2000 to 2009 but at a rate that was less than that at lower latitudes. Despite numerous recent advances, a number of knowledge gaps remain, including uncertainties in the identification of oxidized Hg species in the air (and how this relates to dry vs. wet deposition), physical–chemical processes in air, snow and water—especially over sea ice—and the relationship between these processes and climate change.

Ten years of atmospheric mercury speciation data and 14 years of mercury in snow data from Alert, Nunavut, Canada, are examined. The speciation data, collected from 2002 to 2011, includes gaseous elemental mercury (GEM), particulate mercury (PHg) and reactive gaseous mercury (RGM). During the winter-spring period of atmospheric mercury depletion events (AMDEs), when GEM is close to being completely depleted from the air, the concentration of both PHg and RGM rise significantly. During this period, the median concentrations for PHg is 28.2 pgm−3 and RGM is 23.9 pgm−3, from March to June, in comparison to the annual median concentrations of 11.3 and 3.2 pgm−3 for PHg and RGM, respectively. In each of the ten years of sampling, the concentration of PHg increases steadily from January through March and is higher than the concentration of RGM. This pattern begins to change in April when the levels of PHg peak and RGM begin to increase. In May, the high PHg and low RGM concentration regime observed in the early spring undergoes a transition to a regime with higher RGM and much lower PHg concentrations. The higher RGM concentration continues into June. The transition is driven by the atmospheric conditions of air temperature and particle availability. Firstly, a high ratio of the concentrations of PHg to RGM is reported at low temperatures which suggests that oxidized gaseous mercury partitions to available particles to form PHg. Prior to the transition, the median air temperature is −24.8 °C and after the transition the median air temperature is −5.8 °C. Secondly, the high PHg concentrations occur in the spring when high particle concentrations are present. The high particle concentrations are principally due to Arctic haze and sea salts. In the snow, the concentrations of mercury peak in May for all years. Springtime deposition of total mercury to the snow at Alert peaks in May when atmospheric conditions favour higher levels of RGM. Therefore, the conditions in the atmosphere directly impact when the highest amount of mercury will be deposited to the snow during the Arctic spring.

Sea-ice leads (open water channels), which increase with an ongoing shift from perennial to seasonal sea ice, are shown to initiate convection in the Arctic boundary layer, thus supplying ozone and gaseous mercury to the surface and possibly leading to additional pollution effects. A shift from perennial to seasonal sea ice is occurring in the Arctic Ocean, producing a higher percentage of seasonal sea ice that is thinner, saltier and less consolidated than perennial ice and so is more susceptible to fracture. This study of the near-surface atmosphere off the coast of Barrow, Alaska, finds that atmospheric mercury and ozone depletion events are facilitated by consolidated sea-ice cover. Recovery from the depletion events is found to be rapid in the presence of open sea-ice leads, probably a result of shallow convection in the stable Arctic boundary layer that supplies mercury and ozone from undepleted air masses aloft. The ongoing regime shift of Arctic sea ice from perennial to seasonal ice is associated with more dynamic patterns of opening and closing sea-ice leads (large transient channels of open water in the ice)1,2,3, which may affect atmospheric and biogeochemical cycles in the Arctic4. Mercury and ozone are rapidly removed from the atmospheric boundary layer during depletion events in the Arctic5,6,7, caused by destruction of ozone along with oxidation of gaseous elemental mercury (Hg(0)) to oxidized mercury (Hg(ii)) in the atmosphere and its subsequent deposition to snow and ice5. Ozone depletion events can change the oxidative capacity of the air by affecting atmospheric hydroxyl radical chemistry8, whereas atmospheric mercury depletion events can increase the deposition of mercury to the Arctic6,9,10,11, some of which can enter ecosystems during snowmelt12. Here we present near-surface measurements of atmospheric mercury and ozone from two Arctic field campaigns near Barrow, Alaska. We find that coastal depletion events are directly linked to sea-ice dynamics. A consolidated ice cover facilitates the depletion of Hg(0) and ozone, but these immediately recover to near-background concentrations in the upwind presence of open sea-ice leads. We attribute the rapid recoveries of Hg(0) and ozone to lead-initiated shallow convection in the stable Arctic boundary layer, which mixes Hg(0) and ozone from undepleted air masses aloft. This convective forcing provides additional Hg(0) to the surface layer at a time of active depletion chemistry, where it is subject to renewed oxidation. Future work will need to establish the degree to which large-scale changes in sea-ice dynamics across the Arctic alter ozone chemistry and mercury deposition in fragile Arctic ecosystems.

Results from ten years of gaseous elemental mercury (GEM) measurements at Zeppelin station, Ny-A° lesund, Svalbard, show no overall annual trend between 2000 and 2009. Seasonal trend analysis showed significantly decreasing trends in January, February, March and June (−4.5 to −14.9 pgm−3 yr−1) and significantly increasing trends in May and July through December (1.5 to 28.7 pgm−3 yr −1). Results showed that atmospheric mercury depletion events (AMDEs) were equally distributed between April and May with only a few having been observed in March and June. A negative correlation between AMDEs and temperature is reported and supports earlier observations that AMDEs tend to occur at low temperatures. Lower concentrations of GEM were seen at lower temperatures below a threshold of 0 C. The occurrence of AMDEs and wind direction were well correlated with the lowest GEM measured when the wind direction was from the Arctic Ocean region. Wind speed was found to not correlate with AMDEs, but the lowest GEM concentrations were observed at low wind speeds between 4 and 11ms−1. AMDEs and relative humidity did not correlate well, but the lowest GEM levels appeared when the relative humidity was between 80 and 90 %. Diurnal variation was observed especially during the month of March and is probably due to daytime snow surface emission induced by solar radiation. Relationships between GEM concentration and the Northern Hemisphere climate indices were investigated to assess if these climate parameters might reflect different atmospheric conditions that enhance or reduce spring AMDE activity. No consistent pattern was observed. © Author(s) 2013. This work is distributed under the Creative Commons Attribution 3.0 License.

