Tropospheric Ozone Depletion Events Research Articles

Year-long ground-based observations of bromine oxide over Bharati Station, Antarctica

Bromine chemistry plays an important role in tropospheric ozone depletion events in polar regions. Autocatalytic reactions lead to bromine explosion events, causing ozone depletion to near-zero levels in the polar troposphere. Bromine chemistry over Antarctica is not fully understood, and ground-based observations are scarce. This work presents year-long observations of bromine oxide (BrO) over the Bharati station (69.41°S, 76.19°E) using Multi-axis Differential Optical Absorption Spectroscopy (MAX-DOAS) from December 2018 to February 2020. The results show that elevated BrO mixing ratios were found during spring (September), with a maximum value of 10.21 ± 4.38 pptv for clear sky conditions and 33.15 ± 2.23 pptv for cloudy conditions. BrO was not observed above the detection limit (∼3 × 1013 molecule cm−2) outside spring on clear days. In general, lower mixing ratios were observed on clear days over Bharati compared to stations in West Antarctica. This indicates a different source strength over East Antarctica compared to West Antarctica. BrO vertical column densities were high during spring, with a maximum value of 1.34 ± 0.35 × 1014 molecule cm−2. The vertical profiles of the BrO mixing ratios show a peak at the surface during spring (average of 6.5 ± 1.91 pptv), decreasing sharply with altitude. Back trajectories show that air masses passing over the first year ice showed higher BrO, although factors such as meteorology play an important role in determining the absolute levels. Using a box model, we show that bromine chemistry can deplete as much as 2.15 ppb of ozone in a day at the Bharati Station on clear days, which shows that it does not lead to complete ozone depletion events over Bharati.

A three-dimensional simulation and process analysis of tropospheric ozone depletion events (ODEs) during the springtime in the Arctic using CMAQ (Community Multiscale Air Quality Modeling System)

Abstract. The tropospheric ozone depletion event (ODE), first observed at Barrow (now known as Utqiaġvik), Alaska, is a phenomenon that frequently occurs during the springtime in the Arctic. In this study, we performed a three-dimensional model study on ODEs occurring at Barrow and its surrounding areas between 28 March and 6 April 2019 using a 3-D multi-scale air quality model, CMAQ (Community Multiscale Air Quality Modeling System). Several ODEs observed at Barrow were captured, and two of them were thoroughly analyzed using the process analysis method to estimate contributions of horizontal transport, vertical transport, dry deposition, and the overall chemical process to the variations in ozone and bromine species during ODEs. We found that the ODE occurring between 30 and 31 March 2019 (referred to as ODE1) was primarily caused by the horizontal transport of low-ozone air from the Beaufort Sea to Barrow. The formation of this low-ozone air over the sea was largely attributed to a release of sea-salt aerosols from the Bering Strait under strong wind conditions, stemming from a cyclone generated on the Chukotka Peninsula. It was also discovered that the surface ozone dropped to less than 5 ppb over the Beaufort Sea, and the overall chemical process contributed up to 10 ppb to the ozone loss. Moreover, BrO over the sea reached a maximum of approximately 80 ppt. This low-ozone air over the sea was then horizontally transported to Barrow, leading to the occurrence of ODE1. Regarding another ODE on 2 April (ODE2), we found that its occurrence was also dominated by the horizontal transport from the sea, but under the control of an anticyclone. The termination of this ODE was mainly attributed to the replenishment of ozone-rich air from the free troposphere by a strong vertical transport.

Influence of total ozone column (TOC) on the occurrence of tropospheric ozone depletion events (ODEs) in the Antarctic

