Polar Boundary Layer Research Articles

A mechanism for biologically induced iodine emissions from sea ice

Abstract. Ground- and satellite-based measurements have reported high concentrations of iodine monoxide (IO) in coastal Antarctica. The sources of such a large iodine burden in the coastal Antarctic atmosphere remain unknown. We propose a mechanism for iodine release from sea ice based on the premise that micro-algae are the primary source of iodine emissions in this environment. The emissions are triggered by the biological production of iodide (I−) and hypoiodous acid (HOI) from micro-algae (contained within and underneath sea ice) and their diffusion through sea-ice brine channels, ultimately accumulating in a thin brine layer (BL) on the surface of sea ice. Prior to reaching the BL, the diffusion timescale of iodine within sea ice is depth-dependent. The BL is also a vital component of the proposed mechanism as it enhances the chemical kinetics of iodine-related reactions, which allows for the efficient release of iodine to the polar boundary layer. We suggest that iodine is released to the atmosphere via three possible pathways: (1) emitted from the BL and then transported throughout snow atop sea ice, from where it is released to the atmosphere; (2) released directly from the BL to the atmosphere in regions of sea ice that are not covered with snowpack; or (3) emitted to the atmosphere directly through fractures in the sea-ice pack. To investigate the proposed biology–ice–atmosphere coupling at coastal Antarctica we use a multiphase model that incorporates the transport of iodine species, via diffusion, at variable depths, within brine channels of sea ice. Model simulations were conducted to interpret observations of elevated springtime IO in the coastal Antarctic, around the Weddell Sea. While a lack of experimental and observational data adds uncertainty to the model predictions, the results nevertheless show that the levels of inorganic iodine (i.e. I2, IBr, ICl) released from sea ice through this mechanism could account for the observed IO concentrations during this timeframe. The model results also indicate that iodine may trigger the catalytic release of bromine from sea ice through phase equilibration of IBr. Considering the extent of sea ice around the Antarctic continent, we suggest that the resulting high levels of iodine may have widespread impacts on catalytic ozone destruction and aerosol formation in the Antarctic lower troposphere.

Interactions of bromine, chlorine, and iodine photochemistry during ozone depletions in Barrow, Alaska

Abstract. The springtime depletion of tropospheric ozone in the Arctic is known to be caused by active halogen photochemistry resulting from halogen atom precursors emitted from snow, ice, or aerosol surfaces. The role of bromine in driving ozone depletion events (ODEs) has been generally accepted, but much less is known about the role of chlorine radicals in ozone depletion chemistry. While the potential impact of iodine in the High Arctic is more uncertain, there have been indications of active iodine chemistry through observed enhancements in filterable iodide, probable detection of tropospheric IO, and recently, observation of snowpack photochemical production of I2. Despite decades of research, significant uncertainty remains regarding the chemical mechanisms associated with the bromine-catalyzed depletion of ozone, as well as the complex interactions that occur in the polar boundary layer due to halogen chemistry. To investigate this, we developed a zero-dimensional photochemical model, constrained with measurements from the 2009 OASIS field campaign in Barrow, Alaska. We simulated a 7-day period during late March that included a full ozone depletion event lasting 3 days and subsequent ozone recovery to study the interactions of halogen radicals under these different conditions. In addition, the effects of iodine added to our Base Model were investigated. While bromine atoms were primarily responsible for ODEs, chlorine and iodine were found to enhance the depletion rates and iodine was found to be more efficient per atom at depleting ozone than Br. The interaction between chlorine and bromine is complex, as the presence of chlorine can increase the recycling and production of Br atoms, while also increasing reactive bromine sinks under certain conditions. Chlorine chemistry was also found to have significant impacts on both HO2 and RO2, with organic compounds serving as the primary reaction partner for Cl atoms. The results of this work highlight the need for future studies on the production mechanisms of Br2 and Cl2, as well as on the potential impact of iodine in the High Arctic.

