Nitric Acid Trihydrate Particles Research Articles

Effects of denitrification on the distributions of trace gas abundances in the polar regions: a comparison of WACCM with observations

Abstract. Polar stratospheric clouds (PSCs) play a key role in the polar chemistry of the stratosphere. Nitric acid trihydrate (NAT) particles have been shown to lead to denitrification of the lower stratosphere. While the existence of large NAT particles (NAT “rocks”) has been verified by many measurements, especially in the Northern Hemisphere (NH), most current chemistry–climate models use simplified parameterizations, often based on evaluations in the Southern Hemisphere where the polar vortex is stable enough that accounting for NAT rocks is not as important as in the NH. Here, we evaluate the probability density functions of various gaseous species in the polar vortex using one such model, the Whole Atmosphere Community Climate Model (WACCM), and compare these with measurements by the Michelson Interferometer for Passive Atmospheric Sounding onboard the Environmental Satellite (MIPAS/Envisat) and two ozonesonde stations for a range of years and in both hemispheres. Using the maximum difference between the distributions of MIPAS and WACCM as a measure of coherence, we find better agreement for HNO3 when reducing the NAT number density from the standard value of 10−2 used in this model to 5×10-4 cm−3 for almost all spring seasons during the MIPAS period in both hemispheres. The distributions of ClONO2 and O3 are not greatly affected by the NAT density. The average difference between WACCM and ozonesondes supports the need to reduce the NAT number density in the model. Therefore, this study suggests using a NAT number density of 5×10-4 cm−3 for future simulations with WACCM.

Statistical analysis of observations of polar stratospheric clouds with a lidar in Kiruna, northern Sweden

Abstract. In the present paper, we analyse 11 years of lidar measurements to derive general characteristics of polar stratospheric clouds (PSCs) and to examine how mountain lee waves influence PSC properties. Measurements of PSCs were made with a backscatter lidar located in Kiruna, northern Sweden, in the lee of the Scandinavian mountain range. The statistical analysis demonstrates that nearly half of all observed PSCs consisted of nitric acid trihydrate (NAT) particles, while ice clouds accounted for only a small fraction, and the remainder consisted of supercooled ternary solution (STS) and mixtures of different compositions. Most PSCs were observed around 22 km altitude. Mountain lee waves provide a distinct influence on PSC chemical composition and cloud height distribution. Ice PSCs were about 5 times as frequent, and NAT clouds were about half as frequent under wave conditions. PSCs were on average at 2 km higher altitudes when under the influence of mountain lee waves.

The importance of acid-processed meteoric smoke relative to meteoric fragments for crystal nucleation in polar stratospheric clouds

Abstract. The crystal formation of nitric acid trihydrate (NAT) in the absence of water ice is important for a subset of polar stratospheric clouds (PSCs) and thereby ozone depletion. It has been suggested that either fragmented meteoroids or meteoric smoke particles (MSPs), or possibly both, are important as heterogeneous nuclei of these crystals. Previous work has focused on the nucleating ability of meteoric material in nitric acid in the absence of sulfuric acid. However, it is known that when immersed in stratospheric sulfuric acid droplets, metal-containing meteoric material particles partially dissolve and components can reprecipitate as silica and alumina that have different morphologies to the original meteoric material. Hence, in this study, we experimentally and theoretically explore the relative role that sulfuric acid-processed MSPs and meteoric fragments may play in NAT nucleation in PSCs. We compared meteoric fragments that had recently been prepared (by milling a meteorite sample) to a sample annealed under conditions designed to simulate heating during entry into the Earth's atmosphere. Whilst the addition of sulfuric acid decreased the nucleating ability of the recently milled meteoric material relative to nucleation in binary nitric acid-water solutions (at similar NAT saturation ratio), the annealed meteoric fragments nucleated NAT with a similar effectiveness in both solutions. However, combining our results with measured fluxes of meteoric material to the Earth, sedimentation modelling and recent experiments on fragmentation of incoming meteoroids suggests that it is unlikely for there to be sufficient fragments to contribute to the nucleation of crystalline NAT particles. We then considered silica formed from sulfuric acid-processed MSPs. Our previous work showed that nanoparticulate silica (radius ∼6 nm) is a relatively poor promoter of nucleation compared with micron-scaled silica particles, which were more effective. Both materials have similar chemical and structural (crystallographically amorphous) properties, indicating that size is critical. Here, we account for surface curvature of primary grains using the Classical Nucleation Theory (CNT) to explore this size dependence. This model is able to explain the discrepancy in nucleation effectiveness of fumed silica and fused quartz by treating their nucleating activity (contact angle) as equal but with differing particle size (or surface curvature), assuming interfacial energies that are physically reasonable. Here, we use this CNT model to present evidence that nucleation of NAT on acid-processed MSPs, where the primary grain size is tens of nanometres, is also effective enough to contribute to NAT crystals in early season PSCs where there is an absence of ice. This study demonstrates that the modelling of crystal nucleation in PSCs and resulting ozone depletion relies on an accurate understanding of the transport and chemical processing of MSPs. This will affect estimated sensitivity of stratospheric chemistry to rare events such as large volcanic eruptions and long-term forecasting of ozone recovery in a changing climate.

