Polar Stratospheric Cloud Particles Research Articles

Ozone depletion in the Arctic and Antarctic stratosphere induced by wildfire smoke

Abstract. A record-breaking stratospheric ozone loss was observed over the Arctic and Antarctica in 2020. Strong ozone depletion occurred over Antarctica in 2021 as well. The ozone holes developed in smoke-polluted air. In this article, the impact of Siberian and Australian wildfire smoke (dominated by organic aerosol) on the extraordinarily strong ozone reduction is discussed. The study is based on aerosol lidar observations in the North Pole region (October 2019–May 2020) and over Punta Arenas in southern Chile at 53.2∘ S (January 2020–November 2021) as well as on respective NDACC (Network for the Detection of Atmospheric Composition Change) ozone profile observations in the Arctic (Ny-Ålesund) and Antarctica (Neumayer and South Pole stations) in 2020 and 2021. We present a conceptual approach on how the smoke may have influenced the formation of polar stratospheric clouds (PSCs), which are of key importance in the ozone-depleting processes. The main results are as follows: (a) the direct impact of wildfire smoke below the PSC height range (at 10–12 km) on ozone reduction seems to be similar to well-known volcanic sulfate aerosol effects. At heights of 10–12 km, smoke particle surface area (SA) concentrations of 5–7 µm2 cm−3 (Antarctica, spring 2021) and 6–10 µm2 cm−3 (Arctic, spring 2020) were correlated with an ozone reduction in terms of ozone partial pressure of 0.4–1.2 mPa (about 30 % further ozone reduction over Antarctica) and of 2–3.5 mPa (Arctic, 20 %–30 % reduction with respect to the long-term springtime mean). (b) Within the PSC height range, we found indications that smoke was able to slightly increase the PSC particle number and surface area concentration. In particular, a smoke-related additional ozone loss of 1–2 mPa (10 %–20 % contribution to the total ozone loss over Antarctica) was observed in the 14–23 km PSC height range in September–October 2020 and 2021. Smoke particle number concentrations ranged from 10 to 100 cm−3 and were about a factor of 10 (in 2020) and 5 (in 2021) above the stratospheric aerosol background level. Satellite observations indicated an additional mean column ozone loss (deviation from the long-term mean) of 26–30 Dobson units (9 %–10 %, September 2020, 2021) and 52–57 Dobson units (17 %–20 %, October 2020, 2021) in the smoke-polluted latitudinal Antarctic belt from 70–80∘ S.

Polar stratospheric nitric acid depletion surveyed from a decadal dataset of IASI total columns

Abstract. In this paper, we exploit the first 10-year data record (2008–2017) of nitric acid (HNO3) total columns measured by the IASI-A/MetOp infrared sounder, characterized by an exceptional daily sampling and a good vertical sensitivity in the lower-to-mid stratosphere (around 50 hPa), to monitor the relationship between the temperature decrease and the observed HNO3 loss that occurs each year in the Antarctic stratosphere during the polar night. Since the HNO3 depletion results from the formation of polar stratospheric clouds (PSCs), which trigger the development of the ozone (O3) hole, its continuous monitoring is of high importance. We verify here, from the 10-year time evolution of HNO3 together with temperature (taken from reanalysis at 50 hPa), the recurrence of specific regimes in the annual cycle of IASI HNO3 and identify (for each year) the day and the 50 hPa temperature (“drop temperature”) corresponding to the onset of strong HNO3 depletion in the Antarctic winter. Although the measured HNO3 total column does not allow for the uptake of HNO3 by different types of PSC particles along the vertical profile to be differentiated, an average drop temperature of 194.2 ± 3.8 K, close to the nitric acid trihydrate (NAT) existence threshold (∼ 195 K at 50 hPa), is found in the region of potential vorticity lower than −10 × 10−5 Km2kg-1s-1 (similar to the 70–90∘ S equivalent latitude region during winter). The spatial distribution and interannual variability of the drop temperature are investigated and discussed. This paper highlights the capability of the IASI sounder to monitor the evolution of polar stratospheric HNO3, a key player in the processes involved in the depletion of stratospheric O3.

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.