L. Zhang et al. (2012), in a recent report, compared model estimates with new observations of oxidized and particulate mercury species (Hg2+ and Hgp) in the Great Lakes region and found that the sum of Hg2+ and Hgp varied between a factor of 2 to 10 between measurements and model. They suggested too high emission inputs as Hg2+ and too fast oxidative conversion of Hg0 to Hg2+ and Hgp as possible causes. This study quantitatively explores measurement uncertainties in detail. These include sampling efficiency, composition of sample, interfering species and calibration errors. Model (Global/Regional Atmospheric Heavy Metals Model – GRAHM) sensitivity experiments are used to examine the consistency between various Hg measurements and speciation of Hg near emission sources to better understand the discrepancies between modelled and measured concentrations of Hg2+ and Hgp. We find that the ratio of Hg0, Hg2+ and Hgp in the emission inventories, measurements of surface air concentrations of oxidized Hg and measurements of wet deposition are currently inconsistent with each other in the vicinity of emission sources. Current speciation of Hg emissions suggests higher concentrations of Hg2+ in air and in precipitation near emission sources; however, measured air concentrations of Hg2+ and measured concentrations of Hg in precipitation are not found to be significantly elevated near emission sources compared to the remote regions. The averaged unbiased root mean square error (RMSE) between simulated and observed concentrations of Hg2+ is found to be reduced by 42% and for Hgp reduced by 40% for 21 North American sites investigated, when a ratio for Hg0 : Hg2+ : Hgp in the emissions is changed from 50 : 40 : 10 (as specified in the original inventories) to 90 : 8 : 2. Unbiased RMSE reductions near emissions sources in the eastern United States and Canada are found to be reduced by up to 58% for Hg2+. Significant improvement in the model simulated spatial distribution of wet deposition of mercury in North America is noticed with the modified Hg emission speciation. Measurement-related uncertainties leading to lower estimation of Hg2+ concentrations are 86%. Uncertainties yielding either to higher or lower Hg2+ concentrations are found to be 36%. Finally, anthropogenic emission uncertainties are 106% for Hg2+. Thus it appears that the identified uncertainties for model estimates related to mercury speciation near sources, uncertainties in measurement methodology and uncertainties in emissions can close the gap between modelled and observed estimates of oxidized mercury found in L. Zhang et al. (2012). Model sensitivity simulations show that the measured concentrations of oxidized mercury, in general, are too low to be consistent with measured wet deposition fluxes in North America. Better emission inventories (with respect to speciation), better techniques for measurements of oxidized species and knowledge of mercury reduction reactions in different environments (including in-plume) in all phases are needed for improving the mercury models.

Mercury contamination in the Great Lakes continues to have important public health and wildlife ecotoxicology impacts, and atmospheric deposition is a significant ongoing loading pathway. The objective of this study was to estimate the amount and source-attribution for atmospheric mercury deposition to each lake, information needed to prioritize amelioration efforts. A new global, Eulerian version of the HYSPLIT-Hg model was used to simulate the 2005 global atmospheric transport and deposition of mercury to the Great Lakes. In addition to the base case, 10 alternative model configurations were used to examine sensitivity to uncertainties in atmospheric mercury chemistry and surface exchange. A novel atmospheric lifetime analysis was used to characterize fate and transport processes within the model. Model-estimated wet deposition and atmospheric concentrations of gaseous elemental mercury (Hg(0)) were generally within ∼10% of measurements in the Great Lakes region. The model overestimated non-Hg(0) concentrations by a factor of 2–3, similar to other modeling studies. Potential reasons for this disagreement include model inaccuracies, differences in atmospheric Hg fractions being compared, and the measurements being biased low. Lake Erie, downwind of significant local/regional emissions sources, was estimated by the model to be the most impacted by direct anthropogenic emissions (58% of the base case total deposition), while Lake Superior, with the fewest upwind local/regional sources, was the least impacted (27%). The U.S. was the largest national contributor, followed by China, contributing 25% and 6%, respectively, on average, for the Great Lakes. The contribution of U.S. direct anthropogenic emissions to total mercury deposition varied between 46% for the base case (with a range of 24–51% over all model configurations) for Lake Erie and 11% (range 6–13%) for Lake Superior. These results illustrate the importance of atmospheric chemistry, as well as emissions strength, speciation, and proximity, to the amount and source-attribution of mercury deposition.

Mercury in the Arctic is an important environmental and human health issue. The reliance of Northern Peoples on traditional foods, such as marine mammals, for subsistence means that they are particularly at risk from mercury exposure. The cycling of mercury in Arctic marine systems is reviewed here, with emphasis placed on the key sources, pathways and processes which regulate mercury levels in marine food webs and ultimately the exposure of human populations to this contaminant. While many knowledge gaps exist limiting our ability to make strong conclusions, it appears that the long-range transport of mercury from Asian emissions is an important source of atmospheric Hg to the Arctic and that mercury methylation resulting in monomethylmercury production (an organic form of mercury which is both toxic and bioaccumulated) in Arctic marine waters is the principal source of mercury incorporated into food webs. Mercury concentrations in biological organisms have increased since the onset of the industrial age and are controlled by a combination of abiotic factors (e.g., monomethylmercury supply), food web dynamics and structure, and animal behavior (e.g., habitat selection and feeding behavior). Finally, although some Northern Peoples have high mercury concentrations of mercury in their blood and hair, harvesting and consuming traditional foods have many nutritional, social, cultural and physical health benefits which must be considered in risk management and communication.