A study of optical scattering modelling for mixed-phase polar stratospheric clouds

Abstract. Scattering codes are used to study the optical properties of polar stratospheric clouds (PSCs). Particle backscattering and depolarization coefficients can be computed with available scattering codes once the particle size distribution (PSD) is known and a suitable refractive index is assumed. However, PSCs often appear as external mixtures of supercooled ternary solution (STS) droplets, solid nitric acid trihydrate (NAT) and possibly ice particles, making the assumption of a single refractive index and a single morphology to model the scatterers questionable. Here we consider a set of 15 coincident measurements of PSCs above McMurdo Station, Antarctica, using ground-based lidar, a balloon-borne optical particle counter (OPC) and in situ observations taken by a laser backscattersonde and OPC during four balloon stratospheric flights from Kiruna, Sweden. This unique dataset of microphysical and optical observations allows us to test the performances of optical scattering models when both spherical and aspherical scatterers of different composition and, possibly, shapes are present. We consider particles as STS if their radius is below a certain threshold value Rth and NAT or possibly ice if it is above it. The refractive indices are assumed known from the literature. Mie scattering is used for the STS, assumed spherical. Scattering from NAT particles, considered spheroids of different aspect ratio (AR), is treated with T-matrix results where applicable. The geometric-optics–integral-equation approach is used whenever the particle size parameter is too large to allow for a convergence of the T-matrix method. The parameters Rth and AR of our model have been varied between 0.1 and 2 µm and between 0.3 and 3, respectively, and the calculated backscattering coefficient and depolarization were compared with the observed ones. The best agreement was found for Rth between 0.5 and 0.8 µm and for AR less than 0.55 and greater than 1.5. To further constrain the variability of AR within the identified intervals, we have sought an agreement with the experimental data by varying AR on a case-by-case basis and further optimizing the agreement by a proper choice of AR smaller than 0.55 and greater than 1.5 and Rth within the interval 0.5 and 0.8 µm. The ARs identified in this way cluster around the values 0.5 and 2.5. The comparison of the calculations with the measurements is presented and discussed. The results of this work help to set limits to the variability of the dimensions and asphericity of PSC solid particles, within the limits of applicability of our model based on the T-matrix theory of scattering and on assumptions on a common particle shape in a PSD and a common threshold radius for all the PSDs.

