scholarly journals Halogens and their role in polar boundary-layer ozone depletion

2007 ◽  
Vol 7 (16) ◽  
pp. 4375-4418 ◽  
Author(s):  
W. R. Simpson ◽  
R. von Glasow ◽  
K. Riedel ◽  
P. Anderson ◽  
P. Ariya ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Atmospheric Chemistry ◽  
Ozone Depletion ◽  
Complete Removal ◽  
Arctic Sea Ice ◽  
The Arctic ◽  
Polar Regions ◽  
Reactive Halogen Species ◽  
Halogen Activation ◽  
Halogen Species

Abstract. During springtime in the polar regions, unique photochemistry converts inert halide salt ions (e.g. Br−) into reactive halogen species (e.g. Br atoms and BrO) that deplete ozone in the boundary layer to near zero levels. Since their discovery in the late 1980s, research on ozone depletion events (ODEs) has made great advances; however many key processes remain poorly understood. In this article we review the history, chemistry, dependence on environmental conditions, and impacts of ODEs. This research has shown the central role of bromine photochemistry, but how salts are transported from the ocean and are oxidized to become reactive halogen species in the air is still not fully understood. Halogens other than bromine (chlorine and iodine) are also activated through incompletely understood mechanisms that are probably coupled to bromine chemistry. The main consequence of halogen activation is chemical destruction of ozone, which removes the primary precursor of atmospheric oxidation, and generation of reactive halogen atoms/oxides that become the primary oxidizing species. The different reactivity of halogens as compared to OH and ozone has broad impacts on atmospheric chemistry, including near complete removal and deposition of mercury, alteration of oxidation fates for organic gases, and export of bromine into the free troposphere. Recent changes in the climate of the Arctic and state of the Arctic sea ice cover are likely to have strong effects on halogen activation and ODEs; however, more research is needed to make meaningful predictions of these changes.

scholarly journals Halogens and their role in polar boundary-layer ozone depletion

2007 ◽  
Vol 7 (2) ◽  
pp. 4285-4403 ◽  
Author(s):  
W. R. Simpson ◽  
R. von Glasow ◽  
K. Riedel ◽  
P. Anderson ◽  
P. Ariya ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Atmospheric Chemistry ◽  
Ozone Depletion ◽  
Complete Removal ◽  
Arctic Sea Ice ◽  
The Arctic ◽  
Polar Regions ◽  
Reactive Halogen Species ◽  
Halogen Activation ◽  
Halogen Species

Abstract. During springtime in the polar regions, unique photochemistry converts inert halide salts ions (e.g. Br−) into reactive halogen species (e.g. Br atoms and BrO) that deplete ozone in the boundary layer to near zero levels. Since their discovery in the late 1980s, research on ozone depletion events (ODEs) has made great advances; however many key processes remain poorly understood. In this article we review the history, chemistry, dependence on environmental conditions, and impacts of ODEs. This research has shown the central role of bromine photochemistry, but how salts are transported from the ocean and are oxidized to become reactive halogen species in the air is still not fully understood. Halogens other than bromine (chlorine and iodine) are also activated through incompletely understood mechanisms that are probably coupled to bromine chemistry. The main consequence of halogen activation is chemical destruction of ozone, which removes the primary precursor of atmospheric oxidation, and generation of reactive halogen atoms/oxides that become the primary oxidizing species. The different reactivity of halogens as compared to OH and ozone has broad impacts on atmospheric chemistry, including near complete removal and deposition of mercury, alteration of oxidation fates for organic gases, and export of bromine into the free troposphere. Recent changes in the climate of the Arctic and state of the Arctic sea ice cover are likely to have strong effects on halogen activation and ODEs; however, more research is needed to make meaningful predictions of these changes.

scholarly journals The mechanism of halogen liberation in the polar troposphere

2004 ◽  
Vol 4 (3) ◽  
pp. 3607-3652 ◽  
Author(s):  
E. Lehrer ◽  
G. Hönninger ◽  
U. Platt
Keyword(s):  
Boundary Layer ◽  
Sea Ice ◽  
Gas Phase ◽  
Ozone Depletion ◽  
Primary Source ◽  
Temperature Inversion ◽  
The Arctic ◽  
Ice Surface ◽  
Reactive Halogen Species ◽  
Halogen Species