Atmospheric deposition of Hg(II) represents a major input of mercury to surface environments. The phase of Hg(II) (gas or particle) has important implications for deposition. We use long-term observations of reactive gaseous mercury (RGM, the gaseous component of Hg(II)), particle-bound mercury (PBM, the particulate component of Hg(II)), fine particulate matter (PM2.5), and temperature (T) at five sites in North America to derive an empirical gas-particle partitioning relationship log10(K−1) = (10±1)–(2500±300)/T where K = (PBM/PM2.5)/RGM with PBM and RGM in common mixing ratio units, PM2.5 in μg m−3, and T in K. This relationship is within the range of previous work but is based on far more extensive data from multiple sites. We implement this empirical relationship in the GEOS-Chem global 3-D Hg model to partition Hg(II) between the gas and particle phases. The resulting gas-phase fraction of Hg(II) ranges from over 90 % in warm air with little aerosol to less than 10 % in cold air with high aerosol. Hg deposition to high latitudes increases because of more efficient scavenging of particulate Hg(II) by precipitating snow. Model comparison to Hg observations at the North American surface sites suggests that subsidence from the free troposphere (warm air, low aerosol) is a major factor driving the seasonality of RGM, while elevated PBM is mostly associated with high aerosol loads. Simulation of RGM and PBM at these sites is improved by including fast in-plume reduction of Hg(II) emitted from coal combustion and by assuming that anthropogenic particulate Hg(p) behaves as semi-volatile Hg(II) rather than as a refractory particulate component. We improve the simulation of Hg wet deposition fluxes in the US relative to a previous version of GEOS-Chem; this largely reflects independent improvement of the washout algorithm. The observed wintertime minimum in wet deposition fluxes is attributed to inefficient snow scavenging of gas-phase Hg(II).

Gaseous elemental mercury (GEM) measurements at Alert, Canada, from 1995 to 2007 were analyzed for statistical time trends and for correlations with meteorological and climate data. A significant decreasing trend in annual GEM concentration is reported at Alert, with an estimated slope of −0.0086 ng m−3 yr−1 (−0.6% yr−1) over this 13-year period. It is shown that there has been a shift in the month of minimum mean GEM concentration from May to April due to a change in the timing of springtime atmospheric mercury depletion events (AMDEs). These AMDEs are found to decrease with increasing local temperature within each month, both at Alert and at Amderma, Russia. These results support the temperature dependence suggested by previous experimental results and theoretical kinetic calculations on both bromine generation and mercury oxidation and highlight the potential for changes in Arctic mercury chemistry with climate. A correlation between total monthly AMDEs at Alert and the Polar/Eurasian Teleconnection Index was observed only in March, perhaps due to higher GEM inputs in early spring in those years with a weak polar vortex. A correlation of AMDEs at Alert with wind direction supports the origin of mercury depletion events over the Arctic Ocean, in agreement with a previous trajectory study of ozone depletion events. Interannual variability in total monthly depletion event frequency at Alert does not appear to correlate significantly with total or first-year northern hemispheric sea ice area or with other major teleconnection patterns. Nor do AMDEs at either Alert or Amderma correlate with local wind speed, as might be expected if depletion events are sustained by stable, low-turbulence atmospheric conditions. The data presented here – both the change in timing of depletion events and their relationship with temperature – can be used as additional constraints to improve the ability of models to predict the cycling and deposition of mercury in the Arctic.

An Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) was deployed at the peak of Whistler Mountain (2182 m above sea level), British Columbia, from 19 April to 16 May 2006, as part of the Intercontinental Chemical Transport Experiment Phase B (INTEX-B) campaign. The mass concentrations and size distributions of non-refractory submicron particle (NR-PM1) species (i.e., sulfate, nitrate, ammonium, chloride, and organics) were measured in situ at 10-min time resolution. The HR-ToF-AMS results agreed well with collocated measurements. The average concentration of non-refractory submicron particulate matter (NR-PM1; 1.9 μg m−3) is similar to those observed at other remote, high elevation sites in North America. Episodes of enhanced aerosol loadings were observed, due to influences of regional and trans-Pacific transport of air pollution. Organics and sulfate were the dominant species, on average accounting for 55% and 30%, respectively, of the NR-PM1 mass. The average size distributions of sulfate and ammonium both showed an accumulation mode peaking at ~500 nm in vacuum aerodynamic diameter (Dva) while those of organic aerosol (OA) and nitrate peaked at ~300 nm. The size differences suggested that sulfate and OA were mostly present in external mixtures from different source origins. We also quantitatively determined the elemental composition of OA using the high resolution mass spectra. Overall, OA at Whistler Peak was highly oxygenated, with an average organic-mass-to-organic-carbon ratio (OM/OC) of 2.28±0.23 and an atomic ratio of oxygen-to-carbon (O/C) of 0.83±0.17. The nominal formula for OA was C1H1.66N0.03O0.83 for the entire study. Two significant trans-Pacific dust events originated from Asia were observed at Whistler Peak during this study. While both events were characterized with significant enhancements of coarse mode particles and mineral contents, the composition and characteristics of NR-PM1 were significantly different between them. One trans-Pacific event occurred on 15 May 2006, during which ammonium sulfate contributed >90% of the total NR-PM1 mass. This event was followed by a high OA episode likely associated with regional emissions. In total, three enhanced regional OA events, each of which lasted 2–3 days, were observed during this study. In contrast to the two dust events, the regional OA events were generally characterized with higher OA/sulfate ratio, less oxidized OA, and lower OM/OC ratio.

