Catalytic Destruction Of Ozone Research Articles

Spontaneous Molecular Bromine Production in Sea-Salt Aerosols.

Bromine chemistry is responsible for the catalytic ozone destruction in the atmosphere. The heterogeneous reactions of sea-salt aerosols are the main abiotic sources of reactive bromine in the atmosphere. Here, we present a novel mechanism for the activation of bromide ions (Br-) by O2 and H2O in the absence of additional oxidants. The laboratory and theoretical calculation results demonstrated that under dark conditions, Br-, O2 and H3O+ could spontaneously generate Br and HO2 radicals through a proton-electron transfer process at the air-water interface and in the liquid phase. Our results also showed that light and acidity could significantly promote the activation of Br- and the production of Br2. The estimated gaseous Br2 production rate was up to 1.55×1010 molecules cm-2 ⋅ s-1 under light and acidic conditions; these results showed a significant contribution to the atmospheric reactive bromine budget. The reactive oxygen species (ROS) generated during Br- activation could promote the multiphase oxidation of SO2 to produce sulfuric acid, while the increase in acidity had a positive feedback effect on Br- activation. Our findings highlight the crucial role of the proton-electron transfer process in Br2 production; here, H3O+ facilitates the activation of Br- by O2, serves as a significant source of atmospheric reactive bromine and exerts a profound impact on the atmospheric oxidation capacity.

Beyond self-healing: stabilizing and destabilizing photochemical adjustment of the ozone layer

Abstract. The ozone layer is often noted to exhibit self-healing, whereby depletion of ozone aloft induces ozone increases below, explained as resulting from enhanced ozone production due to the associated increase in ultraviolet (UV) radiation below. Similarly, ozone enhancement aloft can reduce ozone below (reverse self-healing). This paper considers self-healing and reverse self-healing to manifest a general mechanism we call photochemical adjustment, whereby ozone perturbations lead to a downward cascade of anomalies in UV and ozone. Conventional explanations for self-healing imply that photochemical adjustment is stabilizing, damping perturbations towards the surface. However, photochemical adjustment can be destabilizing if the enhanced UV disproportionately increases the ozone sink, as can occur if the enhanced UV photolyzes ozone to produce atomic oxygen, which speeds up catalytic destruction of ozone. We analyze photochemical adjustment in two linear ozone models (Cariolle v2.9 and LINOZ), finding that (1) photochemical adjustment is destabilizing above 40 km in the tropical stratosphere and (2) self-healing often represents only a small fraction of the total photochemical stabilization. The destabilizing regime above 40 km is reproduced in a much simpler model: the Chapman cycle augmented with destruction of O and O3 by generalized catalytic cycles and transport (the Chapman+2 model). The Chapman+2 model reveals that photochemical destabilization occurs where the ozone sink is more sensitive than the source to perturbations in overhead column ozone, which is found to occur when the window of overlapping absorption by O2 and O3 is optically unsaturated, i.e., when overhead slant column ozone is below approximately 1018 molec. cm−2.

Spontaneous Molecular Bromine Production in Sea‐Salt Aerosols

AbstractBromine chemistry is responsible for the catalytic ozone destruction in the atmosphere. The heterogeneous reactions of sea‐salt aerosols are the main abiotic sources of reactive bromine in the atmosphere. Here, we present a novel mechanism for the activation of bromide ions (Br−) by O2 and H2O in the absence of additional oxidants. The laboratory and theoretical calculation results demonstrated that under dark conditions, Br−, O2 and H3O+ could spontaneously generate Br and HO2 radicals through a proton–electron transfer process at the air–water interface and in the liquid phase. Our results also showed that light and acidity could significantly promote the activation of Br− and the production of Br2. The estimated gaseous Br2 production rate was up to 1.55×1010 molecules cm−2 ⋅ s−1 under light and acidic conditions; these results showed a significant contribution to the atmospheric reactive bromine budget. The reactive oxygen species (ROS) generated during Br− activation could promote the multiphase oxidation of SO2 to produce sulfuric acid, while the increase in acidity had a positive feedback effect on Br− activation. Our findings highlight the crucial role of the proton‐electron transfer process in Br2 production; here, H3O+ facilitates the activation of Br− by O2, serves as a significant source of atmospheric reactive bromine and exerts a profound impact on the atmospheric oxidation capacity.