Aircraft‐based observations of atmospheric boundary‐layer modification over Arctic leads

Leads are elongated channels in sea ice which play an important role for the heat and moisture exchange between the polar ocean and atmosphere. The aircraft campaign STABLE aimed to improve our current understanding of the formation of convective plumes over leads and their impact on the polar atmospheric boundary layer. It was carried out over the pack ice in the northern Fram Strait in March 2013. We present case studies of the boundary layer modification and turbulent fluxes over four wide leads, which differed strongly with respect to lead characteristics and environmental conditions. The observed near‐surface sensible heat fluxes ranged from 15 to 180 W m−2. The leads also induced an increase of the near‐surface temperature of up to 3.2 °C and a humidity increase of up to 0.2 g kg−1. In one of the cases, large entrainment fluxes exceeding 30% of the surface fluxes were observed. Vertical profiles of turbulent sensible heat and momentum fluxes were nonlinear downstream of the leads with a distinct flux maximum in the core of the convective plumes. In two cases, the plumes also strongly affected the wind field within the atmospheric boundary layer. Low‐level jets that existed in those cases in the region upstream of the leads disappeared in the plume region. Finally, it is shown that large errors can occur when flux measurements are derived from lead orthogonal flight legs only. Therefore, complex flight patterns, as presented in this study, are necessary to accurately determine the energy fluxes in the environment of leads.

Steady, barotropic wind and boundary-driven circulation on a polar plane

Steady, linear, barotropic wind and boundary forced circulation solutions in the presence of linear bottom friction are analytically derived in a circular basin of uniform depth on a polar tangent plane in which only first order effects of the Earth’s curvature are retained. Approximate solutions are constructed by using the well known method of aggregating the interior inviscid Sverdrup balance solution and the frictional wall boundary layer solution. In contrast to the width of mid-latitude frictional western boundary layers that scale as , the width of the polar frictional boundary layer adjacent to the basin wall is wider, scaling as , where is the bottom friction coefficient, is the coriolis parameter. Solutions are presented for a variety of wind stress curl distributions and for a prescribed inflow/outflow representative of the exchange of water masses between the Arctic and Atlantic basins. Boundary forced solutions are also derived in a basin with a uniform width step shelf. For this basin geometry the flow is mainly confined to the shelf, although a parameter regime is identified that supports significant flow in the deep basin.

Surface-enhanced nitrate photolysis on ice.

Heterogeneous nitrate photolysis is the trigger for many chemical processes occurring in the polar boundary layer and is widely believed to occur in a quasi-liquid layer (QLL) at the surface of ice. The dipole-forbidden character of the electronic transition relevant to boundary layer atmospheric chemistry and the small photolysis/photoproduct yields in ice (and in water) may confer a significant enhancement and interfacial specificity to this important photochemical reaction at the surface of ice. Using amorphous solid water films at cryogenic temperatures as models for the disordered interstitial air-ice interface within the snowpack suppresses the diffusive uptake kinetics, thereby prolonging the residence time of nitrate anions at the surface of ice. This approach allows their slow heterogeneous photolysis kinetics to be studied, providing the first direct evidence that nitrates adsorbed onto the first molecular layer at the surface of ice are photolyzed more effectively than those dissolved within the bulk. Vibrational spectroscopy allows the ∼3-fold enhancement in photolysis rates to be correlated with the nitrates' distorted intramolecular geometry, thereby hinting at the role played by the greater chemical heterogeneity in their solvation environment at the surface of ice than that in the bulk. A simple 1D kinetic model suggests (1) that a 3(6)-fold enhancement in photolysis rate for nitrates adsorbed onto the ice surface could increase the photochemical NO2 emissions from a 5(8) nm thick photochemically active interfacial layer by 30(60)%, and (2) that 25(40)% of the NO2 photochemical emissions to the snowpack interstitial air are released from the topmost molecularly thin surface layer on ice. These findings may provide a new paradigm for heterogeneous (photo)chemistry at temperatures below those required for a QLL to form at the ice surface.