Abstract. Sudden depletions of tropospheric ozone during spring were reported from the Arctic and also from Antarctic coastal sites. Field studies showed that those depletion events are caused by reactive halogen species, especially bromine compounds. However the source and seasonal variation of reactive halogen species is still not completely understood. There are several indications that the halogen mobilisation from the sea ice surface of the polar oceans may be the most important source for the necessary halogens. Here we present a 1-D model study aimed at determining the primary source of reactive halogens. The model includes gas phase and heterogeneous bromine and chlorine chemistry as well as vertical transport between the surface and the top of the boundary layer. The autocatalytic Br release by photochemical processes (bromine explosion) and subsequent rapid bromine catalysed ozone depletion is well reproduced in the model and the major source of reactive bromine appears to be the sea ice surface. The sea salt aerosol alone is not sufficient to yield the high levels of reactive bromine in the gas phase necessary for fast ozone depletion. However, the aerosol efficiently 'recycles' less reactive bromine species (e.g. HBr) and feeds them back into the ozone destruction cycle. Isolation of the boundary layer air from the free troposphere by a strong temperature inversion was found to be critical for boundary layer ozone depletion to happen. The combination of strong surface inversions and presence of sunlight occurs only during polar spring.

scholarly journals Numerical analysis of the chemical kinetic mechanisms of ozone depletion and halogen release in the polar troposphere

2013 ◽  
Vol 13 (9) ◽  
pp. 24171-24222 ◽  
Author(s):  
L. Cao ◽  
H. Sihler ◽  
U. Platt ◽  
E. Gutheil
Keyword(s):  
Boundary Layer ◽  
Surface Area ◽  
Ozone Depletion ◽  
Reaction Rates ◽  
The Arctic ◽  
Strong Impact ◽  
Reactive Surface ◽  
A Value ◽  
Halogen Species

Abstract. In recent years, the role of halogen species (e.g. Br, Cl) in the troposphere of polar regions is investigated after the discovery of their importance for boundary layer ozone destruction in the polar spring. Halogen species take part in an auto-catalytic chemical cycle including key self reactions. In this study, several chemical reaction schemes are investigated, and the importance of specific reactions and their rate constants is identified by a sensitivity analysis. A category of heterogeneous reactions related to HOBr activate halogen ions from sea salt aerosols, fresh sea ice or snow pack, driving the "bromine explosion". In the Arctic, a small amount of NOx may exist, which comes from nitrate contained in the snow, and this NOx may have a strong impact on ozone depletion. The heterogeneous reaction rates are parameterized by considering the aerodynamic resistance, a reactive surface ratio, β, i.e. ratio of reactive surface area to total ground surface area, and the boundary layer height, Lmix. It is found that for β = 1, the ozone depletion process starts after five days and lasts for 40 h for Lmix = 200 m. Ozone depletion duration becomes independent of the height of the boundary layer for about β≥20, and it approaches a value of two days for β=100. The role of nitrogen and chlorine containing species on the ozone depletion rate is studied. The calculation of the time integrated bromine and chlorine atom concentrations suggests a value in the order of 103 for the [Br] / [Cl] ratio, which reveals that atomic chlorine radicals have minor direct influence on the ozone depletion. The NOx concentrations are influenced by different chemical cycles over different time periods. During ozone depletion, the reaction cycle involving the BrONO2 hydrolysis is dominant. A critical value of 0.002 of the uptake coefficient of the BrONO2 hydrolysis reaction at the aerosol and saline surfaces is identified, beyond which the existence of NOx species accelerate the ozone depletion event – for lower values, deceleration occurs.

Separating tropospheric and stratospheric BrO columns over the Arctic using TROPOMI data

2020 ◽  
Author(s):  
Moritz Schöne ◽  
Holger Sihler ◽  
Simon Warnach ◽  
Christian Borger ◽  
Steffen Beirle ◽  
...  
Keyword(s):  
Atmospheric Chemistry ◽  
Ozone Depletion ◽  
Meteorological Data ◽  
The Arctic ◽  
Optical Absorption Spectroscopy ◽  
Polar Regions ◽  
Bromine Oxide ◽  
Spatial Coverage ◽  
Meteorological Influences ◽  
Boundary Layer Ozone

