Reproducing polar springtime bromine explosion events, ozone depletion events and atmospheric mercury depletion events in an outdoor mesocosm sea-ice facility

Air Temperatures

Every year during polar sunrise, a series of photochemical events are observed episodically in the troposphere over the Arctic and Antarctic, including bromine explosion events (BEEs), ozone depletion events (ODEs), and mercury depletion events (MDEs). Extensive studies show that all these events are triggered by gas-phase reactive bromine species that are photochemically activated from sea-salt bromide via multi-phase reactions under freezing air temperatures. However, major knowledge gaps exist in both fundamental cryo-photochemical processes and local meteorological conditions that may affect the timing and magnitude of those events. Here, we present an outdoor mesocosm-scale experiment in which we studied the depletion of surface ozone and gaseous elemental mercury at the Sea-ice Environmental Research Facility (SERF) in Winnipeg, Canada, in an urban and non-polar region. Temporal changes in ozone and gaseous elemental mercury concentrations inside acrylic tubes were monitored over bromide-enriched artificial seawater during entire sea ice freeze-and-melt cycles and open water periods. Mid-day photochemical loss of both gas species was observed in the boundary layer air immediately above the sea ice surface, in a pattern that is characteristic of BEE-induced ODEs and MDEs in the Arctic. The importance of UV radiation and sea ice presence in causing such observations was demonstrated by sampling from UV-transmitting and UV-blocking acrylic tubes under different air temperatures. The ability of reproducing mesocosm-scale BEE-induced ODEs and MDEs in a non-polar region provides a new platform with opportunities to systematically study the cryo-photochemical mechanisms leading to BEEs, ODEs, and MDEs in the Arctic, their role in biogeochemical cycles across the ocean-sea ice-atmosphere interfaces, and their sensitivities to a changing climate.&#160;

Reproducing springtime Arctic tropospheric ozone depletion events in an outdoor mesocosm sea-ice facility

10.5194/acp-2021-157 ◽

2021 ◽

Author(s):

Zhiyuan Gao ◽

Nicolas-Xavier Geilfus ◽

Alfonso Saiz-Lopez ◽

Feiyue Wang

Keyword(s):

Boundary Layer ◽

Sea Ice ◽

Gas Phase ◽

Ozone Depletion ◽

Surface Ozone ◽

Environmental Research ◽

The Arctic ◽

Ozone Loss ◽

Ozone Concentrations ◽

Air Temperatures

Abstract. The episodic build-up of gas-phase reactive bromine species over sea ice and snowpack in the springtime Arctic plays an important role in the boundary layer, causing annual concurrent depletion of ozone and gaseous elemental mercury during polar sunrise. Extensive studies have shown that these phenomena, known as bromine explosion events (BEEs), ozone depletion events (ODEs) and mercury depletion events (MDEs), respectively, are all triggered by gas-phase reactive bromine species that are photochemically activated from bromide via multi-phase reactions under freezing air temperatures. However, major knowledge gaps exist in both fundamental cryo-photochemical processes causing these events and meteorological conditions that may affect their timing and magnitude. Here, we report an outdoor mesocosm-scale study in which we successfully reproduced ODEs at the Sea-ice Environmental Research Facility (SERF) in Winnipeg, Canada. By monitoring ozone concentrations inside large, acrylic tubes over bromide-enriched artificial seawater during entire sea ice freeze-and-melt cycles, we observed mid-day photochemical ozone loss in winter in the boundary layer air immediately above the sea ice surface in a pattern that is characteristic of BEE-induced ODEs in the Arctic. The importance of UV radiation and the presence of a condensed phase (experimental sea ice or snow) in causing such surface ozone loss was demonstrated by comparing ozone concentrations between UV-transmitting and UV-blocking acrylic tubes under different air temperatures. The ability of reproducing BEE-induced ODEs at a mesocosm scale in a non-polar region provides a new approach to systematically studying the cryo-photochemical and meteorological processes leading to BEEs, ODEs, and MDEs in the Arctic, their role in biogeochemical cycles across the ocean-sea ice-atmosphere interfaces, and their sensitivities to climate change.

A synthesis of atmospheric mercury depletion event chemistry linking atmosphere, snow and water

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-7-10837-2007 ◽

2007 ◽

Vol 7 (4) ◽

pp. 10837-10931 ◽

Cited By ~ 19

Author(s):

A. Steffen ◽

T. Douglas ◽

M. Amyot ◽

P. Ariya ◽

K. Aspmo ◽

...