Global Hawk dropsonde observations of the Arctic atmosphere obtained during the Winter Storms and Pacific Atmospheric Rivers (WISPAR) field campaign

Abstract. In February and March of 2011, the Global Hawk unmanned aircraft system (UAS) was deployed over the Pacific Ocean and the Arctic during the Winter Storms and Pacific Atmospheric Rivers (WISPAR) field campaign. The WISPAR science missions were designed to (1) mprove our understanding of Pacific weather systems and the polar atmosphere; (2) evaluate operational use of unmanned aircraft for investigating these atmospheric events; and (3) demonstrate operational and research applications of a UAS dropsonde system at high latitudes. Dropsondes deployed from the Global Hawk successfully obtained high-resolution profiles of temperature, pressure, humidity, and wind information between the stratosphere and surface. The 35 m wingspan Global Hawk, which can soar for ~ 31 h at altitudes up to ~ 20 km, was remotely operated from NASA's Dryden Flight Research Center at Edwards Air Force Base (AFB) in California. During the 25 h polar flight on 9–10 March 2011, the Global Hawk released 35 sondes between the North Slope of Alaska and 85° N latitude, marking the first UAS Arctic dropsonde mission of its kind. The polar flight transected an unusually cold polar vortex, notable for an associated record-level Arctic ozone loss, and documented polar boundary layer variations over a sizable ocean–ice lead feature. Comparison of dropsonde observations with atmospheric reanalyses reveal that, for this day, large-scale structures such as the polar vortex and air masses are captured by the reanalyses, while smaller-scale features, including low-level jets and inversion depths, are mischaracterized. The successful Arctic dropsonde deployment demonstrates the capability of the Global Hawk to conduct operations in harsh, remote regions. The limited comparison with other measurements and reanalyses highlights the potential value of Arctic atmospheric dropsonde observations where routine in situ measurements are practically nonexistent.

Air–snowpack exchange of bromine, ozone and mercury in the springtime Arctic simulated by the 1-D model PHANTAS – Part 1: In-snow bromine activation and its impact on ozone

Abstract. To provide a theoretical framework towards a better understanding of ozone depletion events (ODEs) and atmospheric mercury depletion events (AMDEs) in the polar boundary layer, we have developed a one-dimensional model that simulates multiphase chemistry and transport of trace constituents from porous snowpack and through the atmospheric boundary layer (ABL) as a unified system. This paper constitutes Part 1 of the study, describing a general configuration of the model and the results of simulations related to reactive bromine release from the snowpack and ODEs during the Arctic spring. A common set of aqueous-phase reactions describes chemistry both within the liquid-like layer (LLL) on the grain surface of the snowpack and within deliquesced "haze" aerosols mainly composed of sulfate in the atmosphere. Gas-phase reactions are also represented by the same mechanism in the atmosphere and in the snowpack interstitial air (SIA). Consequently, the model attains the capacity of simulating interactions between chemistry and mass transfer that become particularly intricate near the interface between the atmosphere and the snowpack. In the SIA, reactive uptake on LLL-coated snow grains and vertical mass transfer act simultaneously on gaseous HOBr, a fraction of which enters from the atmosphere while another fraction is formed via gas-phase chemistry in the SIA itself. A "bromine explosion", by which HOBr formed in the ambient air is deposited and then converted heterogeneously to Br2, is found to be a dominant process of reactive bromine formation in the top 1 mm layer of the snowpack. Deeper in the snowpack, HOBr formed within the SIA leads to an in-snow bromine explosion, but a significant fraction of Br2 is also produced via aqueous radical chemistry in the LLL on the surface of the snow grains. These top- and deeper-layer productions of Br2 both contribute to the release of Br2 to the atmosphere, but the deeper-layer production is found to be more important for the net outflux of reactive bromine. Although ozone is removed via bromine chemistry, it is also among the key species that control both the conventional and in-snow bromine explosions. On the other hand, aqueous-phase radical chemistry initiated by photolytic OH formation in the LLL is also a significant contributor to the in-snow source of Br2 and can operate without ozone, whereas the delivery of Br2 to the atmosphere becomes much smaller after ozone is depleted. Catalytic ozone loss via bromine radical chemistry occurs more rapidly in the SIA than in the ambient air, giving rise to apparent dry deposition velocities for ozone from the air to the snow on the order of 10−3 cm s−1 during daytime. Overall, however, the depletion of ozone in the system is caused predominantly by ozone loss in the ambient air. Increasing depth of the turbulent ABL under windy conditions will delay the buildup of reactive bromine and the resultant loss of ozone, while leading to the higher column amount of BrO in the atmosphere. During the Arctic spring, if moderately saline and acidic snowpack is as prevalent as assumed in our model runs on sea ice, the shallow, stable ABL under calm weather conditions may undergo persistent ODEs without substantial contributions from blowing/drifting snow and wind-pumping mechanisms, whereas the column densities of BrO in the ABL will likely remain too low in the course of such events to be detected unambiguously by satellite nadir measurements.