Abstract. The occurrence of tropospheric ozone depletion events (ODEs) in the Antarctic can be influenced by many factors, such as the total ozone column (TOC). In this study, we analyzed the observational data obtained from ground observation stations and used two numerical models (TUV and KINAL), to discover the relationship between the TOC and the occurrence of ODEs in the Antarctic. A sensitivity analysis was also performed on ozone and major bromine species (BrO, HOBr and HBr) to find out key photolysis reactions determining the impact on the occurrence of tropospheric ODEs brought by TOC. From the analysis of the observational data and the numerical results, we suggest that the occurrence frequency of ODEs in the Antarctic is negatively associated with TOC, after screening out the impact on ODEs caused by the solar zenith angle (SZA). This negative impact of TOC on the occurrence of ODEs was suggested to be exerted through altering the solar radiation reaching the ground surface and changing the rates of photolysis reactions. Moreover, major ODE accelerating reactions (i.e., photolysis of tropospheric ozone, H2O2 and HCHO) and decelerating reactions (i.e., photolysis of BrO and HOBr), which heavily control the start of ODEs, were also identified. We found that when TOC decreases, the major ODE accelerating reactions significantly speed up. In contrast, the major ODE decelerating reactions are only slightly affected. As a result of the different impacts of TOC on photolysis reactions, the occurrence of ODEs depends negatively on TOC.

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

Abstract. The episodic buildup of gas-phase reactive bromine species over sea ice and snowpack in the springtime Arctic plays an important role in boundary layer processes, causing annual concurrent depletion of ozone and gaseous elemental mercury (GEM) 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) are all triggered by 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 study in which we successfully reproduced ODEs and MDEs at the Sea-ice Environmental Research Facility (SERF) in Winnipeg, Canada. By monitoring ozone and GEM concentrations inside large acrylic tubes over bromide-enriched artificial seawater during sea ice freeze-and-melt cycles, we observed mid-day photochemical ozone and GEM loss in winter in the in-tube 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 the presence of a condensed phase (experimental sea ice or snow) in causing such reactions were demonstrated by comparing ozone and GEM concentrations between the UV-transmitting and UV-blocking acrylic tubes under different air temperatures. The ability of reproducing BEE-induced photochemical phenomena in a mesocosm in a non-polar region provides a new approach to systematically studying the cryo-photochemical processes and meteorological conditions leading to BEEs, ODEs, and MDEs in the Arctic, their role in biogeochemical cycles across the ocean–sea ice–atmosphere interface, and their sensitivities to climate change.

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)

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.

Influence of the Background Nitrogen Oxides on the Tropospheric Ozone Depletion Events in the Arctic during Springtime

Ozone depletion events (ODEs) in the springtime of the Arctic have been frequently observed since the early 1980s, and the correlation between the ozone mixing ratio during the ODEs and the nitrogen oxides (NOx) concentration is still unclear. In the present study, the role of the background level of NOx in ODEs was investigated by using a box model implementing a chemical reaction mechanism containing 49 chemical species and 141 related reactions. A concentration sensitivity analysis was also applied to discover the dependence of the ozone mixing ratio during the ODEs on each constituent of the initial air composition. The simulation results showed that a critical value of the NOx background level exists, with which the ozone depletion rate is independent of the initial concentration of NOx, and the critical value was found to be approximately 55 ppt (ppt = part per trillion, 10−12 mol/mol) in the present study. The concentration sensitivity analysis also showed that the existence of NOx has a two-sided impact on the depletion of ozone, depending on the initial amount of NOx. With a low background level of NOx (less than 55 ppt), the increase of the initial NOx can advance the ozone depletion. On the contrary, with a high initial NOx level (more than 55 ppt), NOx would delay the consumption of ozone during the ODEs.

On the contribution of chemical oscillations to ozone depletion events in the polar spring

Abstract. This paper presents a numerical study of the oscillations (or recurrences) of tropospheric ozone depletion events (ODEs) using the further-developed one-dimensional KInetic aNALysis of reaction mechanics with Transport (KINAL-T) chemistry transport model. Reactive bromine is the major contributor to the occurrence of ODEs. After the termination of an ODE, the reactive bromine in the air is deposited onto aerosols or on the snow surface, and the ozone may regenerate via NOx-catalyzed photochemistry or by turbulent transport from the free troposphere into the boundary layer. The replenished ozone then is available for the next cycle of autocatalytic bromine release (bromine explosion) leading to another ODE. The oscillation periods are found to be as short as 5 d for the purely chemically NOx-driven oscillation and 30 d for a diffusion-driven oscillation. An important requirement for oscillation of ODEs to occur is found to be a sufficiently strong inversion layer. In a parameter study, the dependence of the oscillation period on the nitrogen oxides' concentration, the inversion layer strength, the ambient temperature, the aerosol density, and the solar radiation is investigated. Parameters controlling the oscillation of ODEs are discussed.

