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Reactive halogen chemistry in the springtime Arctic causes ozone depletion events and alters the rate of pollution processing. There are still many uncertainties regarding this chemistry, including the multiphase recycling of halogens and how sea ice impacts the source strength of reactive bromine. Adding to these uncertainties are the impacts of a rapidly warming Arctic. We present observations from the CHACHA (CHemistry in the Arctic: Clouds, Halogens, and Aerosols) field campaign based out of Utqiaġvik, Alaska, from mid-February to mid-April of 2022 to provide information on the vertical distribution of bromine monoxide (BrO), which is a tracer for reactive bromine chemistry. Data were gathered using the Heidelberg Airborne Imaging DOAS (differential optical absorption spectroscopy) Instrument (HAIDI) on the Purdue University Airborne Laboratory for Atmospheric Research (ALAR) and employing a unique sampling technique of vertically profiling the lower atmosphere with the aircraft via "porpoising" maneuvers. Observations from HAIDI were coupled to radiative transfer model calculations to retrieve mixing ratio profiles throughout the lower atmosphere (below 1000 m), with unprecedented vertical resolution (50 m) and total information gathered (average of 17.5 degrees of freedom) for this region. A cluster analysis was used to categorize 245 retrieved BrO mixing ratio vertical profiles into four common profile shapes. We often found the highest BrO mixing ratios at the Earth's surface with a mean of nearly 30 pmol mol -1 in the lowest 50 m, indicating an important role for multiphase chemistry on the snowpack in reactive bromine production. Most lofted-BrO profiles corresponded with an aerosol profile that peaked at the same altitude (225 m above the ground), suggesting that BrO was maintained due to heterogeneous reactions on particle surfaces aloft during these profiles. A majority (11 of 15) of the identified lofted-BrO profiles occurred on a single day, 19 March 2022, over an area covering more than 24 000 km 2 , indicating that this was a large-scale lofted-BrO event. The clustered BrO mixing ratio profiles should be particularly useful for some MAX-DOAS (multi-axis DOAS) studies, where a priori BrO profiles and their uncertainties, used in optimal estimation inversion algorithms, are not often based on previous observations. Future MAX-DOAS studies (and past reanalyses) could rely on the profiles provided in this work to improve BrO retrievals. [ABSTRACT FROM AUTHOR]

Reactive halogens play a prominent role in the atmospheric chemistry of the Arctic during springtime. Field measurements and modeling studies suggest that halogens are emitted into the atmosphere from snowpack and reactions on wind-blown snow-sourced aerosols. The relative importance of snowpack and blowing snow sources is still debated, both at local scales and regionally throughout the Arctic. To understand the implications of these halogen sources on a pan-Arctic scale, we simulate Arctic reactive bromine chemistry in the atmospheric chemical transport model GEOS-Chem. Two mechanisms are included: (1) a blowing snow sea salt aerosol formation mechanism and (2) a snowpack mechanism assuming uniform molecular bromine production from all snow surfaces. We compare simulations including neither mechanism, each mechanism individually, and both mechanisms to examine conditions where one process may dominate or the mechanisms may interact. We compare the models using these mechanisms to observations of bromine monoxide (BrO) derived from multiple-axis differential optical absorption spectroscopy (MAX-DOAS) instruments on O-Buoy platforms on the sea ice and at a coastal site in Utqiaġvik, Alaska, during spring 2015. Model estimations of hourly and monthly average BrO are improved by assuming a constant yield of 0.1 % molecular bromine from all snowpack surfaces on ozone deposition. The blowing snow aerosol mechanism increases modeled BrO by providing more bromide-rich aerosol surface area for reactive bromine recycling. The snowpack mechanism led to increased model BrO across the Arctic Ocean with maximum production in coastal regions, whereas the blowing snow aerosol mechanism increases BrO in specific areas due to high surface wind speeds. Our uniform snowpack source has a greater impact on BrO mixing ratios than the blowing snow source. Model results best replicate several features of BrO observations during spring 2015 when using both mechanisms in conjunction, adding evidence that these mechanisms are both active during the Arctic spring. Extending our transport model throughout the entire year leads to predictions of enhanced fall BrO that are not supported by observations. [ABSTRACT FROM AUTHOR]