Ekman dynamics of the atmospheric boundary layer over the Antarctic Plateau in summer

The dynamics of the polar atmospheric boundary layer and its impact on the global atmospheric circulation are important issues in earth science research. We used GPS sounding data collected during summer 2012-2013 at Kunlun Station, Antarctica, to analyze dynamic characteristics of the atmospheric boundary layer over the Antarctic Plateau. Results showed that observed changes in wind speed and direction with height in the boundary layer coincided with the theoretical calculation of the Ekman spiral. The wind speed increased rapidly with height and the wind direction moved to the left. The vertical structure was therefore characteristic of the Ekman layer in the Southern Hemisphere. The Ekman boundary layer was high in the atmosphere, from 900 to 3400 m, with a dry, cold, and stable stratification throughout the layer, while the convective mixing layer was below 900 m. Our observations revealed a complex and dynamic structure in the atmospheric boundary layer over the Antarctic Plateau. Ekman equation calculations showed that turbulent friction stress over the Antarctic Plateau is significantly higher than over the lower latitudes. Dynamic friction from the atmospheric boundary layer over the Antarctic Plateau is likely to have important impacts on the global atmospheric circulation.

Numerical simulation of tropospheric ozone depletion in the polar spring

This study addresses the modeling of the tropospheric ozone depletion event in polar spring where the aim is an improved understanding of the underlying physical and chemical processes. For this purpose, a model is developed and implemented into the open source software Open source Field Operations And Manipulations (OpenFOAM). A detailed chemical reaction mechanism is analyzed with the software package KInetic aNALysis of reaction mechanics (KINAL), and a skeletal mechanism is derived for use in the three-dimensional simulations. The 3D compressible Navier–Stokes equations are solved to predict the effect of turbulent mixing, advection of the fluid, and chemical reactions. Large eddy simulation accounts for the turbulence, and the Smagorinsky model is employed as sub-grid model. The temporal and spatial distributions of the chemical species are captured. The mixing ratio of ozone in the troposphere drops to a value near zero within several days including an “induction stage” and a “depletion stage,” which confirms previous findings. Moreover, the vertical turbulent mixing of air parcels occurs below the height of the polar boundary layer, leading to a nonuniform vertical distribution of the chemical species concentrations. Both the wind speed and the boundary layer stability may affect the boundary layer height, thus influencing the ozone depletion rate.