Role of the boundary layer in the occurrence and termination of the tropospheric ozone depletion events in polar spring

Tropospheric ozone depletion events (ODEs) in the polar spring are frequently observed in a stable boundary layer condition, and the end of the events occurs when there is a breakup of the boundary layer. In order to improve the understanding of the role of the boundary layer in the ozone depletion event, a one-dimensional model is developed, focusing on the occurrence and the termination period of the ozone depletion episode. A module accounting for the vertical air transport is added to a previous box model, and a first-order parameterization is used for the estimation of the vertical distribution of the turbulent diffusivity. Simulations are performed for different strengths of temperature inversion as well as for different wind speeds. The simulation results suggest that the reactive bromine species released from the underlying surface into the lowest part of the troposphere initially stay in the boundary layer, leading to an increase of the bromine concentration. This bromine accumulation causes the ozone destruction below the top of the boundary layer. After the ozone is totally depleted, if the temperature inversion intensity decreases or the wind speed increases, the severe ozone depletion event tends to transit into a partial ozone depletion event or it recovers to the normal ozone background level of 30–40 ppb. This recovery process takes about 2 h. Due to the presence of high-level HBr left from the initial occurrence of ODEs, the complete removal of ozone in the boundary layer is achieved a few days after the first termination of ODE. The time required for the recurrence of the ozone depletion in a 1000 m boundary layer is approximately 5 days, while the initial occurrence of the complete ozone consumption takes 15 days. The present model is suitable to clarify the reason for both the start and the termination of the severe ozone depletion as well as the partial ozone depletion in the observations.

Role of sea ice in global biogeochemical cycles: emerging views and challenges

Observations from the last decade suggest an important role of sea ice in the global biogeochemical cycles, promoted by (i) active biological and chemical processes within the sea ice; (ii) fluid and gas exchanges at the sea ice interface through an often permeable sea ice cover; and (iii) tight physical, biological and chemical interactions between the sea ice, the ocean and the atmosphere. Photosynthetic micro-organisms in sea ice thrive in liquid brine inclusions encased in a pure ice matrix, where they find suitable light and nutrient levels. They extend the production season, provide a winter and early spring food source, and contribute to organic carbon export to depth. Under-ice and ice edge phytoplankton blooms occur when ice retreats, favoured by increasing light, stratification, and by the release of material into the water column. In particular, the release of iron – highly concentrated in sea ice – could have large effects in the iron-limited Southern Ocean. The export of inorganic carbon transport by brine sinking below the mixed layer, calcium carbonate precipitation in sea ice, as well as active ice-atmosphere carbon dioxide (CO2) fluxes, could play a central role in the marine carbon cycle. Sea ice processes could also significantly contribute to the sulphur cycle through the large production by ice algae of dimethylsulfoniopropionate (DMSP), the precursor of sulphate aerosols, which as cloud condensation nuclei have a potential cooling effect on the planet. Finally, the sea ice zone supports significant ocean–atmosphere methane (CH4) fluxes, while saline ice surfaces activate springtime atmospheric bromine chemistry, setting ground for tropospheric ozone depletion events observed near both poles. All these mechanisms are generally known, but neither precisely understood nor quantified at large scales. As polar regions are rapidly changing, understanding the large-scale polar marine biogeochemical processes and their future evolution is of high priority. Earth system models should in this context prove essential, but they currently represent sea ice as biologically and chemically inert. Palaeoclimatic proxies are also relevant, in particular the sea ice proxies, inferring past sea ice conditions from glacial and marine sediment core records and providing analogues for future changes. Being highly constrained by marine biogeochemistry, sea ice proxies would not only contribute to but also benefit from a better understanding of polar marine biogeochemical cycles.