Implications of Snowpack Reactive Bromine Production for Arctic Ice Core Bromine Preservation

AbstractSnowpack emissions are recognized as an important source of gas‐phase reactive bromine in the Arctic and are necessary to explain ozone depletion events in spring caused by the catalytic destruction of ozone by halogen radicals. Quantifying bromine emissions from snowpack is essential for interpretation of ice‐core bromine. We present ice‐core bromine records since the pre‐industrial (1750 CE) from six Arctic locations and examine potential post‐depositional loss of snowpack bromine using a global chemical transport model. Trend analysis of the ice‐core records shows that only the high‐latitude coastal Akademii Nauk (AN) ice core from the Russian Arctic preserves significant trends since pre‐industrial times that are consistent with trends in sea ice extent and anthropogenic emissions from source regions. Model simulations suggest that recycling of reactive bromine on the snow skin layer (top 1 mm) results in 9–17% loss of deposited bromine across all six ice‐core locations. Reactive bromine production from below the snow skin layer and within the snow photic zone is potentially more important, but the magnitude of this source is uncertain. Model simulations suggest that the AN core is most likely to preserve an atmospheric signal compared to five Greenland ice cores due to its high latitude location combined with a relatively high snow accumulation rate. Understanding the sources and amount of photochemically reactive snow bromide in the snow photic zone throughout the sunlit period in the high Arctic is essential for interpreting ice‐core bromine, and warrants further lab studies and field observations at inland locations.

The future ozone trends in changing climate simulated with SOCOLv4

Abstract. This study evaluates the future evolution of atmospheric ozone simulated with the Earth system model (ESM) SOCOLv4. Simulations have been performed based on two potential shared socioeconomic pathways (SSPs): the middle-of-the-road (SSP2-4.5) and fossil-fueled (SSP5-8.5) scenarios. The future changes in ozone, as well as in chemical drivers (NOx and CO) and temperature, were estimated between 2015 and 2099 and for several intermediate subperiods (i.e., 2015–2039, 2040–2069, and 2070–2099) via dynamic linear modeling. In both scenarios, the model projects a decline in tropospheric ozone in the future that starts in the 2030s in SSP2-4.5 and after the 2060s in SSP5-8.5 due to a decrease in concentrations of NOx and CO. The results also suggest a very likely ozone increase in the mesosphere and the upper and middle stratosphere, as well as in the lower stratosphere at high latitudes. Under SSP5-8.5, the ozone increase in the stratosphere is higher because of stronger cooling (>1 K per decade) induced by greenhouse gases (GHGs), which slows the catalytic ozone destruction cycles. In contrast, in the tropical lower stratosphere, ozone concentrations decrease in both experiments and increase over the middle and high latitudes of both hemispheres due to the speeding up of the Brewer–Dobson circulation, which is stronger in SSP5-8.5. No evidence was found of a decline in ozone levels in the lower stratosphere at mid-latitudes. In both future scenarios, the total column ozone is expected to be distinctly higher than present in middle to high latitudes and might be lower in the tropics, which causes a decrease in the mid-latitudes and an increase in the tropics in the surface level of ultraviolet radiation. The results of SOCOLv4 suggest that the stratospheric-ozone evolution throughout the 21st century is strongly governed not only by a decline in halogen concentration but also by future GHG forcing. In addition, the tropospheric-ozone column changes, which are mainly due to the changes in anthropogenic emissions of ozone precursors, also have a strong impact on the total column. Therefore, even though the anthropogenic halogen-loading problem has been brought under control to date, the sign of future ozone column changes, globally and regionally, is still unclear and largely depends on diverse future human activities. The results of this work are, thus, relevant for developing future strategies for socioeconomic pathways.