Two years of atmospheric boundary layer observations on a 45‐m tower at Dome C on the Antarctic plateau

The lower atmospheric boundary layer at Dome C on the Antarctic plateau has been continuously monitored along a 45‐m tower since 2009. Two years of observations (2009 and 2010) are presented. A strong diurnal cycle is observed near the surface in summer but almost disappears at the top of the tower, indicating that the summer nocturnal inversion is very shallow. Very steep inversions reaching almost 1 °C m−1 on average along the tower are observed in winter. They are stronger and more frequent during the colder 2010 winter, reaching a maximum in a layer ~10–15 m above the surface. Winter temperature is characterized by strong synoptic variability. An extreme warm event occurred in July 2009. The temperature reached −30 °C, typical of midsummer weather. Meteorological analyses which agree with the observations near the surface confirm that heat is propagated downward from higher elevations. A high total water column indicates moist air masses aloft originating from the lower latitudes. The coldest temperatures and strongest inversions are associated with characteristic synoptic patterns and a particularly dry atmosphere. Measurement of moisture in the clean and cold Antarctic plateau atmosphere is a challenging task. Supersaturations are very likely but are not revealed by the observations. This is possibly an instrumental artifact that would affect other moisture measurements made in similar conditions. In spite of this, such observations offer a stringent test of the robustness of the polar boundary layer in meteorological and climate models, addressing a major concern raised in the IPCC 2007 report.

Polar boundary layer processes: Important factors for investigating biogeochemistry and climate

Ice at the Interface: Atmosphere‐Ice‐Ocean Boundary Layer Processes and Their Role in Polar Change; Boulder, Colorado, 25–27 June 2012 The atmosphere‐ocean boundary layer in which sea ice resides includes many complex physical processes requiring a more realistic treatment in climate models, particularly as models incorporate biogeochemical feedback mechanisms such as aerosol effects on clouds. The primary purpose of a workshop recently held at the National Oceanic and Atmospheric Administration's David Skaggs Research Center was to define and discuss such coupled processes. Several scientific themes crucial for biogeochemical cycling emerged from the workshop, such as the importance of episodic events, precipitation, stratification, and the marginal ice zone.

Halogen activation via interactions with environmental ice and snow in the polar lower troposphere and other regions

Abstract. The role of ice in the formation of chemically active halogens in the environment requires a full understanding because of its role in atmospheric chemistry, including controlling the regional atmospheric oxidizing capacity in specific situations. In particular, ice and snow are important for facilitating multiphase oxidative chemistry and as media upon which marine algae live. This paper reviews the nature of environmental ice substrates that participate in halogen chemistry, describes the reactions that occur on such substrates, presents the field evidence for ice-mediated halogen activation, summarizes our best understanding of ice-halogen activation mechanisms, and describes the current state of modeling these processes at different scales. Given the rapid pace of developments in the field, this paper largely addresses advances made in the past five years, with emphasis given to the polar boundary layer. The integrative nature of this field is highlighted in the presentation of work from the molecular to the regional scale, with a focus on understanding fundamental processes. This is essential for developing realistic parameterizations and descriptions of these processes for inclusion in larger scale models that are used to determine their regional and global impacts.

Kinetic studies on the temperature dependence of the BrO + BrO reaction using laser flash photolysis

The BrO self-reaction, BrO + BrO → products (1), has been studied using laser flash photolysis coupled with UV absorption spectroscopy over the temperature range T = 266.5-321.6 K, under atmospheric pressure. BrO radicals were generated via laser photolysis of Br(2) in the presence of excess ozone. Both BrO and O(3) were monitored via UV absorption spectroscopy using charge-coupled device (CCD) detection. Simultaneous fitting to both temporal concentration traces allowed determination of the rate constant of the two channels of , BrO + BrO → 2Br + O(2) (1a); BrO + BrO → Br(2) + O(2) (1b), hence the calculation of the overall rate of and the branching ratio, α: k(1a)/cm(3) molecule(-1) s(-1) = (1.92 ± 1.54) × 10(-12) exp[(126 ± 214)/T], k(1b)/cm(3) molecule(-1) s(-1) = (3.4 ± 0.8) × 10(-13) exp[(181 ± 70)/T], k(1)/cm(3) molecule(-1) s(-1) = (2.3 ± 1.5) × 10(-12) exp(134 ± 185 /T) and α = k(1a)/k(1) = (0.84 ± 0.09) exp[(-7 ± 32)/T]. Errors are 1σ, statistical only. Results from this work show a weaker temperature dependence of the branching ratio for channel (1a) than that found in previous work, leading to values of α at temperatures typical of the Polar Boundary Layer higher than those reported by previous studies. This implies a shift of the partitioning between the two channels of the BrO self-reaction towards the bromine atom and hence directly ozone-depleting channel (1a).