Iodine compounds destroy ozone (O 3) in the global troposphere and form new aerosols, thereby affecting the global radiative balance. However, few reports have described the latitudinal distribution of atmospheric iodine compounds. This work reports iodine monoxide (IO) measurements taken over unprecedented sampling areas from the Arctic to the Southern Hemisphere and spanning sea surface temperatures (SSTs) of approximately 0 to 31.5 ∘ C. The highest IO concentrations were observed over the Western Pacific warm pool (WPWP), where O 3 minima were also measured. There, a negative correlation was found between O 3 and IO mixing ratios at extremely low O 3 concentrations. This correlation is not explained readily by the O 3 -dependent oceanic fluxes of photolabile inorganic iodine compounds, which is the dominant source in recent global-scale chemistry transport models representing iodine chemistry. Actually, the correlation rather implies that O 3 -independent pathways can be similarly important in the WPWP. The O 3 -independent fluxes result in a 15 % greater O 3 loss than that estimated for O 3 -dependent processes alone. The daily O 3 loss rate related to iodine over the WPWP is as high as approximately 2 ppbv (parts per billion by volume) despite low O 3 concentrations of approximately 10 ppbv, with the loss being up to 100 % greater than that without iodine. This finding suggests that warming SST driven by climate change might affect the marine atmospheric chemical balance through iodine–ozone chemistry. [ABSTRACT FROM AUTHOR]

Chlorine dioxide (OClO) is a by-product of the ozone-depleting halogen chemistry in the stratosphere. Although it is rapidly photolysed at low solar zenith angles (SZAs), it plays an important role as an indicator of the chlorine activation in polar regions during polar winter and spring at twilight conditions because of the nearly linear dependence of its formation on chlorine oxide (ClO). Here, we compare slant column densities (SCDs) of chlorine dioxide (OClO) retrieved by means of differential optical absorption spectroscopy (DOAS) from spectra measured by the TROPOspheric Monitoring Instrument (TROPOMI) with meteorological data for both Antarctic and Arctic regions for the first three winters in each of the hemispheres (November 2017–October 2020). TROPOMI, a UV–Vis–NIR–SWIR instrument on board of the Sentinel-5P satellite, monitors the Earth's atmosphere in a near-polar orbit at an unprecedented spatial resolution and signal-to-noise ratio and provides daily global coverage at the Equator and thus even more frequent observations at polar regions. The observed OClO SCDs are generally well correlated with the meteorological conditions in the polar winter stratosphere; for example, the chlorine activation signal appears as a sharp gradient in the time series of the OClO SCDs once the temperature drops to values well below the nitric acid trihydrate (NAT) existence temperature (TNAT). Also a relation of enhanced OClO values at lee sides of mountains can be observed at the beginning of the winters, indicating a possible effect of lee waves on chlorine activation. The dataset is also compared with CALIPSO Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) polar stratospheric cloud (PSC) observations. In general, OClO SCDs coincide well with CALIOP measurements for which PSCs are detected. Very high OClO levels are observed for the northern hemispheric winter 2019/20, with an extraordinarily long period with a stable polar vortex being even close to the values found for southern hemispheric winters. An extraordinary winter in the Southern Hemisphere was also observed in 2019, with a minor sudden stratospheric warming at the beginning of September. In this winter, similar OClO values were measured in comparison to the previous (usual) winter till that event but with a OClO deactivation that was 1–2 weeks earlier. [ABSTRACT FROM AUTHOR]