The spatial scale of ozone depletion events derived from an autonomous surface ozone network in coastal Antarctica

Abstract. To probe the spatial extent of tropospheric ozone depletion events during Antarctic spring, a network of 10 autonomous ozone monitors was established around the Dronning Maud Land sector of Antarctica for a full calendar year. Together with manned stations in the area, the network covered a ~1200 km stretch of coast, as well as a transect ~300 km inland and to ~2000 m above sea level (a.s.l.). Here we present results from the spring period (August to October 2008). While some ozone depletion events were evident at only a single site, implying localised ozone destruction, others were evident across the network. The fact that, on occasions, ozone depletion events were observed at all coastal sites simultaneously, suggests the depleted air mass had a scale of at least 1200 km. As the ozone-poor air was advected from the Weddell Sea sea ice zone, the data imply that large areas over the Weddell Sea sea ice zone are significantly depleted in ozone on occasions during Antarctic spring.

Characteristics of tropospheric ozone depletion events in the Arctic spring: analysis of the ARCTAS, ARCPAC, and ARCIONS measurements and satellite BrO observations

Abstract. Arctic ozone depletion events (ODEs) are caused by halogen catalyzed ozone loss. In situ chemistry, advection of ozone-poor air mass, and vertical mixing in the lower troposphere are important factors affecting ODEs. To better characterize the ODEs, we analyze the combined set of surface, ozonesonde, and aircraft in situ measurements of ozone and bromine compounds during the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS), the Aerosol, Radiation, and Cloud Processes affecting Arctic Climate (ARCPAC), and the Arctic Intensive Ozonesonde Network Study (ARCIONS) experiments (April 2008). Tropospheric BrO columns retrieved from satellite measurements and back trajectory calculations are also used to investigate the characteristics of observed ODEs. In situ observations from these field experiments are inadequate to validate tropospheric BrO columns derived from satellite measurements. In view of this difficulty, we construct an ensemble of tropospheric column BrO estimates from two satellite (OMI and GOME-2) measurements and with three independent methods of calculating stratospheric BrO columns. Furthermore, we select analysis methods that do not depend on the absolute magnitude of column BrO, such as time-lagged correlation analysis of ozone and tropospheric column BrO, to understand characteristics of ODEs. Time-lagged correlation analysis between in situ (surface and ozonesonde) measurements of ozone and satellite derived tropospheric BrO columns indicates that the ODEs are due to either local halogen-driven ozone loss or short-range (∼1 day) transport from nearby regions with ozone depletion. The effect of in situ ozone loss is also evident in the diurnal variation difference between low (10th and 25th percentiles) and higher percentiles of surface ozone concentrations at Alert, Canada. Aircraft observations indicate low-ozone air mass transported from adjacent high-BrO regions. Correlation analyses of ozone with potential temperature and time-lagged tropospheric BrO column show that the vertical extent of local ozone loss is surprisingly deep (1–2 km) at Resolute and Churchill, Canada. The unstable boundary layer during ODEs at Churchill could potentially provide a source of free-tropospheric BrO through convective transport and explain the significant negative correlation between free-tropospheric ozone and tropospheric BrO column at this site.

Vertical structure of Antarctic tropospheric ozone depletion events: characteristics and broader implications

Abstract. The majority of tropospheric ozone depletion event (ODE) studies have focussed on time-series measurements, with comparatively few studies of the vertical component. Those that exist have almost exclusively used free-flying balloon-borne ozonesondes and almost all have been conducted in the Arctic. Here we use measurements from two separate Antarctic field experiments to examine the vertical profile of ozone during Antarctic ODEs. We use tethersonde data to probe details in the lowest few hundred meters and find considerable structure in the profiles associated with complex atmospheric layering. The profiles were all measured at wind speeds less than 7 ms−1, and on each occasion the lowest inversion height lay between 10 m and 40 m. We also use data from a free-flying ozonesonde study to select events where ozone depletion was recorded at altitudes >1 km above ground level. Using ERA-40 meteorological charts, we find that on every occasion the high altitude depletion was preceded by an atmospheric low pressure system. An examination of limited published ozonesonde data from other Antarctic stations shows this to be a consistent feature. Given the link between BrO and ODEs, we also examine ground-based and satellite BrO measurements and find a strong association between atmospheric low pressure systems and enhanced BrO that must arise in the troposphere. The results suggest that, in Antarctica, such depressions are responsible for driving high altitude ODEs and for generating the large-scale BrO clouds observed from satellites. In the Arctic, the prevailing meteorology differs from that in Antarctica, but, while a less common effect, major low pressure systems in the Arctic can also generate BrO clouds. Such depressions thus appear to be fundamental when considering the broader influence of ODEs, certainly in Antarctica, such as halogen export and the radiative influence of ozone-depleted air masses.