Freeze-Induced Reactions: Formation of Iodine−Bromine Interhalogen Species from Aqueous Halide Ion Solutions

Interhalide ion formation resulting from the freezing of dilute solutions containing components found in natural sea salt are investigated as a potential mechanism for the release of interhalogens to the polar atmosphere. Acidified solutions containing iodide, bromide, and nitrite ions have been frozen and then thawed, with changes in speciation analyzed using UV-visible spectrophotometry. The freezing process is shown to induce the formation of the important interhalide ion, IBr(2)(-). This species has previously been predicted to be a precursor of iodine monobromide, IBr, and represents a potentially important source of halogen atoms in the polar marine boundary layer. The reaction mechanisms that lead to the formation of IBr(2)(-) under freezing conditions are explored using both experimental and computational methodologies. The chemistry involved was subsequently modified in order to mimic naturally occurring conditions more closely and also incorporated the use of hydrogen peroxide as an oxidant. In contrast to previous studies, the freeze-induced production of IBr(2)(-) was thereby observed to occur up to pH <5.1, where the acidity levels are comparable to those found in the polar snowpack.

Spectroscopic studies of the heterogeneous reaction between O3(g) and halides at the surface of frozen salt solutions

Springtime ozone depletion events have been linked to elevated levels of bromine in the polar boundary layer. It has also been suggested that iodine may play an important role in boundary layer chemistry. However, the mechanism(s) for initial halogen activation is not well understood. We report results of experiments using glancing‐angle laser‐induced fluorescence (LIF) and glancing‐angle Raman spectroscopy to investigate the heterogeneous reaction of gas‐phase ozone with bromide and iodide ions at the surface of frozen salt solutions. The results suggest that halides that have been excluded to the ice surface during the freezing process react in the dark and under non‐acidified conditions to produce molecular halogen species. At environmentally relevant bromide concentrations, the reaction proceeds ∼60 times more rapidly at ice surfaces than at the surface of aqueous solutions. At an ozone concentration of ∼8 × 1015 molec cm−3, and sea water concentrations of bromide and iodide, we estimate uptake coefficients γ(Br−) = (1.3 ± 0.5) × 10−8 and γ(I−) = (1.6 ± 0.5) × 10−9. We estimate that at atmospheric ozone concentrations, the uptake coefficients will be approximately a factor of ten greater.

Observation of halogen species in the Amundsen Gulf, Arctic, by active long-path differential optical absorption spectroscopy

In the polar tropospheric boundary layer, reactive halogen species (RHS) are responsible for ozone depletion as well as the oxidation of elemental mercury and dimethyl sulphide. After polar sunrise, air masses enriched in reactive bromine cover areas of several million square kilometers. Still, the source and release mechanisms of halogens are not completely understood. We report measurements of halogen oxides performed in the Amundsen Gulf, Arctic, during spring 2008. Active long-path differential optical absorption spectroscopy (LP-DOAS) measurements were set up offshore, several kilometers from the coast, directly on the sea ice, which was never done before. High bromine oxide concentrations were detected frequently during sunlight hours with a characteristic daily cycle showing morning and evening maxima and a minimum at noon. The, so far, highest observed average mixing ratio in the polar boundary layer of 41 pmol/mol (equal to pptv) was detected. Only short sea ice contact is required to release high amounts of bromine. An observed linear decrease of maximum bromine oxide levels with ambient temperature during sunlight, between -24 degrees C and -15 degrees C, provides indications on the conditions required for the emission of RHS. In addition, the data indicate the presence of reactive chlorine in the Arctic boundary layer. In contrast to Antarctica, iodine oxide was not detected above a detection limit of 0.3 pmol/mol.

