scholarly journals The role of bromine and chlorine chemistry for arctic ozone depletion events in Ny-Ålesund and comparison with model calculations

1999 ◽  
Vol 17 (7) ◽  
pp. 941-956 ◽  
Author(s):  
M. Martinez ◽  
T. Arnold ◽  
D. Perner
Keyword(s):  
Ozone Depletion ◽  
Atmospheric Composition ◽  
The Arctic ◽  
Natural Phenomenon ◽  
Optical Absorption Spectroscopy ◽  
Peroxy Radicals ◽  
Source Strength ◽  
Model Calculations ◽  
Pack Ice

Abstract. During the Arctic Tropospheric Ozone Chemistry (ARCTOC) campaigns at Ny-Ålesund, Spitsbergen, the role of halogens in the depletion of boundary layer ozone was investigated. In spring 1995 and 1996 up to 30 ppt bromine monoxide were found whenever ozone decreased from normal levels of about 40 ppb. Those main trace gases and others were specifically followed in the UV-VIS spectral region by differential optical absorption spectroscopy (DOAS) along light paths running between 20 and 475 m a.s.l.. The daily variation of peroxy radicals closely followed the ozone photolysis rate J(O3(O1D)) in the absence of ozone depletion most of the time. However, during low ozone events this close correlation was no longer found because the measurement of radicals by chemical amplification (CA) turned out to be sensitive to peroxy radicals and ClOx. Large CA signals at night can sometimes definitely be assigned to ClOx and reached up to 2 ppt. Total bromine and iodine were both stripped quantitatively from air by active charcoal traps and measured after neutron activation of the samples. Total bromine increased from background levels of about 15 ppt to a maximum of 90 ppt during an event of complete ozone depletion. For the spring season a strong source of bromine is identified in the pack ice region according to back trajectories. Though biogenic emission sources cannot be completely ruled out, a primary activation of halogenides by various oxidants seems to initiate an efficient autocatalytic process, mainly driven by ozone and light, on ice and perhaps on aerosols. Halogenides residing on pack ice surfaces are continuously oxidised by hypohalogenous acids releasing bromine and chlorine into the air. During transport and especially above open water this air mixes with upper layer pristine air. As large quantities of bromine, often in the form of BrO, have been observed at polar sunrise also around Antarctica, its release seems to be a natural phenomenon. The source strength of bromine from halogen activation on the pack ice, as based on the measured inorganic bromine levels, averages about 1012 Br-atoms m-2 s-1 during sunlit periods in Arctic spring. The total source strength of inorganic bromine from sunlit polar regions may therefore amount to 30 kt y-1.Key words. Atmospheric composition and structure (troposphere · composition and chemistry; instruments and techniques)

Record springtime stratospheric ozone depletion at 80°N in 2020

2021 ◽  
Author(s):  
Ramina Alwarda ◽  
Kristof Bognar ◽  
Kimberly Strong ◽  
Martyn Chipperfield ◽  
Sandip Dhomse ◽  
...  
Keyword(s):  
Ozone Depletion ◽  
Transport Model ◽  
Stratospheric Ozone ◽  
Polar Vortex ◽  
The Arctic ◽  
Optical Absorption Spectroscopy ◽  
Chemical Transport Model ◽  
Polar Stratospheric Clouds ◽  
Ozone Loss ◽  
Stratospheric Clouds