Introducing the bromide/alkalinity ratio for a follow-up discussion on "Precipitation of salts in freezing seawater and ozone depletion events: a status report", by Morin et al., published in Atmos. Chem. Phys., 8, 7317–7324, 2008

Abstract. Sander et al. (2006) proposed that CaCO3 precipitation can be an important factor in triggering tropospheric ozone depletion events. Recently, Morin et al. (2008b) presented calculations with the FREZCHEM model and concluded that their results and interpretation cast doubt on the validity of this hypothesis. In this joint publication, we have re-analyzed the implications of the FREZCHEM results and show how they can be reconciled with the proposal of Sander et al. (2006). The chemical predictions of both approaches are consistent. Although an interpretation solely based on the alkalinity change in the brine does not support the conclusion of Sander et al. (2006), we show that the bromide/alkalinity ratio (which increases during the cooling of the brine) can be used as an indicator of the potential for triggering bromine explosions.

BrO, blizzards, and drivers of polar tropospheric ozone depletion events

Abstract. The source of bromine that drives polar boundary layer ozone depletion events (ODEs) is still open to some debate. While ODEs are generally noted to form under conditions of a shallow stable boundary layer, observations of depleted air under high wind conditions are taken as being transport-related. Here we report observations from Antarctica in which an unusually large cloud of BrO formed over the Weddell Sea. The enhanced BrO was observed over Halley station in coastal Antarctica, providing an opportunity to probe the conditions within an active "bromine explosion" event. On this occasion, enhanced BrO and depleted boundary layer ozone coincided with high wind speeds and saline blowing snow. We derive a simple model to consider the environmental conditions that favour ODEs and find two maxima, one at low wind/stable boundary layer and one at high wind speeds with blowing snow. Modelling calculations aiming to reproduce the wider regional or global impacts of ODEs, either via radiative effects or as a halogen source, will also need to account for high wind speed mechanisms.

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

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).

Carbonate precipitation in brine – a potential trigger for tropospheric ozone depletion events

Abstract. Tropospheric ozone depletion events (ODEs) at high latitudes were discovered 20 years ago and are attributed to bromine explosions. However, an unresolved issue is the explanation of how the acid-catalyzed reaction cycle is triggered in atmospheric particles derived from alkaline sea water. By simulating the chemistry occuring in polar regions over recently formed sea ice, we can model successfully the transformation of inert sea-salt bromide to reactive bromine monoxide (BrO) and the subsequent ODE when precipitation of calcium carbonate from freezing sea water is taken into account. In addition, we found the temperature dependence of the equilibrium BrCl+Br−↔Br2Cl− to be important.

Polar tropospheric ozone depletion events observed in the International Geophysical Year of 1958

Abstract. The Royal Society expedition to Antarctica established a base at Halley Bay, in support of the International Geophysical Year of 1957–1958. Surface ozone was measured during 1958 only, using a prototype Brewer-Mast sonde. The envelope of maximum ozone was an annual cycle from 10 ppbv in January to 22 ppbv in August. These values are 35% less at the start of the year and 15% less at the end than modern values from Neumayer, also a coastal site. This may reflect a general increase in surface ozone since 1958 and differences in summer at the less windy site of Halley, or it may reflect ozone loss on the inlet together with long-term conditioning. There were short periods in September when ozone values decreased rapidly to near-zero, and some in August when ozone values were rapidly halved. Such ozone-loss episodes, catalysed by bromine compounds, became well-known in the Artic in the 1980s, and were observed more recently in the Antarctic. In 1958, very small ozone values were recorded for a week in midwinter during clear weather with light winds. The absence of similar midwinter reductions at Neumayer, or at Halley in the few measurements during 1987, means we must remain suspicious of these small values, but we can find no obvious reason to discount them. The dark reaction of ozone and seawater ice observed in the laboratory may be fast enough to explain them if the salinity and surface area of the ice is sufficiently amplified by frost flowers.