Vortex‐Wide Detection of Large Aspherical NAT Particles in the Arctic Winter 2011/12 Stratosphere

AbstractMicron‐sized HNO3‐containing particles in polar stratospheric clouds are known to denitrify the polar winter stratosphere and support chemical ozone loss. We show that populations of nitric acid trihydrate (NAT) particles with volume‐equivalent median radii of 3–7 μm can be detected vortex‐wide by means of infrared limb sounding. Key for detection are the applied optical characteristics of highly aspherical particles consisting of the β‐NAT phase. Spectroscopic signatures and ambient conditions of detected populations show that these particles play a key role in denitrification of the Arctic winter stratosphere. Complementary gas‐phase HNO3 observations indicate collocated highly efficient HNO3 sequestration within days and are consistent with measured spectral signals of populations of large NAT particles. High amounts of condensed gas‐phase equivalent HNO3 exceeding 10 ppbv and long persistence of detected populations, despite expected gravitational settling, imply that our understanding of the particles is incomplete.

Lagrangian simulation of ice particles and resulting dehydration in the polar winter stratosphere.

Polar stratospheric clouds (PSCs) and cold stratospheric aerosols drive heterogeneous chemistry and play a major role in polar ozone depletion. The Chemical Lagrangian Model of the Stratosphere (CLaMS) simulates the nucleation, growth, sedimentation, and evaporation of PSC particles along individual trajectories. Particles consisting of nitric acid trihydrate (NAT), which contain a substantial fraction of the stratospheric nitric acid (HNO3), were the focus of previous modeling work and are known for their potential to denitrify the polar stratosphere. Here, we carried this idea forward and introduced the formation of ice PSCs and related dehydration into the sedimentation module of CLaMS. Both processes change the simulated chemical composition of the lower stratosphere. Due to the Lagrangian transport scheme, NAT and ice particles move freely in three-dimensional space. Heterogeneous NAT and ice nucleation on foreign nuclei as well as homogeneous ice nucleation and NAT nucleation on preexisting ice particles are now implemented into CLaMS and cover major PSC formation pathways.We show results from the Arctic winter 2009/2010 and from the Antarctic winter 2011 to demonstrate the performance of the model over two entire PSC seasons. For both hemispheres, we present CLaMS results in comparison to measurements from the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP), the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS), and the Microwave Limb Sounder (MLS). Observations and simulations are presented on season-long and vortex-wide scales as well as for single PSC events. The simulations reproduce well both the timing and the extent of PSC occurrence inside the entire vortex. Divided into specific PSC classes, CLaMS results show predominantly good agreement with CALIOP and MIPAS observations, even for specific days and single satellite orbits. CLaMS and CALIOP agree that NAT mixtures are the first type of PSC to be present in both winters. NAT PSC areal coverages over the entire season agree satisfactorily. However, cloud-free areas, next to or surrounded by PSCs in the CALIOP data, are often populated with NAT particles in the CLaMS simulations. Looking at the temporal and vortex-averaged evolution of HNO3, CLaMS shows an uptake of HNO3 from the gas into the particle phase which is too large and happens too early in the simulation of the Arctic winter. In turn, the permanent redistribution of HNO3 is smaller in the simulations than in the observations. The Antarctic model run shows too little denitrification at lower altitudes towards the end of the winter compared to the observations. The occurrence of synoptic-scale ice PSCs agrees satisfactorily between observations and simulations for both hemispheres and the simulated vertical redistribution of water vapor (H2O) is in very good agreement with MLS observations. In summary, a conclusive agreement between CLaMS simulations and a variety of independent measurements is presented.

The MIPAS/Envisat climatology (2002–2012) of polar stratospheric cloud volume density profiles