Keyword(s):

Sea Ice ◽

Current Knowledge ◽

Kinetic Studies ◽

Elemental Mercury ◽

Atmospheric Mercury ◽

The Arctic ◽

Polar Regions ◽

Environmental Media ◽

History Of

Abstract. 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 the history of Hg in Polar Regions, 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 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 roles that the snow pack, oceans, fresh water and the sea ice play in the cycling of Hg are 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 have occurred but 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. Mercury, Atmospheric mercury depletion events (AMDE), Polar, Arctic, Antarctic, Ice

A synthesis of atmospheric mercury depletion event chemistry in the atmosphere and snow

10.5194/acp-8-1445-2008 ◽

2008 ◽

Vol 8 (6) ◽

pp. 1445-1482 ◽

Cited By ~ 314

Author(s):

A. Steffen ◽

T. Douglas ◽

M. Amyot ◽

P. Ariya ◽

K. Aspmo ◽

...

Keyword(s):

Sea Ice ◽

Current Knowledge ◽

Kinetic Studies ◽

Elemental Mercury ◽

Atmospheric Mercury ◽

The Arctic ◽

Polar Regions ◽

Environmental Media ◽

Low Concentrations

Abstract. 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.

Atmospheric mercury over sea ice during the OASIS-2009 campaign

10.5194/acp-13-7007-2013 ◽

2013 ◽

Vol 13 (14) ◽

pp. 7007-7021 ◽

Cited By ~ 27

Author(s):

A. Steffen ◽

J. Bottenheim ◽

A. Cole ◽

T. A. Douglas ◽

R. Ebinghaus ◽

...

Keyword(s):

Sea Ice ◽

Elemental Mercury ◽

Atmospheric Mercury ◽

The Arctic ◽

Mercury Deposition ◽

International Polar Year ◽

Bromine Oxide ◽

Significant Difference ◽

Mercury Cycle

Abstract. Measurements of gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and particulate mercury (PHg) were collected on the Beaufort Sea ice near Barrow, Alaska, in March 2009 as part of the Ocean-Atmosphere-Sea Ice-Snowpack (OASIS) and OASIS-Canada International Polar Year programmes. These results represent the first atmospheric mercury speciation measurements collected on the sea ice. Concentrations of PHg averaged 393.5 pg m−3 (range 47.1–900.1 pg m−3) and RGM concentrations averaged 30.1 pg m−3 (range 3.5–105.4 pg m−3) during the two-week-long study. The mean concentration of GEM during the study was 0.59 ng m−3 (range 0.01–1.51 ng m−3) and was depleted compared to annual Arctic ambient boundary layer concentrations. It is shown that when ozone (O3) and bromine oxide (BrO) chemistry were active there is a positive linear relationship between GEM and O3, a negative one between PHg and O3, a positive correlation between RGM and BrO, and none between RGM and O3. 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, with significantly higher emission over the tundra. Elevated chloride levels in snow over sea ice are proposed to be the cause of lower GEM emissions over the sea ice because chloride has been shown to suppress photoreduction processes of RGM to GEM in snow. Since the snowpack on sea ice retains more mercury than inland snow, current models of the Arctic mercury cycle may greatly underestimate atmospheric deposition fluxes because they are based predominantly on land-based measurements. Land-based measurements of atmospheric mercury deposition may also underestimate the impacts of sea ice changes on the mercury cycle in the Arctic. The predicted changes in sea ice conditions and a more saline future snowpack in the Arctic could enhance retention of atmospherically deposited mercury and increase the amount of mercury entering the Arctic Ocean and coastal ecosystems.

Simulation of atmospheric mercury depletion events (AMDEs) during polar springtime using the MECCA box model

10.5194/acp-8-7165-2008 ◽

2008 ◽

Vol 8 (23) ◽

pp. 7165-7180 ◽

Cited By ~ 35

Author(s):

Z.-Q. Xie ◽

R. Sander ◽

U. Pöschl ◽

F. Slemr

Keyword(s):