Within the framework of the International Arctic Systems for Observing the Atmosphere (IASOA), we report a modelling-based study on surface ozone across the Arctic. We use surface ozone from six sites – Summit (Greenland), Pallas (Finland), Barrow (USA), Alert (Canada), Tiksi (Russia), and Villum Research Station (VRS) at Station Nord (North Greenland, Danish realm) – and ozone-sonde data from three Canadian sites: Resolute, Eureka, and Alert. Two global chemistry models – a global chemistry transport model (parallelised-Tropospheric Offline Model of Chemistry and Transport, p-TOMCAT) and a global chemistry climate model (United Kingdom Chemistry and Aerosol, UKCA) – are used for model data comparisons. Remotely sensed data of BrO from the GOME-2 satellite instrument and ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) at Eureka, Canada, are used for model validation. The observed climatology data show that spring surface ozone at coastal sites is heavily depleted, making ozone seasonality at Arctic coastal sites distinctly different from that at inland sites. Model simulations show that surface ozone can be greatly reduced by bromine chemistry. In April, bromine chemistry can cause a net ozone loss (monthly mean) of 10–20 ppbv, with almost half attributable to open-ocean-sourced bromine and the rest to sea-ice-sourced bromine. However, the open-ocean-sourced bromine, via sea spray bromide depletion, cannot by itself produce ozone depletion events (ODEs; defined as ozone volume mixing ratios, VMRs, < 10 ppbv). In contrast, sea-ice-sourced bromine, via sea salt aerosol (SSA) production from blowing snow, can produce ODEs even without bromine from sea spray, highlighting the importance of sea ice surface in polar boundary layer chemistry. Modelled total inorganic bromine (Br Y) over the Arctic sea ice is sensitive to model configuration; e.g. under the same bromine loading, Br Y in the Arctic spring boundary layer in the p-TOMCAT control run (i.e. with all bromine emissions) can be 2 times that in the UKCA control run. Despite the model differences, both model control runs can successfully reproduce large bromine explosion events (BEEs) and ODEs in polar spring. Model-integrated tropospheric-column BrO generally matches GOME-2 tropospheric columns within ∼ 50 % in UKCA and a factor of 2 in p-TOMCAT. The success of the models in reproducing both ODEs and BEEs in the Arctic indicates that the relevant parameterizations implemented in the models work reasonably well, which supports the proposed mechanism of SSA production and bromide release on sea ice. Given that sea ice is a large source of SSA and halogens, changes in sea ice type and extent in a warming climate will influence Arctic boundary layer chemistry, including the oxidation of atmospheric elemental mercury. Note that this work dose not necessary rule out other possibilities that may act as a source of reactive bromine from the sea ice zone. [ABSTRACT FROM AUTHOR]

Every polar spring, phenomena called bromine explosions occur over sea ice. These bromine explosions comprise photochemical heterogeneous chain reactions that release bromine molecules, Br2 , to the troposphere and lead to tropospheric plumes of bromine monoxide, BrO. This autocatalytic mechanism depletes ozone, O3 , in the boundary layer and troposphere and thereby changes the oxidizing capacity of the atmosphere. The phenomenon also leads to accelerated deposition of metals (e.g., Hg). In this study, we present a 22-year (1996 to 2017) consolidated and consistent tropospheric BrO dataset north of 70 ∘ N, derived from four different ultraviolet–visible (UV–VIS) satellite instruments (GOME, SCIAMACHY, GOME-2A and GOME-2B). The retrieval data products from the different sensors are compared during periods of overlap and show good agreement (correlations of 0.82–0.98 between the sensors). From our merged time series of tropospheric BrO vertical column densities (VCDs), we infer changes in the bromine explosions and thus an increase in the extent and magnitude of tropospheric BrO plumes during the period of Arctic warming. We determined an increasing trend of about 1.5 % of the tropospheric BrO VCDs per year during polar springs, while the size of the areas where enhanced tropospheric BrO VCDs can be found has increased about 896 km 2 yr -1. We infer from comparisons and correlations with sea ice age data that the reported changes in the extent and magnitude of tropospheric BrO VCDs are moderately related to the increase in first-year ice extent in the Arctic north of 70 ∘ N, both temporally and spatially, with a correlation coefficient of 0.32. However, the BrO plumes and thus bromine explosions show significant variability, which also depends, apart from sea ice, on meteorological conditions. [ABSTRACT FROM AUTHOR]