<p>Halogen radicals can drastically alter the atmospheric chemistry. In the polar regions, this is made evident, among others, by the almost complete destruction of boundary layer ozone during polar springs. These recurrent episodes of catalytic ozone depletion, referred to as Ozone Depletion Events (ODE), are caused by enhanced concentrations of reactive bromine compounds. The proposed mechanism by which these are released into the atmosphere is called bromine explosions -  reactive bromine is formed autocatalytically from the condensed phase. Enhanced bromine oxide concentrations have been observed by ground-based measurements as well as from aircraft and satellite, where the large spatial coverage allows to study the spatial extent of the phenomenon and its correlation with meteorological data as well as climate change.</p><p>The spatial resolution of S-5P/TROPOMI of 3,5 km x 7 km allows improved localization of these events and to resolve finer structures compared to previous satellite measurements. Together with the better than daily coverage over the polar regions, this allows investigations of the spatio-temporal variability of enhanced BrO levels and their relation to different possible bromine sources and release mechanisms.</p><p>We present tropospheric BrO column densities retrieved from TROPOMI data using Differential Optical Absorption Spectroscopy (DOAS). Building on methods from statistical data analysis and machine learning, we separate the tropospheric partial column from the total column using solely data (BrO, O3 and NO2) measured by satellite. The observations are discussed with regards to sea ice coverage and meteorological influences.</p>

scholarly journals A one dimensional model study of the mechanism of halogen liberation and vertical transport in the polar troposphere

2004 ◽  
Vol 4 (11/12) ◽  
pp. 2427-2440 ◽  
Author(s):  
E. Lehrer ◽  
G. Hönninger ◽  
U. Platt
Keyword(s):  
Boundary Layer ◽  
Sea Ice ◽  
Gas Phase ◽  
Ozone Depletion ◽  
Dimensional Model ◽  
One Dimensional ◽  
Ice Surface ◽  
Model Study ◽  
Reactive Halogen Species ◽  
Halogen Species

Abstract. Sudden depletions of tropospheric ozone during spring were reported from the Arctic and also from Antarctic coastal sites. Field studies showed that those depletion events are caused by reactive halogen species, especially bromine compounds. However the source and seasonal variation of reactive halogen species is still not completely understood. There are several indications that the halogen mobilisation from the sea ice surface of the polar oceans may be the most important source for the necessary halogens. Here we present a one dimensional model study aimed at determining the primary source of reactive halogens. The model includes gas phase and heterogeneous bromine and chlorine chemistry as well as vertical transport between the surface and the top of the boundary layer. The autocatalytic Br release by photochemical processes (bromine explosion) and subsequent rapid bromine catalysed ozone depletion is well reproduced in the model and the major source of reactive bromine appears to be the sea ice surface. The sea salt aerosol alone is not sufficient to yield the high levels of reactive bromine in the gas phase necessary for fast ozone depletion. However, the aerosol efficiently "recycles" less reactive bromine species (e.g. HBr) and feeds them back into the ozone destruction cycle. Isolation of the boundary layer air from the free troposphere by a strong temperature inversion was found to be critical for boundary layer ozone depletion to happen. The combination of strong surface inversions and presence of sunlight occurs only during polar spring.

scholarly journals Polar boundary layer bromine explosion and ozone depletion events in the chemistry-climate model EMAC v2.52: Implementation and evaluation of AirSnow algorithm

2017 ◽  
Author(s):  
Stefanie Falk ◽  
Björn-Martin Sinnhuber
Keyword(s):  
Boundary Layer ◽  
Sea Ice ◽  
Atmospheric Chemistry ◽  
Dry Deposition ◽  
Ozone Depletion ◽  
Climate Model ◽  
Surface Ozone ◽  
The Arctic ◽  
Vertical Column ◽  
Model Studies

Abstract. Ozone depletion events (ODE) in the polar boundary layer have been observed frequently during spring-time. Most likely, they are related to events of boundary layer enhancement of bromine. Consequently, increased vertical column densities (VCD) of BrO have been observed from satellites. These so called bromine explosion events have been discussed serving as source of tropospheric BrO at high latitudes. We have implemented a treatment of bromine release and recycling on sea ice and snow covered surfaces in the global chemistry-climate model EMAC (ECHAM/MESSy Atmospheric Chemistry) based on the scheme of Toyota et al. (2011). In this scheme, dry deposition fluxes of HBr, HOBr, and BrNO3 over ice and snow covered surfaces are recycled into Br2 fluxes. In addition, dry deposition of O3, dependent on temperature and sunlight, triggers a Br2 release from surfaces associated with first-year sea ice. Many aspects of observed bromine enhancements and associated episodes of near-complete depletion of boundary layer ozone, both in the Arctic and in the Antarctic, are reproduced by this relatively simple approach. We present first results from our global model studies extending over a full annual cycle, including comparisons with GOME satellite BrO VCD and surface ozone observations.