Long-term mesospheric record of EPP-IE NO measured by Odin/SMR

Due to the long lifetime of nitric oxide (NO) in darkness conditions, during polar winter, the NO produced by energetic particle precipitation (EPP) in the mesosphere and lower thermosphere (MLT) can descend, via the middle atmospheric residual circulation, to the lower mesosphere and stratosphere, where it is involved in catalytic destruction of ozone (O3). This process is known as energetic particle precipitation indirect effect (EPP-IE). There are still significant uncertainties on the estimated amount of EPP-IE NO. To improve such estimations, we measure the total winter flux of EPP-IE NO descending through three isentropic levels in the mesosphere, that is 2600K, 3300K and 4000K, based on 15 years of NO nighttime observations from the Sub-Millimetre Radiometer (SMR) on board Odin satellite. At the moment, Odin/SMR is the only instrument ensuring a global coverage of mesospheric NO observations within a few days and this is the first time EPP-IE NO has been quantified using its NO data set. Moreover, such an estimate had never been calculated for the most recent winters which are included in this study. In our method we calculate the median nighttime NO inside the polar vortex during the month prior to the descent of NO-rich air; this value is assumed as a background, produced by N2O oxidation, to be subtracted from the daily median nighttime concentrations inside the vortex; the result of this subtraction is then multiplied by the area of the vortex and the descent rate to obtain the flux; finally these daily quantities and integrated to calculate the total NO flux for each winter. We thus calculated the total EPP-IE NO flux through the mentioned levels for Northern Hemisphere (NH) winters between 2006–07 and 2020–21 and for Southern Hemisphere (SH) winters between 2007 and 2012. The total winter EPP-IE NO fluxes presented in this study are consistent with the quantities presented in similar studies. NH winters 2008–09, 2012–13 and 2018–19 are the ones presenting the highest NO fluxes at all levels. They are winters characterised by sudden stratospheric warmings followed by elevated stratopause (SSW-ES) events. The measured fluxes vary between 490 and 1000 Mmol at 4000K, 310 and 720 Mmol at 3300K, 270 and 510 Mmol at 2600K. All other NH and SH winters are characterised by sensibly lower values than SSW-ES winters. The fluxes from these more dynamically quiet winters vary from winter to winter following a trend similar to the one of geomagnetic activity, as indicated by the variations in Ap index. These results indicate that the variability in the total EPP-IE NO fluxes is dominated by dynamics during the SSW-ES winters, whereas during the remaining winters it is geomagnetic activity that plays a major role.

Ozone catalytic oxidation of low-concentration formaldehyde over ternary Mn-Ce-Ni oxide catalysts modified with FeOx.

Manganese oxide-based catalysts have attracted extensive attention due to their relatively low cost and remarkable performance for removing VOCs. In this research, we used the Pechini method to synthesize manganese-cerium-nickel ternary oxide catalysts (MCN) and evaluated the effectiveness of catalytic destruction of formaldehyde (HCHO) and ozone at room temperature. FeOx prepared by the impregnation method was applied to modify the catalyst. After FeOx treatment, the catalyst represented the best performance on both HCHO destruction and ozone decomposition under dry conditions and exhibited excellent water vapor resistance.The as-prepared catalystswere next characterized via H2-temperature programmed reduction (H2-TPR), temperature programmed desorption of O2 (O2-TPD), and X-ray photoelectron spectroscopy (XPS), and the results demonstrated that addition of FeOx increased Mn3+ and Ce3+ concentrations, oxygen vacancies and surface lattice oxygen species, facilitated adsorption, and redox properties. Based on the results of in situ diffuse reflectance infrared Fourier transform spectrometry (DRIFTS), possible mechanisms of ozone catalytic oxidation of HCHO were proposed. Overall, the ternary mixed-oxide catalyst developed in this study holds great promise for HCHO and ozone decomposition in the indoor environment.

Impact of stratospheric planetary wave and ozone variabilities on the austral polar middle atmospheric circulation

Analysis of the meteor radar wind observations in the upper mesosphere and lower thermosphere (UMLT) region (82–98 km) over Rothera (67.5°S, 68.1°W) reveals that the monthly mean zonal winds show a large interannual variability during November-December, when compared to other months. Large westward winds are observed during November-December of the years 2006–2011, 2015, 2018 and 2020, when the amount of ozone loss is more in the southern high-latitude stratosphere (57.5°S–77.5°S). The ERA-5 reanalysis winds at 30 hPa over 67.5°S also show an interannual variability with large eastward winds at stratospheric heights during October-November of those years. The presence of high meridional heat flux due primarily to the planetary wave (PW) of zonal wavenumber 1 in the other years increases the polar stratospheric temperature and subsequently reduces the catalytic destruction of ozone by preventing the formation of polar stratospheric clouds (PSCs). Further, it is also found that the ozone loss influences the migrating semi-diurnal (SW2) tidal variabilities at upper mesospheric heights with low activity corresponding to the years having more ozone loss. These results indicate the impact of planetary waves on the catalytic destruction of Antarctic ozone leading to the circulation and tidal amplitude changes extending up to the UMLT region.