<p>The Arctic winter of 2019-2020 was characterized by an unusually persistent polar vortex and temperatures in the lower stratosphere that were consistently below the threshold for the formation of polar stratospheric clouds (PSCs). These conditions led to ozone loss that is comparable to the Antarctic ozone hole. Ground-based measurements from a suite of instruments at the Polar Environment Atmospheric Research Laboratory (PEARL) in Eureka, Canada (80.05°N, 86.42°W) were used to investigate chemical ozone depletion. The vortex was located above Eureka longer than in any previous year in the 20-year dataset and lidar measurements provided evidence of polar stratospheric clouds (PSCs) above Eureka. Additionally, UV-visible zenith-sky Differential Optical Absorption Spectroscopy (DOAS) measurements showed record ozone loss in the 20-year dataset, evidence of denitrification along with the slowest increase of NO<sub>2</sub> during spring, as well as enhanced reactive halogen species (OClO and BrO). Complementary measurements of HCl and ClONO<sub>2</sub> (chlorine reservoir species) from a Fourier transform infrared (FTIR) spectrometer showed unusually low columns that were comparable to 2011, the previous year with significant chemical ozone depletion. Record low values of HNO<sub>3</sub> in the FTIR dataset are in accordance with the evidence of PSCs and a denitrified atmosphere. Estimates of chemical ozone loss were derived using passive ozone from the SLIMCAT offline chemical transport model to account for dynamical contributions to the stratospheric ozone budget.</p>

scholarly journals Active molecular iodine photochemistry in the Arctic

2017 ◽  
Vol 114 (38) ◽  
pp. 10053-10058 ◽  
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 ◽  
Gaseous Elemental Mercury ◽  
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.

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.

Major influence of BrO on the NOx and nitrate budgets in the Arctic spring, inferred from Δ17O(NO3 - ) measurements during ozone depletion events

2007 ◽  
Vol 4 (4) ◽  
pp. 238 ◽  
Author(s):  
S. Morin ◽  
J. Savarino ◽  
S. Bekki ◽  
A. Cavender ◽  
P. B. Shepson ◽  
...  
Keyword(s):  
Nitrogen Oxides ◽  
Isotopic Composition ◽  
Atmospheric Chemistry ◽  
Ozone Depletion ◽  
Lower Atmosphere ◽  
The Arctic ◽  
Major Influence ◽  
Peroxy Radicals ◽  
Bromine Oxide ◽  
Atmospheric Nitrate

Environmental context. Ozone depletion events (ODEs) in the Arctic lower atmosphere drive profound changes in the chemistry of nitrogen oxides (NOx) because of the presence of bromine oxide (BrO). These are investigated using the isotopic composition of atmospheric nitrate (NO3–), which is a ubiquitous species formed through the oxidation of nitrogen oxides. Since BrO is speculated to play a key role in the atmospheric chemistry of marine regions and in the free troposphere, our studies contribute to the improvement of the scientific knowledge on this new topic in atmospheric chemistry. Abstract. The triple oxygen isotopic composition of atmospheric inorganic nitrate was measured in samples collected in the Arctic in springtime at Alert, Nunavut and Barrow, Alaska. The isotope anomaly of nitrate (Δ17O = δ17O–0.52δ18O) was used to probe the influence of ozone (O3), bromine oxide (BrO), and peroxy radicals (RO2) in the oxidation of NO to NO2, and to identify the dominant pathway that leads to the production of atmospheric nitrate. Isotopic measurements confirm that the hydrolysis of bromine nitrate (BrONO2) is a major source of nitrate in the context of ozone depletion events (ODEs), when brominated compounds primarily originating from sea salt catalytically destroy boundary layer ozone. They also show a case when BrO is the main oxidant of NO into NO2.

scholarly journals Copernicus stratospheric ozone service, 2009–2012: validation, system intercomparison and roles of input data sets

2015 ◽  
Vol 15 (5) ◽  
pp. 2269-2293 ◽  
Author(s):  
K. Lefever ◽  
R. van der A ◽  
F. Baier ◽  
Y. Christophe ◽  
Q. Errera ◽  
...  
Keyword(s):  
Data Assimilation ◽  
Atmospheric Chemistry ◽  
Ozone Depletion ◽  
Total Ozone ◽  
Chemical Constituents ◽  
Stratospheric Ozone ◽  
Atmospheric Composition ◽  
The Arctic ◽  
Data Sets ◽  
The Tropics