It was discovered in 1995 that, during the spring time, unexpectedly low concentrations of gaseous elemental mercury (GEM) occurred in the Arctic air. This was surprising for a pollutant known to have a long residence time in the atmosphere; however conditions appeared to exist in the Arctic that promoted this depletion of mercury (Hg). This phenomenon is termed atmospheric mercury depletion events (AMDEs) and its discovery has revolutionized our understanding of the cycling of Hg in Polar Regions while stimulating a significant amount of research to understand its impact to this fragile ecosystem. Shortly after the discovery was made in Canada, AMDEs were confirmed to occur throughout the Arctic, sub-Artic and Antarctic coasts. It is now known that, through a series of photochemically initiated reactions involving halogens, GEM is converted to a more reactive species and is subsequently associated to particles in the air and/or deposited to the polar environment. AMDEs are a means by which Hg is transferred from the atmosphere to the environment that was previously unknown. In this article we review Hg research taken place in Polar Regions pertaining to AMDEs, the methods used to collect Hg in different environmental media, research results of the current understanding of AMDEs from field, laboratory and modeling work, how Hg cycles around the environment after AMDEs, gaps in our current knowledge and the future impacts that AMDEs may have on polar environments. The research presented has shown that while considerable improvements in methodology to measure Hg have been made but the main limitation remains knowing the speciation of Hg in the various media. The processes that drive AMDEs and how they occur are discussed. As well, the role that the snow pack and the sea ice play in the cycling of Hg is presented. It has been found that deposition of Hg from AMDEs occurs at marine coasts and not far inland and that a fraction of the deposited Hg does not remain in the same form in the snow. Kinetic studies undertaken have demonstrated that bromine is the major oxidant depleting Hg in the atmosphere. Modeling results demonstrate that there is a significant deposition of Hg to Polar Regions as a result of AMDEs. Models have also shown that Hg is readily transported to the Arctic from source regions, at times during springtime when this environment is actively transforming Hg from the atmosphere to the snow and ice surfaces. The presence of significant amounts of methyl Hg in snow in the Arctic surrounding AMDEs is important because this species is the link between the environment and impacts to wildlife and humans. Further, much work on methylation and demethylation processes has occurred but these processes are not yet fully understood. Recent changes in the climate and sea ice cover in Polar Regions are likely to have strong effects on the cycling of Hg in this environment; however more research is needed to understand Hg processes in order to formulate meaningful predictions of these changes. It was discovered in 1995 that, during the spring time, unexpectedly low concentrations of gaseous elemental mercury (GEM) occurred in the Arctic air. This was surprising for a pollutant known to have a long residence time in the atmosphere; however conditions appeared to exist in the Arctic that promoted this depletion of mercury (Hg). This phenomenon is termed atmospheric mercury depletion events (AMDEs) and its discovery has revolutionized our understanding of the cycling of Hg in Polar Regions while stimulating a significant amount of research to understand its impact to this fragile ecosystem. Shortly after the discovery was made in Canada, AMDEs were confirmed to occur throughout the Arctic, sub-Artic and Antarctic coasts. It is now known that, through a series of photochemically initiated reactions involving halogens, GEM is converted to a more reactive species and is subsequently associated to particles in the air and/or deposited to the polar environment. AMDEs are a means by which Hg is transferred from the atmosphere to the environment that was previously unknown. In this article we review Hg research taken place in Polar Regions pertaining to AMDEs, the methods used to collect Hg in different environmental media, research results of the current understanding of AMDEs from field, laboratory and modeling work, how Hg cycles around the environment after AMDEs, gaps in our current knowledge and the future impacts that AMDEs may have on polar environments. The research presented has shown that while considerable improvements in methodology to measure Hg have been made but the main limitation remains knowing the speciation of Hg in the various media. The processes that drive AMDEs and how they occur are discussed. As well, the role that the snow pack and the sea ice play in the cycling of Hg is presented. It has been found that deposition of Hg from AMDEs occurs at marine coasts and not far inland and that a fraction of the deposited Hg does not remain in the same form in the snow. Kinetic studies undertaken have demonstrated that bromine is the major oxidant depleting Hg in the atmosphere. Modeling results demonstrate that there is a significant deposition of Hg to Polar Regions as a result of AMDEs. Models have also shown that Hg is readily transported to the Arctic from source regions, at times during springtime when this environment is actively transforming Hg from the atmosphere to the snow and ice surfaces. The presence of significant amounts of methyl Hg in snow in the Arctic surrounding AMDEs is important because this species is the link between the environment and impacts to wildlife and humans. Further, much work on methylation and demethylation processes has occurred but these processes are not yet fully understood. Recent changes in the climate and sea ice cover in Polar Regions are likely to have strong effects on the cycling of Hg in this environment; however more research is needed to understand Hg processes in order to formulate meaningful predictions of these changes.

Five months of gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and particle bound mercury ( Hg p ) concentrations as well as fluxes of GEM were measured at Alert, Nunavut, Canada above the Arctic snow pack. The study spanned February to June of 2005 to capture the effects of polar night, the transition period between night and day as well as polar day on the behaviour of mercury in the near surface atmosphere. A micrometeorological approach was used to infer the flux of GEM using a continuous two-level sampling system to measure the GEM concentration gradient. The required turbulent transfer coefficients were derived from meteorological parameters measured on site. The flux of GEM was approximately zero during atmospheric mercury depletion events (AMDEs) demonstrating that mercury is not being deposited as GEM to the snow pack. Following AMDEs, there was no evidence of a net emission of GEM. The highest depositional fluxes of GEM occurred during polar night and the largest emission occurred when the tundra was first visible, followed by significant emission and deposition fluxes during the snow melt. Fluxes continued until the snow had completely melted ( ∼ JD 170) before returning to near zero. Average concentrations of RGM ( 44.4 ± 49.8 pg m - 3 ) , Hg p ( 102.6 ± 124.9 pg m - 3 ) and GEM ( 1.0 ± 0.4 ng m - 3 ) were variable throughout the study due to the dynamic nature of atmospheric mercury during AMDEs. Increases in Hg p preceded elevated levels of RGM during AMDEs by 60 days, yielding peak levels at 694 and 344 pg m - 3 , respectively. Elevated concentrations of Hg p typically occurred when the specific humidity dropped below 0.75 g kg - 1 , winds were light ( 3 m s - 1 ) and the air temperature dropped below - 20 ∘ C . Increased levels of RGM were also noted when the winds were light ( 3 m s - 1 ) but when the temperature increased above - 10 ∘ C and the specific humidity was in the range of 1 and 3 g kg - 1 . As different environmental conditions were observed for the elevated concentrations of Hg p versus RGM at Alert, it suggests that the formation mechanisms for each species may be different but tied to the atmospheric temperature and water content. Total mercury (TM) levels in fresh snow measured approximately 5– 10 ng l - 1 during AMDEs and reached nearly 80 ng l - 1 outside of depletion events, suggesting that wet deposition may not be a significant removal mechanism of GEM during depletion events. An unusually high concentration of TM was measured during a non-depletion event which coincided with the transitional period where atmospheric loading of RGM exceeded levels of Hg p .