Catalytic Destruction of Ozone in the Gas Systems of Accelerator Detector Units

The physicochemical calculations of the required amount of the GTT grade goptalum catalyst of ozone decomposition and the pressure drop on the catalyst bed under the operating conditions of the gas systems of particle accelerators were presented. The results of calculations were compared with the experimental data obtained in the gas system of the ATLAS detector unit of the Large Hadron Collider. The obtained physicochemical data make it possible to optimize the parameters of ozone filter destructors and the amount of catalyst required for purification of gas mixtures from ozone in detector units of accelerators.

Observational evidence of energetic particle precipitation NO<sub><i>x</i></sub> (EPP-NO<sub><i>x</i></sub>) interaction with chlorine curbing Antarctic ozone loss

Abstract. We investigate the impact of the so-called energetic particle precipitation (EPP) indirect effect on lower stratospheric ozone, ClO, and ClONO2 in the Antarctic springtime. We use observations from the Microwave Limb Sounder (MLS) and Ozone Monitoring Instrument (OMI) on Aura, the Atmospheric Chemistry Experiment – Fourier Transform Spectrometer (ACE-FTS) on SCISAT, and the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on Envisat, covering the period from 2005 to 2017. Using the geomagnetic activity index Ap as a proxy for EPP, we find consistent ozone increases with elevated EPP during years with an easterly phase of the quasi-biennial oscillation (QBO) in both OMI and MLS observations. While these increases are the opposite of what has previously been reported at higher altitudes, the pattern in the MLS O3 follows the typical descent patterns of EPP-NOx. The ozone enhancements are also present in the OMI total O3 column observations. Analogous to the descent patterns found in O3, we also found consistent decreases in springtime MLS ClO following winters with elevated EPP. To verify if this is due to a previously proposed mechanism involving the conversion of ClO to the reservoir species ClONO2 in reaction with NO2, we used ClONO2 observations from ACE-FTS and MIPAS. As ClO and NO2 are both catalysts in ozone destruction, the conversion to ClONO2 would result in an ozone increase. We find a positive correlation between EPP and ClONO2 in the upper stratosphere in the early spring and in the lower stratosphere in late spring, providing the first observational evidence supporting the previously proposed mechanism relating to EPP-NOx modulating Clx-driven ozone loss. Our findings suggest that EPP has played an important role in modulating ozone depletion in the last 15 years. As chlorine loading in the polar stratosphere continues to decrease in the future, this buffering mechanism will become less effective, and catalytic ozone destruction by EPP-NOx will likely become a major contributor to Antarctic ozone loss.

Evaluation of polar stratospheric clouds in the global chemistry–climate model SOCOLv3.1 by comparison with CALIPSO spaceborne lidar measurements

Abstract. Polar stratospheric clouds (PSCs) contribute to catalytic ozone destruction by providing surfaces for the conversion of inert chlorine species into active forms and by denitrification. The latter describes the removal of HNO3 from the stratosphere by sedimenting PSC particles, which hinders chlorine deactivation by the formation of reservoir species. Therefore, an accurate representation of PSCs in chemistry–climate models (CCMs) is of great importance to correctly simulate polar ozone concentrations. Here, we evaluate PSCs as simulated by the CCM SOCOLv3.1 for the Antarctic winters 2006, 2007 and 2010 by comparison with backscatter measurements by CALIOP on board the CALIPSO satellite. The year 2007 represents a typical Antarctic winter, while 2006 and 2010 are characterized by above- and below-average PSC occurrence. The model considers supercooled ternary solution (STS) droplets, nitric acid trihydrate (NAT) particles, water ice particles and mixtures thereof. PSCs are parameterized in terms of temperature and partial pressures of HNO3 and H2O, assuming equilibrium between the gas and particulate phase. The PSC scheme involves a set of prescribed microphysical parameters, namely ice number density, NAT particle radius and maximum NAT number density. In this study, we test and optimize the parameter settings through several sensitivity simulations. The choice of the value for the ice number density affects simulated optical properties and dehydration, while modifying the NAT parameters impacts stratospheric composition via HNO3 uptake and denitrification. Depending on the NAT parameters, reasonable denitrification can be modeled. However, its impact on ozone loss is minor. The best agreement with the CALIOP optical properties and observed denitrification was for this case study found with the ice number density increased from the hitherto used value of 0.01 to 0.05 cm−3 and the maximum NAT number density from 5×10-4 to 1×10-3 cm−3. The NAT radius was kept at the original value of 5 µm. The new parameterization reflects the higher importance attributed to heterogeneous nucleation of ice and NAT particles following recent new data evaluations of the state-of-the-art CALIOP measurements. A cold temperature bias in the polar lower stratosphere results in an overestimated PSC areal coverage in SOCOLv3.1 by up to 40 %. Offsetting this cold bias by +3 K delays the onset of ozone depletion by about 2 weeks, which improves the agreement with observations. Furthermore, the occurrence of mountain-wave-induced ice, as observed mainly over the Antarctic Peninsula, is continuously underestimated in the model due to the coarse model resolution (T42L39) and the fixed ice number density. Nevertheless, we find overall good temporal and spatial agreement between modeled and observed PSC occurrence and composition. This work confirms previous studies indicating that simplified PSC schemes, which avoid nucleation and growth calculations in sophisticated but time-consuming microphysical process models, may also achieve good approximations of the fundamental properties of PSCs needed in CCMs.