Abstract. A global data set of vertical profiles of polar stratospheric cloud (PSC) volume density has been derived from Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) space-borne infrared limb measurements between 2002 and 2012. To develop a well characterized and efficient retrieval scheme, systematic tests based on limb-radiance simulations for PSCs from in situ balloon observations have been performed. The finally selected wavenumber range was 831–832.5 cm−1. Optical constants of nitric acid trihydrate (NAT) have been used to derive maximum and minimum profiles of volume density which are compatible with MIPAS observations under the assumption of small, non-scattering and larger, scattering PSC particles. These max/min profiles deviate from their mean value at each altitude by about 40 %–45 %, which is attributed as the maximum systematic error of the retrieval. Further, the retrieved volume density profiles are characterized by a random error due to instrumental noise of 0.02–0.05 µm3 cm−3, a detection limit of about 0.1–0.2 µm3 cm−3 and a vertical resolution of around 3 km. Comparisons with coincident observations by the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) on the CALIPSO (Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations) satellite showed good agreement regarding the vertical profile shape. Quantitatively, in the case of supercooled ternary solution (STS) PSCs, the CALIOP dataset fits to the MIPAS retrievals obtained under the assumptions of small particles. Unlike for STS and NAT, in the case of ice PSCs the MIPAS retrievals are limited by the clouds becoming optically thick in the limb-direction. In these cases, the MIPAS volume densities represent lower limits. Among other interesting features, this climatology helps to study quantitatively the on-set of PSC formation very near to the South Pole and the large variability of the PSC volume densities between different Arctic stratospheric winters.

Comparison of ECHAM5/MESSy Atmospheric Chemistry (EMAC) simulations of the Arctic winter 2009/2010 and 2010/2011 with Envisat/MIPAS and Aura/MLS observations

Abstract. We present model simulations with the atmospheric chemistry–climate model ECHAM5/MESSy Atmospheric Chemistry (EMAC) nudged toward European Centre for Medium-Range Weather Forecasts (ECMWF) ERA-Interim reanalyses for the Arctic winters 2009/2010 and 2010/2011. This study is the first to perform an extensive assessment of the performance of the EMAC model for Arctic winters as previous studies have only made limited evaluations of EMAC simulations which also were mainly focused on the Antarctic winter stratosphere. We have chosen the two extreme Arctic winters 2009/2010 and 2010/2011 to evaluate the formation of polar stratospheric clouds (PSCs) and the representation of the chemistry and dynamics of the polar winter stratosphere in EMAC. The EMAC simulations are compared to observations by the Michelson Interferometer for Passive Atmospheric Soundings (Envisat/MIPAS) and the observations from the Aura Microwave Limb Sounder (Aura/MLS). The Arctic winter 2010/2011 was one of the coldest stratospheric winters on record, leading to the strongest depletion of ozone measured in the Arctic. The Arctic winter 2009/2010 was, from the climatological perspective, one of the warmest stratospheric winters on record. However, it was distinguished by an exceptionally cold stratosphere (colder than the climatological mean) from mid-December 2009 to mid-January 2010, leading to prolonged PSC formation and existence. Significant denitrification, the removal of HNO3 from the stratosphere by sedimentation of HNO3-containing polar stratospheric cloud particles, occurred in that winter. In our comparison, we focus on PSC formation and denitrification. The comparisons between EMAC simulations and satellite observations show that model and measurements compare well for these two Arctic winters (differences for HNO3 generally within ±20 %) and thus that EMAC nudged toward ECMWF ERA-Interim reanalyses is capable of giving a realistic representation of the evolution of PSCs and associated sequestration of gas-phase HNO3 in the polar winter stratosphere. However, simulated PSC volume densities are smaller than the ones derived from Envisat/MIPAS observations by a factor of 3–7. Further, PSCs in EMAC are not simulated as high up (in altitude) as they are observed. This underestimation of PSC volume density and vertical extension of the PSCs results in an underestimation of the vertical redistribution of HNO3 due to denitrification/re-nitrification. The differences found here between model simulations and observations stipulate further improvements in the EMAC set-up for simulating PSCs.

On the discrepancy of HCl processing in the core of the wintertime polar vortices