Abstract. This paper evaluates and discusses the quality of the stratospheric ozone analyses delivered in near real time by the MACC (Monitoring Atmospheric Composition and Climate) project during the 3-year period between September 2009 and September 2012. Ozone analyses produced by four different chemical data assimilation (CDA) systems are examined and compared: the Integrated Forecast System coupled to the Model for OZone And Related chemical Tracers (IFS-MOZART); the Belgian Assimilation System for Chemical ObsErvations (BASCOE); the Synoptic Analysis of Chemical Constituents by Advanced Data Assimilation (SACADA); and the Data Assimilation Model based on Transport Model version 3 (TM3DAM). The assimilated satellite ozone retrievals differed for each system; SACADA and TM3DAM assimilated only total ozone observations, BASCOE assimilated profiles for ozone and some related species, while IFS-MOZART assimilated both types of ozone observations. All analyses deliver total column values that agree well with ground-based observations (biases < 5%) and have a realistic seasonal cycle, except for BASCOE analyses, which underestimate total ozone in the tropics all year long by 7 to 10%, and SACADA analyses, which overestimate total ozone in polar night regions by up to 30%. The validation of the vertical distribution is based on independent observations from ozonesondes and the ACE-FTS (Atmospheric Chemistry Experiment – Fourier Transform Spectrometer) satellite instrument. It cannot be performed with TM3DAM, which is designed only to deliver analyses of total ozone columns. Vertically alternating positive and negative biases are found in the IFS-MOZART analyses as well as an overestimation of 30 to 60% in the polar lower stratosphere during polar ozone depletion events. SACADA underestimates lower stratospheric ozone by up to 50% during these events above the South Pole and overestimates it by approximately the same amount in the tropics. The three-dimensional (3-D) analyses delivered by BASCOE are found to have the best quality among the three systems resolving the vertical dimension, with biases not exceeding 10% all year long, at all stratospheric levels and in all latitude bands, except in the tropical lowermost stratosphere. The northern spring 2011 period is studied in more detail to evaluate the ability of the analyses to represent the exceptional ozone depletion event, which happened above the Arctic in March 2011. Offline sensitivity tests are performed during this month and indicate that the differences between the forward models or the assimilation algorithms are much less important than the characteristics of the assimilated data sets. They also show that IFS-MOZART is able to deliver realistic analyses of ozone both in the troposphere and in the stratosphere, but this requires the assimilation of observations from nadir-looking instruments as well as the assimilation of profiles, which are well resolved vertically and extend into the lowermost stratosphere.

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

&lt;p&gt;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 - &amp;#160;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.&lt;/p&gt;&lt;p&gt;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.&lt;/p&gt;&lt;p&gt;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.&lt;/p&gt;

Model calculations of ozone depletion in the Arctic Polar Vortex for 1991/92 to 1994/95

1996 ◽  
Vol 23 (5) ◽  
pp. 559-562 ◽  
Author(s):  
M. P. Chipperfield ◽  
A. M. Lee ◽  
J. A. Pyle
Keyword(s):  
Ozone Depletion ◽  
Polar Vortex ◽  
The Arctic ◽  
Model Calculations

scholarly journals Time-dependent 3D simulations of tropospheric ozone depletion events in the Arctic spring using the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem)

2021 ◽  
Vol 21 (10) ◽  
pp. 7611-7638
Author(s):  
Maximilian Herrmann ◽  
Holger Sihler ◽  
Udo Frieß ◽  
Thomas Wagner ◽  
Ulrich Platt ◽  
...  
Keyword(s):  
Ozone Depletion ◽  
Heterogeneous Reactions ◽  
The Arctic ◽  
Optical Absorption Spectroscopy ◽  
Weather Research And Forecasting ◽  
Forecasting Model ◽  
Time Interval ◽  
Good Prediction ◽  
Weather Research