Long-term monitoring data of total gaseous mercury (TGM) concentrations from the Canadian Atmospheric Mercury Measurement Network (CAMNet) were analysed for temporal trends, seasonality and comparability within the network and compared to other network and model results. Data collected from 11 Canadian measurement sites between 1995 and 2005 were analysed. Sites within CAMNet were characterized by principle component analysis (PCA) into four main categories. For the first time since automated TGM measurements have been made within CAMNet, this paper reveals statistically significant decreasing TGM concentrations from rural locations in Canada during this time period. The largest declines were observed close to the urban areas of Toronto and Montreal, where levels fell by 17% at Point Petre, and 13% at St. Anicet, respectively. Many of the TGM changes are comparable with the overall trends observed in total mercury concentrations in precipitation, for similar time periods, at co-located or nearby National Atmospheric Deposition programme's Mercury Deposition Network (NADP-MDN) sites. The results show that these changes are mostly driven by local or regional changes in mercury emissions. Other sites within CAMNet reflect reported changes in hemispherical global background concentrations of airborne mercury, where slight decreases or no statistically significant trend in TGM concentrations exist over the same time period.

International audience; An international campaign involving six teams was organized in Ny-Ålesund, Svalbard, in order to understand better the origin of atmospheric mercury depletion events (AMDEs). Special emphasis was given to determining the source region of the observed events and the physical and chemical processes leading to AMDEs. Five AMDEs were recorded during a one-month field experiment (10 April-10 May, 2003). The different events presented various characteristics, especially in terms of mercury species formation, atmospheric particle variations and meteorological conditions. After careful examination of each event, we postulate that two were probably due to advection of already depleted air masses and three were a product of local or regional chemistry. The roles of different surfaces (frost flowers, snow, ice aerosol in clouds) involved in heterogeneous reactions leading to AMDEs are also discussed. We speculate that ice clouds may explain the particle variations observed during the three more local events.

International audience; Six groups participated in an international study of springtime atmospheric mercury depletion events (AMDEs) at Ny-Ålesund in the Norwegian Arctic during April and May 2003 with the aim to compare analytical methods for measurements of atmospheric mercury species and study the physical and chemical processes leading to AMDEs. Five groups participated in the method comparison that was conducted at three different locations within Ny-Ålesund. Various automated and manual instrumentation were used to sample, measure and compare gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and mercury associated with particles (Hg-P). The concentration of GEM was reproducible during background conditions. For the first time using ambient air, the statistics associated with round robin test procedures were applied. This was found to be an appropriate tool to investigate the reproducibility of GEM measurements in ambient air. The precision for each group measuring GEM concentrations was found to be consistently good (within 5%). Five AMDEs were recorded during the study. Using four different methods, including single and replicate samples, all groups recorded higher values of RGM and Hg-P during AMDEs. The results show that measuring comparable atmospheric mercury species at both the same and different locations (within the Ny-Ålesund area) is difficult. Not only do site location and site characteristics create challenges when trying to intercompare results but there are difficulties, as well, in obtaining comparable results with similar sampling and analysis methods. Nevertheless, with our current procedures for atmospheric mercury identification we can differentiate with certainty between “high” and “low” concentration values of RGM and Hg-P.

In an effort to investigate both large-scale (spatial) and short/long-term (temporal) distribution characteristics of atmospheric mercury, we have combined and analyzed the Hg concentration data sets collected continuously by four different scientific groups for the areas and periods covering (1) America (three sites near the Canadian Great Lakes (CGL): 1997–2000), (2) Asia (Seoul, Korea (SEL): 1997–2002), (3) Arctic (Alert, Canada (ALT): 1995–2001), and (4) Europe (Mace Head, Ireland (MH): 1996–2002). The mean concentrations of Hg data from those widely dispersed monitoring stations were computed to be (1) 1.58 ± 0.23, 1.69 ± 0.32, and 1.93 ± 0.44 (three sites in CGL), (2) 5.06 ± 2.46 ng m−3 (SEL), (3) 1.55 ± 0.41 (ALT), and (4) 1.76 ± 0.31 (MH). Intersite relationships were investigated among all different stations using the data groups divided into different temporal intervals. The analysis of diurnal variation patterns of Hg indicated differences in regional source/sink characteristics, with increasing amplitudes of variability toward areas under the strong influence of anthropogenic sources. When the analysis was made over different seasons, the patterns contrasted greatly between the Arctic and the other areas. It was found that the relative enhancement of Hg concentrations was dominant during winter/spring in most areas due to direct or indirect influences of anthropogenic emissions. However, the pattern for the Arctic area was distinguished pronouncedly from others with the spring minimum and summer maximum both of which reflect the potent effects of mercury depletion phenomenon (MDP). By contrast, no long-term trend, either being an increase or decrease, was evident from any of the stations during each respective study period. Although our initial attempts to examine the distribution characteristics of Hg analyzed by different scientific groups were successful, we feel that these efforts should be continued further to extend the compatibility of the global database of Hg.

Accentuated by a new record low in 2012, the springtime extent of Arctic perennial sea ice continues its precipitous decline. Consequently, the Arctic sea ice cover is increasingly dominated by seasonal sea ice, consisting of thinner and saltier ice with more leads (fractures), polynyas (areas of open water), nilas (sea ice crust less than about 10 centimeters thick), frost flowers (clusters of salty ice crystals on sea ice surface), and saline snow. The increase in the salinity of the sea ice cover is potentially conducive to ice-mediated photochemical and meteorological processes leading to ozone (O3) and gaseous elemental mercury depletion from the atmosphere.

The role of formaldehyde in the atmospheric chemistry of the Arctic marine boundary layer has been studied during both polar day and night at Alert, Nunavut, Canada. Formaldehyde concentrations were determined during two separate field campaigns (PSE 1998 and ALERT2000) from polar night to the light period. The large differences in the predominant chemistry and transport issues in the dark and light periods are examined here. Formaldehyde concentrations during the dark period were found to be dependent on the transport of air masses to the Alert site. Three regimes were identified during the dark period, including background (free-tropospheric) air, transported polluted air from Eurasia, and halogen-processed air transported across the dark Arctic Ocean. In the light period, background formaldehyde levels were compared to a calculation of the steady-state formaldehyde concentrations under background and low-ozone conditions. We found that, for sunlit conditions, the ambient formaldehyde concentrations cannot be reproduced by known gas-phase chemistry. We suggest that snowpack photochemistry contributes to production and emission of formaldehyde in the light period, which could account for the high concentrations observed at Alert.