Abstract. More than 3 decades after the discovery of the ozone hole, the processes involved in its formation are believed to be understood in great detail. Current state-of-the-art models can reproduce the observed chemical composition in the springtime polar stratosphere, especially regarding the quantification of halogen-catalysed ozone loss. However, we report here on a discrepancy between simulations and observations during the less-well-studied period of the onset of chlorine activation. During this period, which in the Antarctic is between May and July, model simulations significantly overestimate HCl, one of the key chemical species, inside the polar vortex during polar night. This HCl discrepancy is also observed in the Arctic. The discrepancy exists in different models to varying extents; here, we discuss three independent ones, the Chemical Lagrangian Model of the Stratosphere (CLaMS) as well as the Eulerian models SD-WACCM (the specified dynamics version of the Whole Atmosphere Community Climate Model) and TOMCAT/SLIMCAT. The HCl discrepancy points to some unknown process in the formulation of stratospheric chemistry that is currently not represented in the models. We characterise the HCl discrepancy in space and time for the Lagrangian chemistry–transport model CLaMS, in which HCl in the polar vortex core stays about constant from June to August in the Antarctic, while the observations indicate a continuous HCl decrease over this period. The somewhat smaller discrepancies in the Eulerian models SD-WACCM and TOMCAT/SLIMCAT are also presented. Numerical diffusion in the transport scheme of the Eulerian models is identified to be a likely cause for the inter-model differences. Although the missing process has not yet been identified, we investigate different hypotheses on the basis of the characteristics of the discrepancy. An underestimated HCl uptake into the polar stratospheric cloud (PSC) particles that consist mainly of H2O and HNO3 cannot explain it due to the temperature correlation of the discrepancy. Also, a direct photolysis of particulate HNO3 does not resolve the discrepancy since it would also cause changes in chlorine chemistry in late winter which are not observed. The ionisation caused by galactic cosmic rays provides an additional NOx and HOx source that can explain only about 20 % of the discrepancy. However, the model simulations show that a hypothetical decomposition of particulate HNO3 by some other process not dependent on the solar elevation, e.g. involving galactic cosmic rays, may be a possible mechanism to resolve the HCl discrepancy. Since the discrepancy reported here occurs during the beginning of the chlorine activation period, where the ozone loss rates are small, there is only a minor impact of about 2 % on the overall ozone column loss over the course of Antarctic winter and spring.

Diurnal variations of BrONO<sub>2</sub> observed by MIPAS-B at midlatitudes and in the Arctic

Abstract. The first stratospheric measurements of the diurnal variation in the inorganic bromine (Bry) reservoir species BrONO2 around sunrise and sunset are reported. Arctic flights of the balloon-borne Michelson Interferometer for Passive Atmospheric Sounding (MIPAS-B) were carried out from Kiruna (68° N, Sweden) in January 2010 and March 2011 inside the stratospheric polar vortices where diurnal variations of BrONO2 around sunrise have been observed. High nighttime BrONO2 volume mixing ratios of up to 21 pptv (parts per trillion by volume) were detected in late winter 2011 in the absence of polar stratospheric clouds (PSCs). In contrast, the amount of measured BrONO2 was significantly lower in January 2010 due to low available NO2 amounts (for the build-up of BrONO2), the heterogeneous destruction of BrONO2 on PSC particles, and the gas-phase interaction of BrO (the source to form BrONO2) with ClO. A further balloon flight took place at midlatitudes from Timmins (49° N, Canada) in September 2014. Mean BrONO2 mixing ratios of 22 pptv were observed after sunset in the altitude region between 21 and 29 km. Measurements are compared and discussed with the results of a multi-year simulation performed with the chemistry climate model ECHAM5/MESSy Atmospheric Chemistry (EMAC). The calculated temporal variation in BrONO2 largely reproduces the balloon-borne observations. Using the nighttime simulated ratio between BrONO2 and Bry, the amount of Bry observed by MIPAS-B was estimated to be about 21–25 pptv in the lower stratosphere.

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.

Meteoric Smoke Deposition in the Polar Regions: A Comparison of Measurements With Global Atmospheric Models

AbstractThe accumulation rate of meteoric smoke particles (MSPs) in ice cores—determined from the trace elements Ir and Pt, and superparamagnetic Fe particles—is significantly higher than expected from the measured vertical fluxes of Na and Fe atoms in the upper mesosphere and the surface deposition of cosmic spherules. The Whole Atmosphere Community Climate Model with the Community Aerosol and Radiation Model for Atmospheres has been used to simulate MSP production, transport, and deposition, using a global MSP input of 7.9 t d−1 based on these other measurements. The modeled MSP deposition rates are smaller than the measurements by factors of ~32 in Greenland and ~12 in Antarctica, even after reanalysis of the Ir/Pt ice core data with inclusion of a volcanic source. Variations of the model deposition scheme and use of the United Kingdom Chemistry and Aerosols model do not improve the agreement. Direct removal of MSP‐nucleated polar stratospheric cloud particles to the surface gives much better agreement, but would result in an unfeasibly high rate of nitrate deposition. The unablated fraction of cosmic dust (~35 t d−1) would provide sufficient Ir and Pt to account for the Antarctic measurements, but the relatively small flux of these large (>3 μm) particles would lead to greater variability in the ice core measurements than is observed, although this would be partly offset if significant fragmentation of cosmic dust particles occurred during atmospheric entry. Future directions to resolve these discrepancies between models and measurements are also discussed.