Abstract. Tropospheric bromine release and ozone depletion events (ODEs) as they commonly occur in the Arctic spring are studied using a regional model based on the open-source software package Weather Research and Forecasting model coupled with Chemistry (WRF-Chem). For this purpose, the MOZART (Model for Ozone and Related chemical Tracers)–MOSAIC (Model for Simulating Aerosol Interactions and Chemistry) chemical reaction mechanism is extended by bromine and chlorine reactions as well as an emission mechanism for reactive bromine via heterogeneous reactions on snow surfaces. The simulation domain covers an area of 5040 km×4960 km, centered north of Utqiaġvik (formerly Barrow), Alaska, and the time interval from February through May 2009. Several simulations for different strengths of the bromine emission are conducted and evaluated by comparison with in situ and ozone sonde measurements of ozone mixing ratios as well as by comparison with tropospheric BrO vertical column densities (VCDs) from the Global Ozone Monitoring Experiment-2 (GOME-2) satellite instrument. The base bromine emission scheme includes the direct emission of bromine due to bromide oxidation by ozone. Results of simulations with the base emission rate agree well with the observations; however, a simulation with 50 % faster emissions performs somewhat better. The bromine emission due to bromide oxidation by ozone is found to be important to provide an initial seed for the bromine explosion. Bromine release due to N2O5 was found to be important from February to mid March but irrelevant thereafter. A comparison of modeled BrO with in situ and multi-axis differential optical absorption spectroscopy (MAX-DOAS) data hints at missing bromine release and recycling mechanisms on land or near coasts. A consideration of halogen chemistry substantially improves the prediction of the ozone mixing ratio with respect to the observations. Meteorological nudging is essential for a good prediction of ODEs over the 3-month period.

scholarly journals Br<sub>2</sub>, BrCl, BrO and surface ozone in coastal Antarctica: a meteorological and chemical analysis

2012 ◽  
Vol 12 (4) ◽  
pp. 11035-11077 ◽  
Author(s):  
Z. Buys ◽  
N. Brough ◽  
G. Huey ◽  
D. Tanner ◽  
R. von Glasow ◽  
...  
Keyword(s):  
Ozone Depletion ◽  
Surface Ozone ◽  
Source Region ◽  
The Arctic ◽  
High Temporal Resolution ◽  
Blowing Snow ◽  
Model Calculations ◽  
Air Mass ◽  
Unusual Event ◽  
Mixing Ratios

Abstract. There is much debate over the source of bromine radicals in the atmosphere that drives polar boundary layer ozone depletion events (ODEs), but there is strong evidence to suggest a source associated with the sea ice zone. Here we report the first high temporal resolution measurements of Br2, BrCl and BrO in coastal Antarctica, made using a Chemical Ionisation Mass Spectrometer (CIMS). Mixing ratios ranged from instrumental detection limits to 13 pptv for BrO, 45 pptv for Br2, and 6 pptv for BrCl. We find evidence for blowing snow as a source of reactive bromine both directly during a storm and subsequently from recycling of bromide deposited on the continental snowpack. An unusual event of trans-continental air mass transport might have been responsible for severe surface ozone depletion observed at Halley. The halogen source region was the Bellingshausen Sea, to the west of the Antarctic Peninsula, the air mass having spent 3 1/2 days in complete darkness prior to arrival at Halley. We, further, identify an artefact in daytime BrCl measurements arising from conversion of HOBr, similar to that already identified for CIMS observations of Br2. Model calculations using the MISTRA 0-D model suggest a 50–60% conversion of HOBr to Br2, and 5–10% conversion to BrCl. Careful data filtering enabled us to use the halogen observations, in conjunction with the MISTRA model, to explore the temperature dependence of the Br2:BrCl ratio. We find evidence of a ratio shift towards Br2 at temperatures below ~−21 °C, suggesting a relationship with hydrohalite (NaCl.2H2O) precipitation. This suite of Antarctic data provides the first analogue to similar measurements made in the Arctic.

Sign in / Sign up

Export Citation Format

Share Document