scholarly journals Numerical analysis of the chemical kinetic mechanisms of ozone depletion and halogen release in the polar troposphere

2014 ◽  
Vol 14 (7) ◽  
pp. 3771-3787 ◽  
Author(s):  
L. Cao ◽  
H. Sihler ◽  
U. Platt ◽  
E. Gutheil
Keyword(s):  
Boundary Layer ◽  
Surface Area ◽  
Chemical Reactions ◽  
Chemical Reaction ◽  
Ozone Depletion ◽  
Polar Regions ◽  
Reaction Cycle ◽  
Reactive Surface ◽  
Halogen Species

Abstract. The role of halogen species (e.g., Br, Cl) in the troposphere of polar regions has been investigated since the discovery of their importance for boundary layer ozone destruction in the polar spring about 25 years ago. Halogen species take part in an auto-catalytic chemical reaction cycle, which releases Br2 and BrCl from the sea salt aerosols, fresh sea ice or snowpack, leading to ozone depletion. In this study, three different chemical reaction schemes are investigated: a bromine-only reaction scheme, which then is subsequently extended to include nitrogen-containing compounds and chlorine species and corresponding chemical reactions. The importance of specific reactions and their rate constants is identified by a sensitivity analysis. The heterogeneous reaction rates are parameterized by considering the aerodynamic resistance, a reactive surface ratio, β, i.e., the ratio of reactive surface area to total ground surface area, and the boundary layer height, Lmix. It is found that for β = 1, a substantial ozone decrease occurs after five days and ozone depletion lasts for 40 h for Lmix = 200 m. For about β ≥ 20, the time required for major ozone depletion ([O3] < 4 ppb) to occur becomes independent of the height of the boundary layer, and for β = 100 it approaches two days, 28 h of which are attributable to the induction and 20 h to the depletion time. In polar regions, a small amount of NOx may exist, which stems from nitrate contained in the snow, and may have a strong impact on the ozone depletion. Therefore, the role of nitrogen-containing species on the ozone depletion rate is studied. The results show that the NOx concentrations are influenced by different chemical reactions over different time periods. During ozone depletion, the reaction cycle involving the BrONO2 hydrolysis is dominant. A critical value of 0.0004 of the uptake coefficient of the BrONO2 hydrolysis reaction at the aerosol and saline surfaces is identified, beyond which the existence of NOx species accelerates the ozone depletion event, whereas for lower values, deceleration occurs.

scholarly journals Polar boundary layer bromine explosion and ozone depletion events in the chemistry–climate model EMAC v2.52: implementation and evaluation of AirSnow algorithm

2018 ◽  
Vol 11 (3) ◽  
pp. 1115-1131 ◽  
Author(s):  
Stefanie Falk ◽  
Björn-Martin Sinnhuber
Keyword(s):  
Boundary Layer ◽  
Sea Ice ◽  
Atmospheric Chemistry ◽  
Dry Deposition ◽  
Ozone Depletion ◽  
Climate Model ◽  
Surface Ozone ◽  
The Arctic ◽  
In Situ Observation ◽  
Vertical Column

Abstract. Ozone depletion events (ODEs) in the polar boundary layer have been observed frequently during springtime. They are related to events of boundary layer enhancement of bromine. Consequently, increased amounts of boundary layer volume mixing ratio (VMR) and vertical column densities (VCDs) of BrO have been observed by in situ observation, ground-based as well as airborne remote sensing, and from satellites. These so-called bromine explosion (BE) events have been discussed serving as a source of tropospheric BrO at high latitudes, which has been underestimated in global models so far. We have implemented a treatment of bromine release and recycling on sea-ice- and snow-covered surfaces in the global chemistry–climate model EMAC (ECHAM/MESSy Atmospheric Chemistry) based on the scheme of Toyota et al. (2011). In this scheme, dry deposition fluxes of HBr, HOBr, and BrNO3 over ice- and snow-covered surfaces are recycled into Br2 fluxes. In addition, dry deposition of O3, dependent on temperature and sunlight, triggers a Br2 release from surfaces associated with first-year sea ice. Many aspects of observed bromine enhancements and associated episodes of near-complete depletion of boundary layer ozone, both in the Arctic and in the Antarctic, are reproduced by this relatively simple approach. We present first results from our global model studies extending over a full annual cycle, including comparisons with Global Ozone Monitoring Experiment (GOME) satellite BrO VCDs and surface ozone observations.