A multi-wavelength classification method for polar stratospheric cloud types using infrared limb spectra

Abstract. The Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) instrument on board the ESA Envisat satellite operated from July 2002 until April 2012. The infrared limb emission measurements represent a unique dataset of daytime and night-time observations of polar stratospheric clouds (PSCs) up to both poles. Cloud detection sensitivity is comparable to space-borne lidars, and it is possible to classify different cloud types from the spectral measurements in different atmospheric windows regions. Here we present a new infrared PSC classification scheme based on the combination of a well-established two-colour ratio method and multiple 2-D brightness temperature difference probability density functions. The method is a simple probabilistic classifier based on Bayes' theorem with a strong independence assumption. The method has been tested in conjunction with a database of radiative transfer model calculations of realistic PSC particle size distributions, geometries, and composition. The Bayesian classifier distinguishes between solid particles of ice and nitric acid trihydrate (NAT), as well as liquid droplets of super-cooled ternary solution (STS). The classification results are compared to coincident measurements from the space-borne lidar Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) instrument over the temporal overlap of both satellite missions (June 2006–March 2012). Both datasets show a good agreement for the specific PSC classes, although the viewing geometries and the vertical and horizontal resolution are quite different. Discrepancies are observed between the CALIOP and the MIPAS ice class. The Bayesian classifier for MIPAS identifies substantially more ice clouds in the Southern Hemisphere polar vortex than CALIOP. This disagreement is attributed in part to the difference in the sensitivity on mixed-type clouds. Ice seems to dominate the spectral behaviour in the limb infrared spectra and may cause an overestimation in ice occurrence compared to the real fraction of ice within the PSC area in the polar vortex. The entire MIPAS measurement period was processed with the new classification approach. Examples like the detection of the Antarctic NAT belt during early winter, and its possible link to mountain wave events over the Antarctic Peninsula, which are observed by the Atmospheric Infrared Sounder (AIRS) instrument, highlight the importance of a climatology of 9 Southern Hemisphere and 10 Northern Hemisphere winters in total. The new dataset is valuable both for detailed process studies, and for comparisons with and improvements of the PSC parameterizations used in chemistry transport and climate models.

Effects of polar stratospheric clouds in the Nimbus 7 LIMS Version 6 data set

Abstract. The historic Limb Infrared Monitor of the Stratosphere (LIMS) measurements of 1978–1979 from the Nimbus 7 satellite were re-processed with Version 6 (V6) algorithms and archived in 2002. The V6 data set employs updated radiance registration methods, improved spectroscopic line parameters, and a common vertical resolution for all retrieved parameters. Retrieved profiles are spaced about every 1.6° of latitude along orbits and include the additional parameter of geopotential height. Profiles of O3 are sensitive to perturbations from emissions of polar stratospheric clouds (PSCs). This work presents results of implementing a first-order screening for effects of PSCs using simple algorithms based on vertical gradients of the O3 mixing ratio. Their occurrences are compared with the co-located, retrieved temperatures and related to the temperature thresholds needed for saturation of H2O and/or HNO3 vapor onto PSC particles. Observed daily locations where the major PSC screening criteria are satisfied are validated against PSCs observed with the Stratospheric Aerosol Monitor (SAM) II experiment also on Nimbus 7. Remnants of emissions from PSCs are characterized for O3 and HNO3 following the screening. PSCs may also impart a warm bias in the co-located LIMS temperatures, but by no more than 1–2 K at the altitudes of where effects of PSCs are a maximum in the ozone; thus, no PSC screening was applied to the V6 temperatures. Minimum temperatures vary between 187 and 194 K and often occur 1 to 2 km above where PSC effects are first identified in the ozone (most often between about 21 and 28 hPa). Those temperature–pressure values are consistent with conditions for the existence of nitric acid trihydrate (NAT) mixtures and to a lesser extent of super-cooled ternary solution (STS) droplets. A local, temporary uptake of HNO3 vapor of order 1–3 ppbv is indicated during mid-January for the 550 K surface. Seven-month time series of the distributions of LIMS O3 and HNO3 are shown based on their gridded Level 3 data following the PSC screening. Zonal coefficients of both species are essentially free of effects from PSCs on the 550 K surface, based on their average values along PV contours and in terms of equivalent latitude. Remnants of PSCs are still present in O3 on the 450 K surface during mid-January. It is judged that the LIMS Level 3 data are of good quality for analyzing the larger-scale, stratospheric chemistry and transport processes during the Arctic winter of 1978–1979.