Modelling the multiphase near-surface chemistry related to ozone depletions in polar spring

Near-total depletions of ozone have been observed in the Arctic spring since the mid 1980s. The autocatalytic reaction cycles involving reactive halogens are now recognized to be of main importance for ozone depletion events in the polar boundary layer. We present sensitivity studies using the model MISTRA in the box-model mode on the influence of chemical species on these ozone depletion processes. In order to test the sensitivity of the chemistry under polar conditions, we compared base runs undergoing fluxes of either Br2, BrCl, or Cl2 to induce ozone depletions, with similar runs including a modification of the chemical conditions. The role of HCHO, H2O2, DMS, Cl2, C2H6, HONO, NO2, and RONO2 was investigated. Cases with elevated mixing ratios of HCHO, H2O2, DMS, Cl2, and HONO induced a shift in bromine speciation from Br / BrO to HOBr/HBr, while high mixing ratios of C2H6 induced a shift from HOBr/HBr to Br/BrO. The shifts from Br/BrO to HOBr/HBr accelerated the aerosol debromination, but also increased the total amount of deposited bromine at the surface (mainly via increased deposition of HOBr). For all NOy species studied (HONO, NO2, RONO2) the chemistry is characterized by an increased bromine deposition on snow reducing the amount of reactive bromine in the air. Ozone is less depleted under conditions of high mixing ratios of NOx. The production of HNO3 led to the acid displacement of HCl, and the release of chlorine out of salt aerosol (Cl2 or BrCl) increased.

A DFT study of the reactions of O 3 with Hg° or Br −

In the mid 1980s the study of ozone reactivity gained a significant interest with the discoveries of the stratospheric ozone hole ( Farman et al., 1985) and of the ozone depletion events in the polar boundary layer ( Oltmans et al., 1989). In the stratosphere, the mechanism involves heterogeneous reactions on polar stratospheric clouds that lead to chlorine activation ( Solomon et al., 1986). In contrast, tropospheric ozone depletion occurring during polar springtime rather involves reactive bromine species. They are released during a series of photochemical and heterogeneous reactions often called the bromine explosion (see the review of Simpson et al., 2007). In this reaction sequence, an essential step is the generation of photolyzable Br 2, the precursor of two Br atoms, via the multiphasic reaction (1): (1) HOBr + Br − + H + → H 2O + Br 2 The production of reactive HOBr could occur with the oxidation of BrO by HO 2.

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.

Radiative Processes in the Stable Boundary Layer: Part I. Radiative Aspects

The structure of the radiatively dominated stable boundary layer is analysed using idealized calculations at high vertical and spectral resolution. The temperature profile of a nocturnal radiative boundary layer, developing after the evening transition, is found to be well described in terms of radiative cooling to the surface, although radiative exchanges within the atmosphere become increasingly important with time. The treatment of non-black surfaces is discussed in some detail and it is shown that the effect of reducing the surface emissivity is to decrease rather than to increase the radiative cooling rate in the surface layer. It is also argued that an accurate assessment of the impact of non-black surfaces requires careful attention to the spectral and directional characteristics of the surface emissivity. A polar nocturnal boundary layer, developing above snow-covered ground, is simulated and found to reach a slowly evolving state characterized by a strong radiative divergence near the surface that is comparable to observed values. Radiative boundary layers are characterized by large temperature gradients near the surface.