The Effect of Forbush Decreases on the Polar-Night HOx Concentration Affecting Stratospheric Ozone

It is well-known that energetic particle precipitations during solar proton events increase ionization rates in the middle atmosphere enhancing the production of hydrogen oxide radicals (HOx) involved in the catalytic ozone destruction cycle. There are many studies where the contribution of energetic particles to the formation of hydrogen oxide radicals and ozone loss has been widely investigated. However, until now, there was no solid evidence that the reduction in galactic cosmic ray fluxes during a magnetic storm, known as Forbush-effect, directly and noticeably affects the polar-night stratospheric chemistry. Here, the impact of the Forbush decrease on the behavior of hydrogen oxide radicals was explored using the chemistry-climate model SOCOLv2. We found that hydrogen oxide radical lost about half of its concentration over the polar boreal night stratosphere owing to a reduction in ionization rates caused by Forbush decreases after solar proton events occurred on 17 and 20 of January 2005. The robust response in ozone was not found. There is not any statistically significant response in (NOx) on Forbush decrease events as well as over summer time in the southern polar region. The results of this study can be used to increase the veracity of ozone loss estimation if stronger Forbush events can have place.

Stratospheric Ozone in the Last Glacial Maximum

AbstractUsing the Whole Atmosphere Community Climate Model version 6, stratospheric ozone in the Last Glacial Maximum (LGM) is investigated. It is shown that, compared with preindustrial (PI) times, LGM modeled stratospheric temperatures are increased by up to 8 K, leading to faster ozone destruction rates for gas phase reactions, especially via the Chapman mechanism. On the other hand, stratospheric hydroxyl radical (OH) and nitrogen oxides (NOx) concentrations are decreased by 10–20%, which decreases catalytic ozone destruction, thereby decreasing ozone loss rates. The net effect of these two compensating mechanisms in the upper stratosphere (above 15 hPa) is a vertically integrated 1–3 Dobson unit (DU) decrease during the LGM. In the lower stratosphere (tropopause to 15 hPa), changes in the stratospheric overturning circulation and resulting transport dominate changes in ozone. Consistent with a weakening of the residual circulation in the LGM, lower stratospheric ozone is increased by 2–5 DU in the tropics and decreased by 5–10 DU in the extratropics, but the latter is partly compensated by ozone increases due to a lower tropopause. It is found that tropospheric ozone is decreased by about 5 DU in the LGM versus PI. Combined changes in stratospheric and tropospheric ozone lead to a decrease in total ozone column everywhere except over the northeast North America, equatorial Indian and West Pacific Oceans. Surface ultraviolet radiation in the LGM versus PI is increased over the Northern Hemisphere middle and high latitudes, especially over the ice caps, and over the Southern Hemisphere near 60°S.

Reformulating the bromine alpha factor and equivalent effective stratospheric chlorine (EESC): evolution of ozone destruction rates of bromine and chlorine in future climate scenarios

Abstract. Future trajectories of the stratospheric trace gas background will alter the rates of bromine- and chlorine-mediated catalytic ozone destruction via changes in the partitioning of inorganic halogen reservoirs and the underlying temperature structure of the stratosphere. The current formulation of the bromine alpha factor, the ozone-destroying power of stratospheric bromine atoms relative to stratospheric chlorine atoms, is invariant with the climate state. Here, we refactor the bromine alpha factor, introducing normalization to a benchmark chemistry–climate state, and formulate Equivalent Effective Stratospheric Benchmark-normalized Chlorine (EESBnC) to reflect changes in the rates of both bromine- and chlorine-mediated ozone loss catalysis with time. We show that the ozone-processing power of the extrapolar stratosphere is significantly perturbed by future climate assumptions. Furthermore, we show that our EESBnC-based estimate of the extrapolar ozone recovery date is in closer agreement with extrapolar ozone recovery dates predicted using more sophisticated 3-D chemistry–climate models than predictions made using equivalent effective stratospheric chlorine (EESC).