Vortex-wide chlorine activation by a mesoscale PSC event in the Arctic winter of 2009/10

Abstract. In the Arctic polar vortex of the 2009/10 winter temperatures were low enough to allow widespread formation of polar stratospheric clouds (PSCs). These clouds occurred during the initial chlorine activation phase which provided the opportunity to investigate the impact of PSCs on chlorine activation. Satellite observations of gas-phase species and PSCs are used in combination with trajectory modeling to assess this initial activation. The initial activation occurred in association with the formation of PSCs over the east coast of Greenland at the beginning of January 2010. Although this area of PSCs covered only a small portion of the vortex, it was responsible for almost the entire initial activation of chlorine vortex wide. Observations show HCl (hydrochloric acid) mixing ratios decreased rapidly in and downstream of this region. Trajectory calculations and simplified heterogeneous chemistry modeling confirmed that the initial chlorine activation continued until ClONO2 (chlorine nitrate) was completely depleted and the activated air masses were advected throughout the polar vortex. For the calculation of heterogeneous reaction rates, surface area density is estimated from backscatter observations. Modeled heterogeneous reaction rates along trajectories intersecting with the PSCs indicate that the initial phase of chlorine activation occurred in just a few hours. These calculations also indicate that chlorine activation on the binary background aerosol is significantly slower than on the PSC particles and the observed chlorine activation can only be explained by an increase in surface area density due to PSC formation. Furthermore, there is a strong correlation between the magnitude of the observed HCl depletion and PSC surface area density.

Sensitivity of polar stratospheric cloud formation to changes in water vapour and temperature

Abstract. More than a decade ago it was suggested that a cooling of stratospheric temperatures by 1 K or an increase of 1 ppmv of stratospheric water vapour could promote denitrification, the permanent removal of nitrogen species from the stratosphere by solid polar stratospheric cloud (PSC) particles. In fact, during the two Arctic winters 2009/10 and 2010/11 the strongest denitrification in the recent decade was observed. Sensitivity studies along air parcel trajectories are performed to test how a future stratospheric water vapour (H2O) increase of 1 ppmv or a temperature decrease of 1 K would affect PSC formation. We perform our study based on measurements made during the Arctic winter 2010/11. Air parcel trajectories were calculated 6 days backward in time based on PSCs detected by CALIPSO (Cloud Aerosol Lidar and Infrared Pathfinder satellite observations). The sensitivity study was performed on single trajectories as well as on a trajectory ensemble. The sensitivity study shows a clear prolongation of the potential for PSC formation and PSC existence when the temperature in the stratosphere is decreased by 1 K and water vapour is increased by 1 ppmv. Based on 15 years of satellite measurements (2000–2014) from UARS/HALOE, Envisat/MIPAS, Odin/SMR, Aura/MLS, Envisat/SCIAMACHY and SCISAT/ACE-FTS it is further investigated if there is a decrease in temperature and/or increase of water vapour (H2O) observed in the polar regions similar to that observed at midlatitudes and in the tropics. Performing linear regression analyses we derive from the Envisat/MIPAS (2002–2012) and Aura/MLS (2004–2014) observations predominantly positive changes in the potential temperature range 350 to 1000 K. The linear changes in water vapour derived from Envisat/MIPAS observations are largely insignificant, while those from Aura/MLS are mostly significant. For the temperature neither of the two instruments indicate any significant changes. Given the strong inter-annual variation observed in water vapour and particular temperature the severe denitrification observed in 2010/11 cannot be directly related to any changes in water vapour and temperature since the millennium. However, the observations indicate a clear correlation between cold winters and enhanced water vapour mixing ratios. This indicates a connection between dynamical and radiative processes that govern water vapour and temperature in the Arctic lower stratosphere.