Satellite observations have shown large areas of elevated bromine monoxide (BrO) covering several thousand square kilometres over the Arctic and Antarctic sea ice regions in polar spring. These enhancements of total BrO columns result from increases in stratospheric or tropospheric bromine amounts or both, and their occurrence may be related to local meteorological conditions. In this study, the spatial distribution of the occurrence of total BrO column enhancements and the associated changes in meteorological parameters are investigated in both the Arctic and Antarctic regions using 10 years of Global Ozone Monitoring Experiment-2 (GOME-2) measurements and meteorological model data. Statistical analysis of the data presents clear differences in the meteorological conditions between the 10-year mean and episodes of enhanced total BrO columns in both polar sea ice regions. These differences show pronounced spatial patterns. In general, atmospheric low pressure, cold surface air temperature, high surface-level wind speed, and low tropopause heights were found during periods of enhanced total BrO columns. In addition, spatial patterns of prevailing wind directions related to the BrO enhancements are identified in both the Arctic and Antarctic sea ice regions. The relevance of the different meteorological parameters on the total BrO column is evaluated based on a Spearman rank correlation analysis, finding that tropopause height and surface air temperature have the largest correlations with the total BrO vertical column density. Our results demonstrate that specific meteorological parameters can have a major impact on the BrO enhancement in some areas, but in general, multiple meteorological parameters interact with each other in their influence on BrO columns. [ABSTRACT FROM AUTHOR]

We use the GEOS-Chem chemical transport model to examine the influence of bromine release from blowing-snow sea salt aerosol (SSA) on springtime bromine activation and O3 depletion events (ODEs) in the Arctic lower troposphere. We evaluate our simulation against observations of tropospheric BrO vertical column densities (VCD tropo) from the GOME-2 (second Global Ozone Monitoring Experiment) and Ozone Monitoring Instrument (OMI) spaceborne instruments for 3 years (2007–2009), as well as against surface observations of O3. We conduct a simulation with blowing-snow SSA emissions from first-year sea ice (FYI; with a surface snow salinity of 0.1 psu) and multi-year sea ice (MYI; with a surface snow salinity of 0.05 psu), assuming a factor of 5 bromide enrichment of surface snow relative to seawater. This simulation captures the magnitude of observed March–April GOME-2 and OMI VCD tropo to within 17 %, as well as their spatiotemporal variability (r=0.76 –0.85). Many of the large-scale bromine explosions are successfully reproduced, with the exception of events in May, which are absent or systematically underpredicted in the model. If we assume a lower salinity on MYI (0.01 psu), some of the bromine explosions events observed over MYI are not captured, suggesting that blowing snow over MYI is an important source of bromine activation. We find that the modeled atmospheric deposition onto snow-covered sea ice becomes highly enriched in bromide, increasing from enrichment factors of ∼5 in September–February to 10–60 in May, consistent with composition observations of freshly fallen snow. We propose that this progressive enrichment in deposition could enable blowing-snow-induced halogen activation to propagate into May and might explain our late-spring underestimate in VCD tropo. We estimate that the atmospheric deposition of SSA could increase snow salinity by up to 0.04 psu between February and April, which could be an important source of salinity for surface snow on MYI as well as FYI covered by deep snowpack. Inclusion of halogen release from blowing-snow SSA in our simulations decreases monthly mean Arctic surface O3 by 4–8 ppbv (15 %–30 %) in March and 8–14 ppbv (30 %–40 %) in April. We reproduce a transport event of depleted O3 Arctic air down to 40 ∘ N observed at many sub-Arctic surface sites in early April 2007. While our simulation captures 25 %–40 % of the ODEs observed at coastal Arctic surface sites, it underestimates the magnitude of many of these events and entirely misses 60 %–75 % of ODEs. This difficulty in reproducing observed surface ODEs could be related to the coarse horizontal resolution of the model, the known biases in simulating Arctic boundary layer exchange processes, the lack of detailed chlorine chemistry, and/or the fact that we did not include direct halogen activation by snowpack chemistry. [ABSTRACT FROM AUTHOR]