Aqueous Phase ◽

Ozone Depletion ◽

Elemental Mercury ◽

Atmospheric Mercury ◽

Box Model ◽

Rate Coefficients ◽

Mercury Species ◽

Phase Reaction ◽

Sea Salt Aerosol

Abstract. Atmospheric mercury depletion events (AMDEs) during polar springtime are closely correlated with bromine-catalyzed tropospheric ozone depletion events (ODEs). To study gas- and aqueous-phase reaction kinetics and speciation of mercury during AMDEs, we have included mercury chemistry into the box model MECCA (Module Efficiently Calculating the Chemistry of the Atmosphere), which enables dynamic simulation of bromine activation and ODEs. We found that the reaction of Hg with Br atoms dominates the loss of gaseous elemental mercury (GEM). To explain the experimentally observed synchronous depletion of GEM and O3, the reaction rate of Hg+BrO has to be much lower than that of Hg+Br. The synchronicity is best reproduced with rate coefficients at the lower limit of the literature values for both reactions, i.e. kHg+Br≈3×10−13 and kHg+BrO≤1×10−15 cm3 molecule−1 s−1, respectively. Throughout the simulated AMDEs, BrHgOBr was the most abundant reactive mercury species, both in the gas phase and in the aqueous phase. The aqueous-phase concentrations of BrHgOBr, HgBr2, and HgCl2 were several orders of magnitude larger than that of Hg(SO3)22−. Considering chlorine chemistry outside depletion events (i.e. without bromine activation), the concentration of total divalent mercury in sea-salt aerosol particles (mostly HgCl42−) was much higher than in dilute aqueous droplets (mostly Hg(SO3)22−), and did not exhibit a diurnal cycle (no correlation with HO2 radicals).

Active molecular iodine photochemistry in the Arctic

Proceedings of the National Academy of Sciences ◽

10.1073/pnas.1702803114 ◽

2017 ◽

Vol 114 (38) ◽

pp. 10053-10058 ◽

Cited By ~ 28

Author(s):

Angela R. W. Raso ◽

Kyle D. Custard ◽

Nathaniel W. May ◽

David Tanner ◽

Matt K. Newburn ◽

...

Keyword(s):

Ozone Depletion ◽

Radiative Forcing ◽

Elemental Mercury ◽

Molecular Iodine ◽

Atmospheric Composition ◽

The Arctic ◽

Ionization Mass ◽

Cloud Properties ◽

Iodine Chemistry

During springtime, the Arctic atmospheric boundary layer undergoes frequent rapid depletions in ozone and gaseous elemental mercury due to reactions with halogen atoms, influencing atmospheric composition and pollutant fate. Although bromine chemistry has been shown to initiate ozone depletion events, and it has long been hypothesized that iodine chemistry may contribute, no previous measurements of molecular iodine (I2) have been reported in the Arctic. Iodine chemistry also contributes to atmospheric new particle formation and therefore cloud properties and radiative forcing. Here we present Arctic atmospheric I2and snowpack iodide (I−) measurements, which were conducted near Utqiaġvik, AK, in February 2014. Using chemical ionization mass spectrometry, I2was observed in the atmosphere at mole ratios of 0.3–1.0 ppt, and in the snowpack interstitial air at mole ratios up to 22 ppt under natural sunlit conditions and up to 35 ppt when the snowpack surface was artificially irradiated, suggesting a photochemical production mechanism. Further, snow meltwater I−measurements showed enrichments of up to ∼1,900 times above the seawater ratio of I−/Na+, consistent with iodine activation and recycling. Modeling shows that observed I2levels are able to significantly increase ozone depletion rates, while also producing iodine monoxide (IO) at levels recently observed in the Arctic. These results emphasize the significance of iodine chemistry and the role of snowpack photochemistry in Arctic atmospheric composition, and imply that I2is likely a dominant source of iodine atoms in the Arctic.

Direct Detection of Atmospheric Atomic Bromine Leading to Mercury and Ozone Depletion

10.5194/egusphere-egu2020-9439 ◽

2020 ◽

Author(s):

Kerri Pratt ◽

Siyuan Wang ◽

Stephen McNamara ◽

Christopher Moore ◽

Daniel Obrist ◽

...

Keyword(s):

Ozone Depletion ◽

Direct Detection ◽

Bromine Atom ◽

Critical Role ◽

Elemental Mercury ◽

Atmospheric Mercury ◽

The Arctic ◽

Molecular Bromine ◽

Near Surface ◽

Halogen Chemistry

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. Yet, 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 near Utqiagvik, Alaska in March 2012. Measured bromine atom levels reached up to 14 ppt (4.2&#215;108 atoms cm-3) and were up to 3-10 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 shows that measured bromine atoms, resulting from photochemical snowpack production of molecular bromine, can quantitatively explain ozone and mercury loss in the near-surface polar atmosphere.

Analysis of reactive bromine production and ozone depletion in the Arctic boundary layer using 3-D simulations with GEM-AQ: inference from synoptic-scale patterns

10.5194/acp-11-3949-2011 ◽

2011 ◽

Vol 11 (8) ◽

pp. 3949-3979 ◽

Cited By ~ 53

Author(s):

K. Toyota ◽

J. C. McConnell ◽

A. Lupu ◽

L. Neary ◽

C. A. McLinden ◽

...