Facet shapes and thermo-stabilities of H₂SO₄•HNO₃ hydrates involved in polar stratospheric clouds.

The nucleation, ice crystal shapes and thermodynamic stability of polar stratospheric clouds particles are interesting concerns owing to their implication in the ozone layer destruction. Some of these particles are formed by conformers of H2O, HNO3, and H2SO4. We carried out calculations using density functional theory (DFT) to obtain optimized structures. Several stable trimers are achieved -divided in two groups, one with HNO3 moiety, second with H2SO4 moiety- after pre-optimization at B3LYP/6-31G and subsequently optimization at B3LYP/aug-cc-pVTZ level of theory. For both most stable conformers five H2O molecules are added to their optimized trimers to calculate hydrated geometries. The OH stretching harmonic frequencies are provided for all aggregates. The zero-point energy correction (ZEPC), relative electronic energies (∆E), relative reaction Gibbs free energies ∆(∆G)k-relative, and cooling constant (K cooling ) are reported at three temperatures: 188 K, 195 K, and 210 K. Shapes given in our calculations are compared with various experimental shapes as well as comparisons with their thermo-stabilities.

Simulation of polar ozone depletion: An update

AbstractWe evaluate polar ozone depletion chemistry using the specified dynamics version of the Whole Atmosphere Community Climate Model for the year 2011. We find that total ozone depletion in both hemispheres is dependent on cold temperatures (below 192 K) and associated heterogeneous chemistry on polar stratospheric cloud particles. Reactions limited to warmer temperatures above 192 K, or on binary liquid aerosols, yield little modeled polar ozone depletion in either hemisphere. An imposed factor of three enhancement in stratospheric sulfate increases ozone loss by up to 20 Dobson unit (DU) in the Antarctic and 15 DU in the Arctic in this model. Such enhanced sulfate loads are similar to those observed following recent relatively small volcanic eruptions since 2005 and imply impacts on the search for polar ozone recovery. Ozone losses are strongly sensitive to temperature, with a test case cooler by 2 K producing as much as 30 DU additional ozone loss in the Antarctic and 40 DU in the Arctic. A new finding of this paper is the use of the temporal behavior and variability of ClONO2 and HCl as indicators of the efficacy of heterogeneous chemistry. Transport of ClONO2 from the southern subpolar regions near 55–65°S to higher latitudes near 65–75°S provides a flux of NOx from more sunlit latitudes to the edge of the vortex and is important for ozone loss in this model. Comparisons between modeled and observed total column and profile ozone perturbations, ClONO2 abundances, and the rate of change of HCl bolster confidence in these conclusions.

Lagrangian analysis of microphysical and chemical processes in the Antarctic stratosphere: a case study

Abstract. We investigated chemical and microphysical processes in the late winter in the Antarctic lower stratosphere, after the first chlorine activation and initial ozone depletion. We focused on a time interval when both further chlorine activation and ozone loss, but also chlorine deactivation, occur. We performed a comprehensive Lagrangian analysis to simulate the evolution of an air mass along a 10-day trajectory, coupling a detailed microphysical box model to a chemistry model. Model results have been compared with in situ and remote sensing measurements of particles and ozone at the start and end points of the trajectory, and satellite measurements of key chemical species and clouds along it. Different model runs have been performed to understand the relative role of solid and liquid polar stratospheric cloud (PSC) particles for the heterogeneous chemistry, and for the denitrification caused by particle sedimentation. According to model results, under the conditions investigated, ozone depletion is not affected significantly by the presence of nitric acid trihydrate (NAT) particles, as the observed depletion rate can equally well be reproduced by heterogeneous chemistry on cold liquid aerosol, with a surface area density close to background values. Under the conditions investigated, the impact of denitrification is important for the abundances of chlorine reservoirs after PSC evaporation, thus stressing the need to use appropriate microphysical models in the simulation of chlorine deactivation. We found that the effect of particle sedimentation and denitrification on the amount of ozone depletion is rather small in the case investigated. In the first part of the analyzed period, when a PSC was present in the air mass, sedimentation led to a smaller available particle surface area and less chlorine activation, and thus less ozone depletion. After the PSC evaporation, in the last 3 days of the simulation, denitrification increases ozone loss by hampering chlorine deactivation.