Frost flowers on sea ice as a source of sea salt and their influence on tropospheric halogen chemistry

Frost flowers grow on newly‐formed sea ice from a saturated water vapour layer. They provide a large effective surface area and a reservoir of sea salt ions in the liquid phase with triple the ion concentration of sea water. Recently, frost flowers have been recognised as the dominant source of sea salt aerosol in the Antarctic, and it has been speculated that they could be involved in processes causing severe tropospheric ozone depletion events during the polar sunrise. These events can be explained by heterogeneous autocatalytic reactions taking place on salt‐laden ice surfaces which exponentially increase the reactive gas phase bromine (“bromine explosion”). We analyzed tropospheric bromine monoxide (BrO) and the sea ice coverage both measured from satellite sensors. Our model based interpretation shows that young ice regions potentially covered with frost flowers seem to be the source of bromine found in bromine explosion events.

Hydrocarbon measurements during tropospheric ozone depletion events: Evidence for halogen atom chemistry

During the Arctic Tropospheric Ozone Chemistry 1996 (ARCTOC 96) field campaign (March 29 to May 15, 1996), in situ measurements of C2‐C8 hydrocarbons, selected C1‐C2 halocarbons, and carbon monoxide were carried out at Ny Ålesund, Svalbard (78°55′N, 11°56′E). Two major tropospheric ozone depletions were observed during this period. In each case, concurrent depletion of alkanes and ethyne but no significant changes in benzene, chloromethane, or CO mixing ratios were detected. The change in the propane/benzene ratio can be used as evidence for the presence of chlorine radicals. Time integrated chlorine and bromine atom concentrations were calculated from the concentration changes of light alkanes and ethyne, respectively. At background ozone mixing ratios (O3 > 30 ppbv) our calculations yielded no significant integrated halogen atom concentrations (Cl: 5 ± 14 × 108 s cm−3, Br: 9 ± 42 × 1010 s cm−3). During major ozone depletion events, these values increase by more than a factor of 10 to values of about 1010 s cm−3 (Cl) and 5 × 1012 s cm−3 (Br). For such events the observed ozone losses can be explained quantitatively with these data. Our results show that free bromine atoms appear to be the major cause for ozone depletion (more than 92%). The contribution of chlorine atoms to the ozone loss is of the order of 1% or less. Highest integrated chlorine and bromine atom concentrations were found at lowest ozone mixing ratios and reached up to 1.4 × 1010 and 1.4 × 1013 s cm−3, respectively. A closer analysis reveals that during each ozone depletion event the integrated chlorine atom concentration increases earlier than the integrated bromine atom concentration and remains at high levels for a longer period of time. The bromine atom concentration starts to increase when ozone mixing ratios are below 15–20 ppbv and reaches very high levels for ozone <5 ppbv. The integrated chlorine concentration appears to be anticorrelated to the ozone mixing ratio (r2 = 0.811), whereas the integrated bromine concentration was found to be anticorrelated to the logarithm of the ozone mixing ratio (r2 = 0.895).

Short‐term variations in the 13C/12C ratio of CO as a measure of Cl activation during tropospheric ozone depletion events in the Arctic

Analyses of the CO stable isotopic composition in surface air samples collected at high northern latitudes during Arctic spring reveal significant depletions in the 13C content of atmospheric CO, which coincide with episodes of tropospheric O3 loss. This isotope signal can be explained by production of small amounts of highly 13C‐depleted CO, formed in Cl‐initiated oxidation of CH4 due to the presence of enhanced Cl levels during O3 depletion events. Using the recently measured fractionation factor for the CH4 + Cl reaction, the observed 13C depletion is employed to estimate the time‐integrated amount of Cl radicals encountered by the O3 depleted air mass. The results support findings obtained from measurements of hydrocarbon mixing ratios during O3 depletion events. The 13C content of atmospheric CO can thus be used as a sensitive indicator for enhanced Cl radical levels in the atmosphere.