Keyword(s):

Boundary Layer ◽

Sea Ice ◽

Ozone Depletion ◽

Surface Ozone ◽

High Arctic ◽

Heterogeneous Reactions ◽

The Arctic ◽

Synoptic Scale ◽

Arctic Boundary Layer ◽

Surface Snow

Abstract. Episodes of high bromine levels and surface ozone depletion in the springtime Arctic are simulated by an online air-quality model, GEM-AQ, with gas-phase and heterogeneous reactions of inorganic bromine species and a simple scheme of air-snowpack chemical interactions implemented for this study. Snowpack on sea ice is assumed to be the only source of bromine to the atmosphere and to be capable of converting relatively stable bromine species to photolabile Br2 via air-snowpack interactions. A set of sensitivity model runs are performed for April 2001 at a horizontal resolution of approximately 100 km×100 km in the Arctic, to provide insights into the effects of temperature and the age (first-year, FY, versus multi-year, MY) of sea ice on the release of reactive bromine to the atmosphere. The model simulations capture much of the temporal variations in surface ozone mixing ratios as observed at stations in the high Arctic and the synoptic-scale evolution of areas with enhanced BrO column amount ("BrO clouds") as estimated from satellite observations. The simulated "BrO clouds" are in modestly better agreement with the satellite measurements when the FY sea ice is assumed to be more efficient at releasing reactive bromine to the atmosphere than on the MY sea ice. Surface ozone data from coastal stations used in this study are not sufficient to evaluate unambiguously the difference between the FY sea ice and the MY sea ice as a source of bromine. The results strongly suggest that reactive bromine is released ubiquitously from the snow on the sea ice during the Arctic spring while the timing and location of the bromine release are largely controlled by meteorological factors. It appears that a rapid advection and an enhanced turbulent diffusion associated with strong boundary-layer winds drive transport and dispersion of ozone to the near-surface air over the sea ice, increasing the oxidation rate of bromide (Br−) in the surface snow. Also, if indeed the surface snowpack does supply most of the reactive bromine in the Arctic boundary layer, it appears to be capable of releasing reactive bromine at temperatures as high as −10 °C, particularly on the sea ice in the central and eastern Arctic Ocean. Dynamically-induced BrO column variability in the lowermost stratosphere appears to interfere with the use of satellite BrO column measurements for interpreting BrO variability in the lower troposphere but probably not to the extent of totally obscuring "BrO clouds" that originate from the surface snow/ice source of bromine in the high Arctic. A budget analysis of the simulated air-surface exchange of bromine compounds suggests that a "bromine explosion" occurs in the interstitial air of the snowpack and/or is accelerated by heterogeneous reactions on the surface of wind-blown snow in ambient air, both of which are not represented explicitly in our simple model but could have been approximated by a parameter adjustment for the yield of Br2 from the trigger.

Ten years trends in atmospheric mercury concentrations, meteorological effects and climate variables at Zeppelin, Ny-Ålesund

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-13-2273-2013 ◽

2013 ◽

Vol 13 (1) ◽

pp. 2273-2312

Author(s):

T. Berg ◽

K. A. Pfaffhuber ◽

A. S. Cole ◽

O. Engelsen ◽

A. Steffen

Keyword(s):

Relative Humidity ◽

Wind Direction ◽

Elemental Mercury ◽

Atmospheric Mercury ◽

The Arctic ◽

Climate Indices ◽

Atmospheric Conditions ◽

Surface Emission ◽

Wind Speeds

Abstract. Results from ten years of gaseous elemental mercury (GEM) measurements at Zeppelin Station, Ny-Ålesund, Svalbard, show no overall annual trend between 2000 and 2009. Seasonal trend analysis showed significantly decreasing trends in January, February, March and June and significantly increasing trends in May and July through December. 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 11 m s−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 March and is likley 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.

Direct detection of atmospheric atomic bromine leading to mercury and ozone depletion

Proceedings of the National Academy of Sciences ◽

10.1073/pnas.1900613116 ◽

2019 ◽

Vol 116 (29) ◽

pp. 14479-14484 ◽

Cited By ~ 17

Author(s):

Siyuan Wang ◽

Stephen M. McNamara ◽

Christopher W. Moore ◽

Daniel Obrist ◽

Alexandra Steffen ◽

...

Keyword(s):

Ozone Depletion ◽

Direct Detection ◽

Bromine Atom ◽

Critical Role ◽

Elemental Mercury ◽

Atmospheric Mercury ◽

The Arctic ◽

Molecular Bromine ◽

Near Surface ◽

Halogen Chemistry

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 × 108 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.