Contribution of liquid, NAT and ice particles to chlorine activation and ozone depletion in Antarctic winter and spring

Abstract. Heterogeneous reactions in the Antarctic stratosphere are the cause of chlorine activation and ozone depletion, but the relative roles of different types of polar stratospheric clouds (PSCs) in chlorine activation is an open question. We use multi-year simulations of the chemistry-climate model ECHAM5/MESSy for Atmospheric Chemistry (EMAC) to investigate the impact that the various types of PSCs have on Antarctic chlorine activation and ozone loss. One standard and three sensitivity EMAC simulations have been performed. In all simulations a Newtonian relaxation technique using the ERA-Interim reanalysis was applied to simulate realistic synoptic conditions. In the three sensitivity simulations, we only changed the heterogeneous chemistry on PSC particles by switching the chemistry on liquid, nitric acid trihydrate (NAT) and ice particles on and off. The results of these simulations show that the significance of heterogeneous reactions on NAT and ice particles for chlorine activation and ozone depletion in Antarctic winter and spring is small in comparison to the significance of heterogeneous reactions on liquid particles. Liquid particles alone are sufficient to activate almost all of the available chlorine, with the exception of the upper PSC regions between 10 and 30 hPa, where temporarily ice particles show a relevant contribution. Shortly after the first PSC occurrence, NAT particles contribute a small fraction to chlorine activation. Heterogeneous chemistry on liquid particles is responsible for more than 90% of the ozone depletion in Antarctic spring in the model simulations. In high southern latitudes, heterogeneous chemistry on ice particles causes only up to 5 DU of additional ozone depletion in the column and heterogeneous chemistry on NAT particles less than 0.5 DU. The simulated HNO3, ClO and O3 results agree closely with observations from the Microwave Limb Sounder (MLS) onboard NASA's Aura satellite.

Microphysical properties of synoptic-scale polar stratospheric clouds: in situ measurements of unexpectedly large HNO<sub>3</sub>-containing particles in the Arctic vortex

Abstract. In January 2010 and December 2011, synoptic-scale polar stratospheric cloud (PSC) fields were probed during seven flights of the high-altitude research aircraft M-55 Geophysica within the RECONCILE (Reconciliation of essential process parameters for an enhanced predictability of Arctic stratospheric ozone loss and its climate interaction) and the ESSenCe (ESSenCe: ESA Sounder Campaign) projects. Particle size distributions in a diameter range between 0.46 and 40μm were recorded by four different optical in situ instruments. Three of these particle instruments are based on the detection of forward-scattered light by single particles. The fourth instrument is a grayscale optical array imaging probe. Optical particle diameters of up to 35μm were detected with particle number densities and total particle volumes exceeding previous Arctic measurements. Also, gas-phase and particle-bound NOy was measured, as well as water vapor concentrations. The optical characteristics of the clouds were measured by the remote sensing lidar MAL (Miniature Aerosol Lidar) and by the in situ backscatter sonde MAS (Multiwavelength Aerosol Scatterometer), showing the synoptic scale of the encountered PSCs. The particle mode below 2μm in size diameter has been identified as supercooled ternary solution (STS) droplets. The PSC particles in the size range above 2μm in diameter are considered to consist of nitric acid hydrates, and the particles' high HNO3 content was confirmed by the NOy instrument. Assuming a particle composition of nitric acid trihydrate (NAT), the optically measured size distributions result in particle-phase HNO3 mixing ratios exceeding available stratospheric values. Therefore the measurement uncertainties concerning probable overestimations of measured particle sizes and volumes are discussed in detail. We hypothesize that either a strong asphericity or an alternate particle composition (e.g., water ice coated with NAT) could explain our observations. In particular, with respect to the denitrification by sedimentation of large HNO3-containing particles, generally considered to be NAT, our new measurements raise questions concerning composition, shape and nucleation pathways. Answering these would improve the numerical simulation of PSC microphysical processes like cloud particle formation, growth and denitrification, which is necessary for better predictions of future polar ozone losses, especially under changing global climate conditions. Generally, it seems that the occurrence of large NAT particles – sometimes termed "NAT rocks" – are a regular feature of synoptic-scale PSCs in the Arctic.