Gaseous elemental mercury (GEM) concentration measurements were made during the Alert 2000 campaign in Alert, Nunavut, Canada, between February and May 2000. GEM exhibits dramatic mercury depletion events (MDE) concurrently with ozone in the troposphere during the Arctic springtime. Using a cold regions pyrolysis unit, it was confirmed that GEM is converted to more reactive mercury species during the MDEs. It was determined that on average 48% of this converted GEM was recovered through pyrolysis suggesting that the remaining converted GEM is deposited on the snow surfaces. Samples collected during this campaign showed an approximate 20 fold increase in mercury concentrations in the snow from the dark to light periods. Vertical gradient air profiling experiments were conducted. In the non-depletion periods GEM was found to be invariant in the air column between surface and 1–2 m heights. During a depletion period, GEM was found to be invariant in the air column except at the surface where a noticeable increase in the GEM concentration was observed. Concurrent ozone concentration profiles showed a small gradient in the air column but a sharp decrease in ozone concentration at the surface. Other profile studies showed a 41% average GEM concentration difference between the interstitial air in the snow pack and ∼2 m above the surface suggesting that GEM is emitted from the snow pack. Further profile studies showed that during MDEs surface level GEM exhibits spikes of mercury concentrations that were over double the ambient GEM concentrations. It is thought that the solar radiation may reduce reactive mercury that is deposited on the snow surface during a MDE back to its elemental form which is then increasingly released from the snow pack as the temperature increases during the day. This is observed when wind speeds are very low.

Atmospheric mercury (Hg) measurements from across Canada were compiled and analysed as part of a national Hg science assessment. Here we update long-term trends of Hg in air and precipitation, and present more extensive measurements on patterns and trends in speciated Hg species (gaseous elemental mercury—GEM, reactive gaseous mercury—RGM, and total particulate mercury on particles

A review of mercury in the Canadian Arctic with a focus on field measurements is presented in part I (see Steffen et al., this issue). Here we provide insights into the dynamics of mercury in the Canadian Arctic from new and published mercury modeling studies using Environment Canada's mercury model. The model simulations presented in this study use global anthropogenic emissions of mercury for the period 1995–2005. The most recent modeling estimate of the net gain of mercury from the atmosphere to the Arctic Ocean is 75 Mg year− 1 and the net gain to the terrestrial ecosystems north of 66.5° is 42 Mg year− 1. Model based annual export of riverine mercury from North American, Russian and all Arctic watersheds to the Arctic Ocean are in the range of 2.8–5.6, 12.7–25.4 and 15.5–31.0 Mg year− 1, respectively. Analysis of long-range transport events of Hg at Alert and Little Fox Lake monitoring sites indicates that Asia contributes the most ambient Hg to the Canadian Arctic followed by contributions from North America, Russia, and Europe. The largest anthropogenic Hg deposition to the Canadian Arctic is from East Asia followed by Europe (and Russia), North America, and South Asia. An examination of temporal trends of Hg using the model suggests that changes in meteorology and changes in anthropogenic emissions equally contribute to the decrease in surface air elemental mercury concentrations in the Canadian Arctic with an overall decline of ~ 12% from 1990 to 2005. A slow increase in net deposition of Hg is found in the Canadian Arctic in response to changes in meteorology. Changes in snowpack and sea-ice characteristics and increase in precipitation in the Arctic related with climate change are found to be primary causes for the meteorology-related changes in air concentrations and deposition of Hg in the region. The model estimates that under the emissions reduction scenario of worldwide implementation of the best emission control technologies by 2020, mercury deposition could potentially be reduced by 18–20% in the Canadian Arctic.

Mercury—in the chemical/physical forms present in the biosphere—is a persistent, toxic, bioaccumulative pollutant that is dispersed throughout the environment on a global scale, mainly via the atmosphere. It is among the “heavy metals” for which the natural biogeochemical cycle has been perturbed by a wide range of human activities, including fossil-fuel combustion and waste incineration. Results of our recent measurements of gaseous elemental mercury (GEM), as well as total particulate-phase mercury (TPM) concentrations in Arctic air, ‘total Hg’ concentrations in Arctic snow, and tropospheric BrO concentrations from an earth-orbiting-satellite platform are presented and discussed. Findings of our research, and the conclusions derived therefrom, are important for environmental protection as well as the health and well-being of aboriginal people in Arctic circumpolar nations.

Ten years of atmospheric mercury speciation data and 14 yr of mercury in snow data from Alert, Nunavut, Canada are examined. The speciation data, collected from 2002 to 2011, includes gaseous elemental mercury (GEM), particulate mercury (PHg) and reactive gaseous mercury (RGM). During the winter-spring period of atmospheric mercury depletion events (AMDEs), when GEM is close to being completely depleted from the air, the concentrations of PHg and RGM rise significantly. During this period, the median concentrations for PHg is 28.2 pg m-3 and RGM is 23.9 pg m-3 from March to June in comparison to the annual median concentrations of 11.3 and 3.2 -3 for PHg and RGM, respectively. In each of the ten years of sampling, PHg increases steadily from January through March and is higher than RGM. This pattern begins to change in April with very high levels of PHg and increasing RGM. In May, RGM transitions to be significantly higher than PHg and continues into June whereas PHg sharply drops down. The transition is thought to be driven by a combination of air temperature and particle availability. Firstly, the ratio of PHg to RGM is favoured by low temperatures suggesting that oxidized mercury may partition to available particles to form PHg. Prior to the transition, the median air temperature is −24.8 °C and after the transition the median air temperature is −5.8 °C. Secondly, high aerosol levels in the spring are a strong driver for the high PHg concentrations. In February through April, partitioning of oxidized mercury to produce PHg was favoured by increased concentrations of particles that are principally the result of Arctic Haze and some sea salts. In the snow, the concentrations of mercury peak in May for all years. The highest deposition of mercury to the snow in the spring at Alert is during and after the transition of PHg to RGM in the atmosphere.