First measurements of ClO in the Venus atmosphere – Altitude dependence and temporal variation

The 352.88 GHz submm absorption spectrum of 35ClO in the Venus atmosphere was observed on Oct 23 and Nov 11, 2010, using the James Clerk Maxwell Telescope (JCMT) on Mauna Kea, HI. This is the first detection of Venus ClO, which is found to exhibit much larger abundances in the upper (85–100 km) versus lower (70–85 km) mesosphere, based upon retrieval of the altitude distribution from the shape of the pressure broadened absorption. The 2-day average of all collected data indicates 2.6 ±0.5 ppb above 85 ±2 km, and undetectable below. Temporal variation is evident between the Oct 23 and Nov 11 observations, which indicate upper mesospheric mixing ratios of 3.7 ±0.9 and 1.5 ±0.5 ppb, respectively. At these abundances catalytic destruction of ozone by highly reactive chlorine compounds (ClOx) must occur, reinforcing the (Montmessin et al., 2011) conclusion that their measured ozone profiles were consistent with chlorine-catalyzed ozone destruction above 90 km. Detection of ClO in the nightside atmosphere reveals that ClOx abundances exceed those of highly reactive nitrogen (NOx). Recent observations of HCl in both the night- and day-side atmosphere (Sandor and Clancy, 2012; 2017) demonstrate that upper mesospheric HCl represents less than half the total chlorine budget. This required a non-HCl reservoir consisting of highly reactive gas-phase chlorine compounds (ClOx), HCl aerosol particles, or both. The measured 1.5–3.7 ppb ClO directly indicates hundreds of ppb of Cl, demonstrating that ClOx (rather than aerosol) is a primary upper mesospheric chlorine reservoir. Finally, this first detection of ClO constitutes the first empirical corroboration that the (Yung and DeMore, 1982) chlorine-catalysis mechanism is responsible for stabilizing the Venus atmosphere as 97% CO2, 3% N2 (rather than comparable (within a factor of 2) CO, O2 and CO2 abundances).

Denitrification, dehydration and ozone loss during the 2015/2016 Arctic winter

Abstract. The 2015/2016 Arctic winter was one of the coldest stratospheric winters in recent years. A stable vortex formed by early December and the early winter was exceptionally cold. Cold pool temperatures dropped below the nitric acid trihydrate (NAT) existence temperature of about 195 K, thus allowing polar stratospheric clouds (PSCs) to form. The low temperatures in the polar stratosphere persisted until early March, allowing chlorine activation and catalytic ozone destruction. Satellite observations indicate that sedimentation of PSC particles led to denitrification as well as dehydration of stratospheric layers. Model simulations of the 2015/2016 Arctic winter nudged toward European Centre for Medium-Range Weather Forecasts (ECMWF) analysis data were performed with the atmospheric chemistry–climate model ECHAM5/MESSy Atmospheric Chemistry (EMAC) for the Polar Stratosphere in a Changing Climate (POLSTRACC) campaign. POLSTRACC is a High Altitude and Long Range Research Aircraft (HALO) mission aimed at the investigation of the structure, composition and evolution of the Arctic upper troposphere and lower stratosphere (UTLS). The chemical and physical processes involved in Arctic stratospheric ozone depletion, transport and mixing processes in the UTLS at high latitudes, PSCs and cirrus clouds are investigated. In this study, an overview of the chemistry and dynamics of the 2015/2016 Arctic winter as simulated with EMAC is given. Further, chemical–dynamical processes such as denitrification, dehydration and ozone loss during the 2015/2016 Arctic winter are investigated. Comparisons to satellite observations by the Aura Microwave Limb Sounder (Aura/MLS) as well as to airborne measurements with the Gimballed Limb Observer for Radiance Imaging of the Atmosphere (GLORIA) performed aboard HALO during the POLSTRACC campaign show that the EMAC simulations nudged toward ECMWF analysis generally agree well with observations. We derive a maximum polar stratospheric O3 loss of ∼ 2 ppmv or 117 DU in terms of column ozone in mid-March. The stratosphere was denitrified by about 4–8 ppbv HNO3 and dehydrated by about 0.6–1 ppmv H2O from the middle to the end of February. While ozone loss was quite strong, but not as strong as in 2010/2011, denitrification and dehydration were so far the strongest observed in the Arctic stratosphere in at least the past 10 years.