The Arctic is one of the most rapidly warming regions of the Earth, with predicted temperature increases of 5–7 ∘ C and the accompanying extensive retreat of Arctic glacial systems by 2100. Retreating glaciers will reveal new land surfaces for microbial colonisation, ultimately succeeding to tundra over decades to centuries. An unexplored dimension to these changes is the impact upon the emission and consumption of halogenated organic compounds (halocarbons). Halocarbons are involved in several important atmospheric processes, including ozone destruction, and despite considerable research, uncertainties remain in the natural cycles of some of these compounds. Using flux chambers, we measured halocarbon fluxes across the glacier forefield (the area between the present-day position of a glacier's ice-front and that at the last glacial maximum) of a high-Arctic glacier in Svalbard, spanning recently exposed sediments (<10 years) to approximately 1950-year-old tundra. Forefield land surfaces were found to consume methyl chloride (CH3Cl) and methyl bromide (CH3Br), with both consumption and emission of methyl iodide (CH3I) observed. Bromoform (CHBr3) and dibromomethane (CH2Br2) have rarely been measured from terrestrial sources but were here found to be emitted across the forefield. Novel measurements conducted on terrestrial cyanobacterial mats covering relatively young surfaces showed similar measured fluxes to the oldest, vegetated tundra sites for CH3Cl , CH3Br , and CH3I (which were consumed) and for CHCl3 and CHBr3 (which were emitted). Consumption rates of CH3Cl and CH3Br and emission rates of CHCl3 from tundra and cyanobacterial mat sites were within the ranges reported from older and more established Arctic tundra elsewhere. Rough calculations showed total emissions and consumptions of these gases across the Arctic were small relative to other sources and sinks due to the small surface area represented by glacier forefields. We have demonstrated that glacier forefields can consume and emit halocarbons despite their young age and low soil development, particularly when cyanobacterial mats are present. [ABSTRACT FROM AUTHOR]

Heterogeneous photochemistry converts bromide (Br-) to reactive bromine species (Br atoms and bromine monoxide, BrO) that dominate Arctic springtime chemistry. This phenomenon has many impacts such as boundary-layer ozone depletion, mercury oxidation and deposition, and modification of the fate of hydrocarbon species. To study environmental controls on reactive bromine events, the B Romine, Ozone, and Mercury EXperiment (BROMEX) was carried out from early March to mid-April 2012 near Barrow (Utqiaġvik), Alaska. We measured horizontal and vertical gradients in BrO with multiple-axis differential optical absorption spectroscopy (MAX-DOAS) instrumentation at three sites, two mobile and one fixed. During the campaign, a large crack in the sea ice (an open lead) formed pushing one instrument package ~250 km downwind from Barrow (Utqiaġvik). Convection associated with the open lead converted the BrO vertical structure from a surface-based event to a lofted event downwind of the lead in?uence. The column abundance of BrO downwind of the refreezing lead was comparable to upwind amounts, indicating direct reactions on frost ?owers or open seawater was not a major reactive bromine source. When these three sites were separated by ~30 km length scales of unbroken sea ice, the BrO amount and vertical distributions were highly correlated for most of the time, indicating the horizontal length scales of BrO events were typically larger than ~30 km in the absence of sea ice features. Although BrO amount and vertical distribution were similar between sites most of the time, rapid changes in BrO with edges significantly smaller than this 30 km length scale episodically transported between the sites, indicating BrO events were large but with sharp edge contrasts. BrO was often found in shallow layers that recycled reactive bromine via heterogeneous reactions on snowpack. Episodically, these surface-based events propagated aloft when aerosol extinction was higher (> 0.1 km-1/; however, the presence of aerosol particles aloft was not sufficient to produce BrO aloft. Highly depleted ozone (< 1 nmol mol-1/ repartitioned reactive bromine away from BrO and drove BrO events aloft in cases. This work demonstrates the interplay between atmospheric mixing and heterogeneous chemistry that affects the vertical structure and horizontal extent of reactive bromine events. [ABSTRACT FROM AUTHOR]