Measurements of gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and particulate mercury (PHg) were collected on sea ice near open leads in the Beaufort Sea near Barrow, Alaska in March 2009 as part of the Ocean-Atmosphere-Sea Ice-Snowpack (OASIS) International Polar Year Program. These results represent the first atmospheric mercury speciation measurements collected on the sea ice. Concentrations of PHg over the sea ice averaged 393.5 pg m−3 (range 47.1–900.1 pg m−3) during the two week long study. RGM concentrations averaged 30.1 pg m−3 (range 3.5–105.4 pg m−3). The mean GEM concentration of 0.59 ng m−3 during the entire study (range 0.01–1.51 ng m−3) was depleted compared to annual Arctic ambient boundary layer concentrations. It was shown that when ozone (O3) and bromine oxide (BrO) chemistry are active there is a~linear relationship between GEM, PHg and O3 but there was no correlation between RGM and O3. There was a linear relationship between RGM and BrO and our results suggest that the origin and age of air masses play a role in determining this relationship. These results were the first direct measurements of these atmospheric components over the sea ice. For the first time, GEM was measured simultaneously over the tundra and the sea ice. The results show a significant difference in the magnitude of the emission of GEM from the two locations where significantly higher emission occurs over the tundra. Elevated chloride levels in snow over sea ice are believed to be the cause of lower GEM emissions over the sea ice because chloride has been shown to suppress photoreduction processes of Hg(II) to Hg(0) (GEM) in snow. These results are important because while GEM is emitted after depletion events on snow inland, less GEM is emitted over sea ice. Since the snow pack on sea ice retains more mercury than inland snow current models of the Arctic mercury cycle, which are based predominantly on land based measurements, may greatly underestimate atmospheric deposition fluxes. Land based measurements of atmospheric mercury deposition may also underestimate the impacts of sea ice changes on the mercury cycle in the Arctic. The findings reported in this study improve the current understanding of mercury cycling in the changing Arctic. The predicted changes in sea ice conditions and a~more saline snow pack in the Arctic could lead to even greater retention of atmospherically deposited mercury in the future. This could severely impact the amount of mercury entering the Arctic Ocean and coastal ecosystems.

Global emissions of mercury continue to change at the same time as the Arctic is experiencing ongoing climatic changes. Continuous monitoring of atmospheric mercury provides important information about long-term trends in the balance between transport, chemistry, and deposition of this pollutant in the Arctic atmosphere. Ten-year records of total gaseous mercury (TGM) from 2000 to 2009 were analyzed from two high Arctic sites at Alert (Nunavut, Canada) and Zeppelin Station (Svalbard, Norway); one sub-Arctic site at Kuujjuarapik (Nunavik, Québec, Canada); and three temperate Canadian sites at St. Anicet (Québec), Kejimkujik (Nova Scotia) and Egbert (Ontario). Five of the six sites examined showed a decreasing trend over this time period. Overall trend estimates at high latitude sites were: −0.9% yr−1 (95% confidence limits: −1.4, 0) at Alert and no trend (−0.5, +0.7) at Zeppelin Station. Faster decreases were observed at the remainder of the sites: −2.1% yr−1 (−3.1, −1.1) at Kuujjuarapik, −1.9% yr−1 (−2.1, −1.8) at St. Anicet, −1.6% yr−1 (−2.4, −1.0) at Kejimkujik and −2.2% yr−1 (−2.8, −1.7) at Egbert. Trends at the sub-Arctic and mid-latitude sites agree with reported decreases in background TGM concentration since 1996 at Mace Head, Ireland, and Cape Point, South Africa, but conflict with estimates showing an increase in global anthropogenic emissions over a similar period. Trends in TGM at the two high Arctic sites were not only less negative (or neutral) overall but much more variable by season. Possible reasons for differences in seasonal and overall trends at the Arctic sites compared to those at lower latitudes are discussed, as well as implications for the Arctic mercury cycle. The first calculations of multi-year trends in reactive gaseous mercury (RGM) and total particulate mercury (TPM) at Alert were also performed, indicating increases from 2002 to 2009 in both RGM and TPM in the spring when concentrations are highest.

Recent drastic reduction of the older perennial sea ice in the Arctic Ocean has resulted in a vast expansion of younger and saltier seasonal sea ice. This increase in the salinity of the overall ice cover could impact tropospheric chemical processes. Springtime perennial ice extent in 2008 and 2009 broke the half-century record minimum in 2007 by about one million km2. In both years seasonal ice was dominant across the Beaufort Sea extending to the Amundsen Gulf, where significant field and satellite observations of sea ice, temperature, and atmospheric chemicals have been made. Measurements at the site of the Canadian Coast Guard Ship Amundsen ice breaker in the Amundsen Gulf showed events of increased bromine monoxide (BrO), coupled with decreases of ozone (O3) and gaseous elemental mercury (GEM), during cold periods in March 2008. The timing of the main event of BrO, O3, and GEM changes was found to be consistent with BrO observed by satellites over an extensive area around the site. Furthermore, satellite sensors detected a doubling of atmospheric BrO in a vortex associated with a spiral rising air pattern. In spring 2009, excessive and widespread bromine explosions occurred in the same region while the regional air temperature was low and the extent of perennial ice was significantly reduced compared to the case in 2008. Using satellite observations together with a Rising-Air-Parcel model, we discover a topographic control on BrO distribution such that the Alaskan North Slope and the Canadian Shield region were exposed to elevated BrO, whereas the surrounding mountains isolated the Alaskan interior from bromine intrusion.

[1] Mercury is a toxic environmental contaminant originating from both natural and anthropogenic sources. Gaseous elemental mercury (GEM) is relatively long lived in the midlatitudes and can be transported long distances in the atmosphere. In the Polar Regions, mercury can have a much shorter lifetime and is known to experience episodic depletions following polar sunrise in concert with ozone depletion events. A series of photochemically initiated reactions involving halogen radicals is believed to be the primary pathway responsible for converting elemental mercury to oxidized forms of reactive gaseous mercury (RGM) that are subsequently deposited to snow and ice surfaces. Using field measurements from the Ocean-Atmosphere-Sea Ice-Snowpack (OASIS) 2009 field campaign of GEM, RGM, ozone, and a large suite of both inorganic halogen and volatile organic compounds, we calculated steady state Br and Cl atom concentrations and investigated the contribution of Br, BrO, Cl, ClO, O3, and OH to the observed decay of GEM for five cases of apparent first-order decay. The results of this study indicate that Br and BrO are the dominant oxidizers for Arctic mercury depletion events, with Br having the greatest overall contribution to GEM decay. Ozone is likely the primary factor controlling the relative contribution of Br and BrO, as BrO is a product of the reaction of Br with ozone, and reaction with O3 can be the largest Br atom sink. Cl was not found to be significant in any of the studied events; however, this result is highly dependent on the rate constant, for which there is a large range in the literature. Modeled 48 h back trajectories of the mercury depletion events studied here indicate significant time spent over sea ice–covered regions, where the concentration of halogen radicals is likely higher than those estimated using local-scale chemical mole fractions.