scholarly journals Ice Concentration Retrieval from the Analysis of Microwaves: A New Methodology Designed for the Copernicus Imaging Microwave Radiometer

2020 ◽  
Vol 12 (7) ◽  
pp. 1060 ◽  
Author(s):  
Lise Kilic ◽  
Catherine Prigent ◽  
Filipe Aires ◽  
Georg Heygster ◽  
Victor Pellet ◽  
...  
Keyword(s):  
Sea Ice ◽  
Spatial Resolution ◽  
Microwave Radiometer ◽  
Optimal Estimation ◽  
Arctic Sea Ice ◽  
The Arctic ◽  
Special Focus ◽  
Polar Regions ◽  
Sea Ice Concentration ◽  
Ice Concentration

Over the last 25 years, the Arctic sea ice has seen its extent decline dramatically. Passive microwave observations, with their ability to penetrate clouds and their independency to sunlight, have been used to provide sea ice concentration (SIC) measurements since the 1970s. The Copernicus Imaging Microwave Radiometer (CIMR) is a high priority candidate mission within the European Copernicus Expansion program, with a special focus on the observation of the polar regions. It will observe at 6.9 and 10.65 GHz with 15 km spatial resolution, and at 18.7 and 36.5 GHz with 5 km spatial resolution. SIC algorithms are based on empirical methods, using the difference in radiometric signatures between the ocean and sea ice. Up to now, the existing algorithms have been limited in the number of channels they use. In this study, we proposed a new SIC algorithm called Ice Concentration REtrieval from the Analysis of Microwaves (IceCREAM). It can accommodate a large range of channels, and it is based on the optimal estimation. Linear relationships between the satellite measurements and the SIC are derived from the Round Robin Data Package of the sea ice Climate Change Initiative. The 6 and 10 GHz channels are very sensitive to the sea ice presence, whereas the 18 and 36 GHz channels have a better spatial resolution. A data fusion method is proposed to combine these two estimations. Therefore, IceCREAM will provide SIC estimates with the good accuracy of the 6+10GHz combination, and the high spatial resolution of the 18+36GHz combination.

scholarly journals Ozone in the Boundary Layer air over the Arctic Ocean – measurements during the TARA expedition

2009 ◽  
Vol 9 (2) ◽  
pp. 8561-8586
Author(s):  
J. W. Bottenheim ◽  
S. Netcheva ◽  
S. Morin ◽  
S. V. Nghiem
Keyword(s):  
Boundary Layer ◽  
Arctic Ocean ◽  
Ozone Depletion ◽  
Surface Ozone ◽  
The Arctic ◽  
Total Absence ◽  
Trajectory Calculations ◽  
The Arctic Ocean ◽  
Ocean Measurements ◽  
Siberian Coast

Abstract. A full year of measurements of surface ozone over the Arctic Ocean far removed from land is presented (81° N – 88° N latitude). The data were obtained during the drift of the French schooner TARA between September 2006 and January 2008, while frozen in the Arctic Ocean. The data confirm that long periods of virtually total absence of ozone occur in the spring (mid March to mid June) after Polar sunrise. At other times of the year ozone concentrations are comparable to other oceanic observations with winter mole fractions of ca. 30–40 nmol mol−1 and summer minima of ca. 20 nmol mol−1. Contrary to earlier observations from ozone sonde data obtained at Arctic coastal observatories, the ambient temperature was well above −20°C during most ODEs (ozone depletion episodes). Backwards trajectory calculations suggest that during these ODEs the air had previously been in contact with the frozen ocean surface for several days and originated largely from the Siberian coast where several large open flaw leads developed in the spring of 2007.

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