Stratospheric ozone profiles are retrieved for the period 2002-2009 from SCIAMACHY measurements of limb-scattered solar radiation in the Hartley and Chappuis absorption bands of ozone. This data set is used to determine the chemical ozone losses in both the Arctic and Antarctic polar vortices by averaging the ozone in the vortex at a given potential temperature. The chemical ozone losses at isentropic levels between 450K and 600K are derived from the difference between observed ozone abundances and the ozone modelled taking diabatic cooling into account, but no chemical ozone loss. Chemical ozone losses of up to 30-40% between mid-January and the end of March inside the Arctic polar vortex are reported. Strong inter-annual variability of the Arctic ozone loss is observed, with the cold winters 2004/2005 and 2006/2007 showing chemical ozone losses inside the polar vortex at 475K, where 1.7 ppmv and 1.4 ppmv of ozone were removed, respectively, over the period from 22 January to beginning of April and 0.9 ppmv and 1.2 ppmv, respectively, during February. For the winters of 2007/2008 and 2002/2003, ozone losses of about 0.8 ppmv and 0.4 ppmv, respectively are estimated at the 475K isentropic level for the period from 22 January to beginning of April. Essentially no ozone losses were diagnosed for the relatively warm winters of 2003/2004 and 2005/2006. The maximum ozone loss in the SCIAMACHY data set was found in 2007 at the 600K level and amounted to about 2.1 ppmv for the period between 22 January and the end of April. Enhanced losses close to this altitude were found in all investigated Arctic springs, in contrast to Antarctic spring. The inter-annual variability of ozone losses and PSC occurrence rates observed during Arctic spring is consistent with the known QBO effects on the Arctic polar vortex, with exception of the unusual Arctic winter 2008/2009. The maximum total ozone mass loss of about 25 million tons was found in the cold Arctic winter of 2004/2005 inside the polar vortex between the 450K and 600K isentropic levels from mid-January until the middle of March. The Antarctic vortex averaged ozone loss as well as the size of the polar vortex do not vary much from year to year. The total ozone mass loss inside the Antarctic polar vortex between the 450K and 600K isentropic levels is about 50-60 million tons and the vortex volume for this altitude range varies between about 150 and 300 km³ for the period between mid-August and mid-November of every year studied, except for 2002. In 2002 a mid-winter major stratospheric warming occurred in the second half of September and the ozone mass loss was only about half of the value in the other years. However, inside the polar vortex we find chemical ozone losses at the 475K isentropic level that are similar to those in all other years studied. At this isentropic level ozone losses of 70-90% between mid-August and mid-November or about 2.5 ppmv are observed every year. At isentropic levels above 500K the chemical ozone losses were found to be larger in 2002 than in all other years studied. Comparisons of the vertical variation of ozone losses derived from SCIAMACHY observations with several independent techniques for the Arctic winter 2004/2005 show that the SCIAMACHY results fall in the middle of the range of previously published results for this winter. For other winters in both hemispheres - for which comparisons with other studies were possible - the SCIAMACHY results are consistent with the range of previously published results. [ABSTRACT FROM AUTHOR]

We derive tropospheric column BrO during the ARCTAS and ARCPAC field campaigns in spring 2008 using retrievals of total column BrO from the satellite UV nadir sensors OMI and GOME-2 using a radiative transfer model and stratospheric column BrO from a photochemical simulation. We conduct a comprehensive comparison of satellitederived tropospheric BrO column to aircraft in-situ observations of BrO and related species. The aircraft profiles reveal that tropospheric BrO, when present during April 2008, was distributed over a broad range of altitudes rather than being confined to the planetary boundary layer (PBL). Perturbations to the total column resulting from tropospheric BrO are the same magnitude as perturbations due to longitudinal variations in the stratospheric component, so proper accounting of the stratospheric signal is essential for accurate determination of satellite-derived tropospheric BrO. We find reasonably good agreement between satellite-derived tropospheric BrO and columns found using aircraft in-situ BrO profiles, particularly when satellite radiances were obtained over bright surfaces (albedo >0.7), for solar zenith angle <80° and clear sky conditions. The rapid activation of BrO due to surface processes (the bromine explosion) is apparent in both the OMI and GOME-2 based tropospheric columns. The wide orbital swath of OMI allows examination of the evolution of tropospheric BrO on about hourly time intervals near the pole. Low surface pressure, strong wind, and high PBL height are associated with an observed BrO activation event, supporting the notion of bromine activation by high winds over snow. [ABSTRACT FROM AUTHOR]