Thermochemistry of halogen-containing organic compounds with influence on atmospheric chemistry

We report a study on the thermochemical properties of a wide variety of halogen-containing organic compounds with relevance on several atmospheric chemical processes, such as catalytic ozone destruction. In particular, we have computationally determined the standard molar enthalpies of formation, ΔfHm∘(g), and the carbon-halogen bond dissociation enthalpies, BDE, in the gas phase at 298.15K. A reliable estimation of these thermodynamic magnitudes was deduced, using atomization and isodesmic reactions methodologies, from ab initio computational methods. The enthalpies of formation of the radicals formed through bond dissociations have also been computed.

Atmospheric effects of stellar cosmic rays on Earth-like exoplanets orbiting M-dwarfs

M-dwarf stars are generally considered favourable for rocky planet detection. However, such planets may be subject to extreme conditions due to possible high stellar activity. The goal of this work is to determine the potential effect of stellar cosmic rays on key atmospheric species of Earth-like planets orbiting in the habitable zone of M-dwarf stars and show corresponding changes in the planetary spectra. We build upon the cosmic rays model scheme of Grenfell et al. (2012), who considered cosmic ray induced NOx production, by adding further cosmic ray induced production mechanisms (e.g. for HOx) and introducing primary protons of a wider energy range (16 MeV - 0.5 TeV). Previous studies suggested that planets in the habitable zone that are subject to strong flaring conditions have high atmospheric methane concentrations, while their ozone biosignature is completely destroyed. Our current study shows, however, that adding cosmic ray induced HOx production can cause a decrease in atmospheric methane abundance of up to 80\%. Furthermore, the cosmic ray induced HOx molecules react with NOx to produce HNO$_3$, which produces strong HNO$_3$ signals in the theoretical spectra and reduces NOx-induced catalytic destruction of ozone so that more than 25\% of the ozone column remains. Hence, an ozone signal remains visible in the theoretical spectrum (albeit with a weaker intensity) when incorporating the new cosmic ray induced NOx and HOx schemes, even for a constantly flaring M-star case. We also find that HNO$_3$ levels may be high enough to be potentially detectable. Since ozone concentrations, which act as the key shield against harmful UV radiation, are affected by cosmic rays via NOx-induced catalytic destruction of ozone, the impact of stellar cosmic rays on surface UV fluxes is also studied.

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.

Mesospheric and stratospheric NOy produced by energetic particle precipitation during 2002–2012

Global distributions of the six principal reactive nitrogen (NOy) compounds (HNO3, NO2, NO, N2O5, ClONO2, and HNO4) have been derived from midinfrared limb emission spectra taken by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on board Envisat during 2002–2012. The obtained data set provides a unique climatological record of NOy in the middle atmosphere. The contribution of NOy produced by energetic particle precipitation (EPP) has been discriminated from that produced by N2O oxidation using a tracer correlation method based on MIPAS CH4 and CO observations. The EPP‐NOy distributions, obtained in the vertical range 20–70km, allow to trace odd nitrogen polar winter descent from the mesosphere down to the middle and lower stratosphere, where it contributes to catalytic ozone destruction. Highest EPP‐NOy concentrations (up to 1 ppmv) are found in the winter solstice mesosphere, decreasing continuously with time and toward lower altitudes. Springtime peak concentrations of a few parts per billion by volume are observed at 22–25km, demonstrating a regular EPP impact on the entire stratosphere. The interannual variation shows a clear solar cycle signal in consonance with geomagnetic activity variations. A pronounced hemispheric asymmetry of EPP‐NOy is observed, with higher concentrations in the Southern Hemisphere (SH) and stronger variability in the Northern Hemisphere (NH). Poleward of 60°, EPP‐NOy contributes to the winter NOy column at 20–70km by 10–40% in the SH and 1–30% in the NH. Smaller contributions (0.1–1%) are found at midlatitudes (30°–60°). This study provides the first assessment of EPP‐NOy intrusions into the stratosphere based on globally available satellite data on a decadal scale.