[1] Frost flowers are ice crystals that grow on refreezing sea ice leads in Polar Regions by wicking brine from the sea ice surface and accumulating vapor phase condensate. These crystals contain high concentrations of mercury (Hg) and are believed to be a source of reactive halogens, but their role in Hg cycling and impact on the fate of Hg deposited during atmospheric mercury depletion events (AMDEs) are not well understood. We collected frost flowers growing on refreezing sea ice near Barrow, Alaska (U.S.A.) during an AMDE in March 2009 and measured Hg concentrations and Hg stable isotope ratios in these samples to determine the origin of Hg associated with the crystals. We observed decreasing Δ199Hg values in the crystals as they grew from new wet frost flowers (mean Δ199Hg = 0.77 ± 0.13‰, 1 s.d.) to older dry frost flowers (mean Δ199Hg = 0.10 ± 0.05‰, 1 s.d.). Over the same time period, mean Hg concentrations in these samples increased from 131 ± 6 ng/L (1 s.d.) to 180 ± 28 ng/L (1 s.d.). Coupled with a previous study of Hg isotopic fractionation during AMDEs, these results suggest that Hg initially deposited to the local snowpack was subsequently reemitted during photochemical reduction reactions and ultimately accumulated on the frost flowers. As a result of this process, frost flowers may lead to enhanced local retention of Hg deposited during AMDEs and may increase Hg loading to the Arctic Ocean.

We have developed a new nested-grid mercury (Hg) simulation over North America with a 1/2° latitude by 2/3° longitude horizontal resolution employing the GEOS-Chem global chemical transport model. Emissions, chemistry, deposition, and meteorology are self-consistent between the global and nested domains. Compared to the global model (4° latitude by 5° longitude), the nested model shows improved skill at capturing the high spatial and temporal variability of Hg wet deposition over North America observed by the Mercury Deposition Network (MDN) in 2008–2009. The nested simulation resolves features such as higher deposition due to orographic precipitation, land/ocean contrast and and predicts more efficient convective rain scavenging of Hg over the southeast United States. However, the nested model overestimates Hg wet deposition over the Ohio River Valley region (ORV) by 27%. We modify anthropogenic emission speciation profiles in the US EPA National Emission Inventory (NEI) to account for the rapid in-plume reduction of reactive to elemental Hg (IPR simulation). This leads to a decrease in the model bias to −2.3% over the ORV region. Over the contiguous US, the correlation coefficient (r) between MDN observations and our IPR simulation increases from 0.60 to 0.78. The IPR nested simulation generally reproduces the seasonal cycle in surface concentrations of speciated Hg from the Atmospheric Mercury Network (AMNet) and Canadian Atmospheric Mercury Network (CAMNet). In the IPR simulation, annual mean gaseous and particulate-bound Hg(II) are within 140% and 11% of observations, respectively. In contrast, the simulation with unmodified anthropogenic Hg speciation profiles overestimates these observations by factors of 4 and 2 for gaseous and particulate-bound Hg(II), respectively. The nested model shows improved skill at capturing the horizontal variability of Hg observed over California during the ARCTAS aircraft campaign. The nested model suggests that North American anthropogenic emissions account for 10–22% of Hg wet deposition flux over the US, depending on the anthropogenic emissions speciation profile assumed. The modeled percent contribution can be as high as 60% near large point sources in ORV. Our results indicate that the North American anthropogenic contribution to dry deposition is 13–20%.

At polar sunrise, gaseous elemental mercury (GEM) undergoes an exceptional dynamic exchange in the air and at the snow surface during which GEM can be rapidly removed from the atmosphere (the so-called atmospheric mercury depletion events (AMDEs)) as well as re-emitted from the snow within a few hours to days in the Polar Regions. Although high concentrations of total mercury in snow following AMDEs is well documented, there is very little data available on the redox transformation processes of mercury in the snow and the fluxes of mercury at the air/snow interface. Therefore, the net gain of mercury in the Polar Regions as a result of AMDEs is still an open question. We developed a new version of the global mercury model, GRAHM, which includes for the first time bidirectional surface exchange of GEM in Polar Regions in spring and summer by developing schemes for mercury halogen oxidation, deposition, and re-emission. Also for the first time, GOME satellite data-derived boundary layer concentrations of BrO have been used in a global mercury model for representation of halogen mercury chemistry. Comparison of model simulated and measured atmospheric concentrations of GEM at Alert, Canada, for 3 years (2002-2004) shows the model's capability in simulating the rapid cycling of mercury during and after AMDEs. Brooks et al. (1) measured mercury deposition, reemission, and net surface gain fluxes of mercury at Barrow, AK, during an intensive measurement campaign for a 2 week period in spring (March 25 to April 7, 2003). They reported 1.7, 1.0 +/- 0.2, and 0.7 +/- 0.2 microg m(-2) deposition, re-emission, and net surface gain, respectively. Using the optimal configuration of the model, we estimated 1.8 microg m(-2) deposition, 1.0 microg m(-2) re-emission, and 0.8 microg m(-2) net surface gain of mercury for the same time period at Barrow. The estimated net annual accumulation of mercury within the Arctic Circle north of 66.5 degrees is approximately 174 t with +/-7 t of interannual variability for 2002-2004 using the optimal configuration. We estimated the uncertainty of the model results to the Hg/Br reaction rate coefficient to be approximately 6%. Springtime is clearly demonstrated as the most active period of mercury exchanges and net surface gain (approximately 46% of annual accumulation) in the Arctic.