Gaseous elemental mercury (GEM) is converted to reactive gaseous mercury (RGM) during springtime Atmospheric Mercury Depletion Events (AMDE). This study reports the longest time series of GEM, RGM and particle-bound mercury (PHg) concentrations from a European Arctic site. From 27 April 2007 until 31 December 2008 composite GEM, RGM and PHg measurements were conducted in Ny-Ålesund (78° 54' N, 11° 53' E). The average concentrations of the complete dataset were 1.6±0.3 ng m-3 , 8±13 pg m-3 and 8±25 p gm-3 for GEM, RGM and PHg, respectively. For the complete dataset the atmosphericmercury distribution was 99%GEM, whereas RGM and PHg constituted <1%. The study revealed a seasonal distribution of GEM, RGMand PHg previously undiscovered in the Arctic. Increased concentrations of RGM were observed during the insolation period from March through August, while increased PHg concentrations occurred almost exclusively during the spring AMDE period in March and April. The elevated RGM concentrations suggest that atmospheric RGMdeposition also occurs during the polar summer. RGM was suggested as the precursor for the PHg existence, but long range transportation of PHg has to be taken into consideration. Still there remain gaps in the knowledge of how RGM and PHg are related in the environment. RGM and PHg accounted for on average about 10% of the depleted GEM during AMDEs. Although speculative, the fairly low RGM and PHg concentrations supported by the predominance of PHg with respect to RGM and no clear meteorological regime associated with these AMDEs would all suggest the events to be of non-local origin. With some exceptions, no clear meteorological regime was associated with the GEM, RGMand PHg concentrations throughout the year. [ABSTRACT FROM AUTHOR]

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 x 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 re-active 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 re-active 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 lower--most 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. [ABSTRACT FROM AUTHOR]

Ozone Depletion Events (ODE) during polar springtime are a well known phenomenon in the Arctic and Antarctic boundary layer. They are caused by the catalytic destruction of ozone by halogens producing reactive halogen oxides like bromine monoxide (BrO). The key halogen bromine can be rapidly transferred into the gas phase in an autocatalytic process - the so called "Bromine Explosion". However, the exact mechanism, which leads to an initial bromine release as well as the influence of transport and chemical processes on BrO, is still not clearly understood. In this study, BrO measurements from the satellite instrument GOME-2 are used together with model calculations with the dispersion model FLEXPART to study an arctic BrO event in March 2007, which could be tracked over several days and a large area. Full BrO activation was observed within one day east of Siberia with subsequent transport to Hudson Bay. The event was linked to a cyclone with very high surface wind speeds, which could have been involved in the production and lifting of aerosols or blowing snow. Considering the short life time of BrO, transported aerosols or snow can also provide the surface for BrO recycling within the plume for several days. The evolution of the BrO plume could be reproduced by FLEXPART simulations of a passive tracer indicating that the activated air mass was transported all the way from Siberia to Hudson Bay. To localise the most probable transport height, model runs initialised in different heights have been performed showing similar transport patterns throughout the troposphere but best agreement with the measurements between the surface and 3 km. The influence of changes in tropopause height on measured BrO values has been considered, but cannot completely explain the observed high BrO values. Backward trajectories from the area of BrO initialisation show upward lifting from the surface up to 3 km and no indication for intrusion of stratospheric air. These observations are consistent with a scenario in which bromine in the air mass was activated on the surface within the cyclone, lifted upwards and transported over several thousand kilometres to Hudson Bay. [ABSTRACT FROM AUTHOR]

We use observations from the April 2008 NASA ARCTAS aircraft campaign to the North American Arctic, interpreted with a global 3-D chemical transport model (GEOS-Chem), to better understand the sources and cycling of hydrogen oxide radicals (HOx≡H+OH+peroxy radicals) and their reservoirs (HOy≡HOx+peroxides) in the springtime Arctic atmosphere. We find that a standard gas-phase chemical mechanism overestimates the observed HO2 and H2O2 concentrations. Computation of HOx and HOy gasphase chemical budgets on the basis of the aircraft observations also indicates a large missing sink for both. We hypothesize that this could reflect HO2 uptake by aerosols, favored by low temperatures and relatively high aerosol loadings, through a mechanism that does not produce H2O2. We implemented such an uptake of HO2 by aerosol in the model using a standard reactive uptake coefficient parameterization with (HO2) values ranging from 0.02 at 275K to 0.5 at 220 K. This successfully reproduces the concentrations and vertical distributions of the different HOx species and HOy reservoirs. HO2 uptake by aerosol is then a major HOx and HOy sink, decreasing mean OH and HO2 concentrations in the Arctic troposphere by 32% and 31% respectively. Better rate and product data for HO2 uptake by aerosol are needed to understand this role of aerosols in limiting the oxidizing power of the Arctic atmosphere. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]