Polar Stratospheric Clouds: Satellite Observations, Processes, and Role in Ozone Depletion

AbstractPolar stratospheric clouds (PSCs) play important roles in stratospheric ozone depletion during winter and spring at high latitudes (e.g., the Antarctic ozone hole). PSC particles provide sites for heterogeneous reactions that convert stable chlorine reservoir species to radicals that destroy ozone catalytically. PSCs also prolong ozone depletion by delaying chlorine deactivation through the removal of gas‐phase HNO3 and H2O by sedimentation of large nitric acid trihydrate (NAT) and ice particles. Contemporary observations by the spaceborne instruments Michelson Interferometer for Passive Atmospheric Sounding (MIPAS), Microwave Limb Sounder (MLS), and Cloud‐Aerosol Lidar with Orthogonal Polarization (CALIOP) have provided an unprecedented polar vortex‐wide climatological view of PSC occurrence and composition in both hemispheres. These data have spurred advances in our understanding of PSC formation and related dynamical processes, especially the firm evidence of widespread heterogeneous nucleation of both NAT and ice PSC particles, perhaps on nuclei of meteoritic origin. Heterogeneous chlorine activation appears to be well understood. Reaction coefficients on/in liquid droplets have been measured accurately, and while uncertainties remain for reactions on solid NAT and ice particles, they are considered relatively unimportant since under most conditions chlorine activation occurs on/in liquid droplets. There have been notable advances in the ability of chemical transport and chemistry‐climate models to reproduce PSC temporal/spatial distributions and composition observed from space. Continued spaceborne PSC observations will facilitate further improvements in the representation of PSC processes in global models and enable more accurate projections of the evolution of polar ozone and the global ozone layer as climate changes.

A new method to detect and classify polar stratospheric nitric acid trihydrate clouds derived from radiative transfer simulations and its first application to airborne infrared limb emission observations

Abstract. Polar stratospheric clouds (PSCs) play an important role in the spatial and temporal evolution of trace gases inside the polar vortex due to different processes, such as chlorine activation and NOy redistribution. As there are still uncertainties in the representation of PSCs in model simulations, detailed observations of PSCs and information on their type – nitric acid trihydrate (NAT), supercooled ternary solution (STS), and ice – are desirable. The measurements inside PSCs made by the CRISTA-NF (CRyogenic Infrared Spectrometers and Telescope for the Atmosphere – New Frontiers) airborne infrared limb sounder during the RECONCILE (Reconciliation of essential process parameters for an enhanced predictability of Arctic stratospheric ozone loss and its climate interactions) aircraft campaign showed a spectral peak at about 816 cm−1. This peak is shifted compared with the known peak at about 820 cm−1, which is recognised as being caused by the emission of radiation by small NAT particles. To investigate the reason for this spectral difference, we performed a large set of radiative transfer simulations of infrared limb emission spectra in the presence of various PSCs (NAT, STS, ice, and mixtures) for the airborne viewing geometry of CRISTA-NF. NAT particles can cause different spectral features in the 810–820 cm−1 region. The simulation results show that the appearance of the feature changes with an increasing median radius of the NAT particle size distribution, from a peak at 820 cm−1 to a shifted peak and, finally, to a step-like feature in the spectrum, caused by the increasing contribution of scattering to the total extinction. Based on the appearance of the spectral feature, we defined different colour indices to detect PSCs containing NAT particles and to subgroup them into three size regimes under the assumption of spherical particles: small NAT (≤ 1.0 µm), medium NAT (1.5–4.0 µm), and large NAT (≥ 3.5 µm). Furthermore, we developed a method to detect the bottom altitude of a cloud by using the cloud index (CI), a colour ratio indicating the optical thickness, and the vertical gradient of the CI. Finally, we applied the methods to observations of the CRISTA-NF instrument during one local flight of the RECONCILE aircraft campaign and found STS and medium-sized NAT.

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.

Polar stratospheric clouds initiated by mountain waves in a global chemistry–climate model: a missing piece in fully modelling polar stratospheric ozone depletion

Abstract. An important source of polar stratospheric clouds (PSCs), which play a crucial role in controlling polar stratospheric ozone depletion, is the temperature fluctuations induced by mountain waves. These enable stratospheric temperatures to fall below the threshold value for PSC formation in regions of negative temperature perturbations or cooling phases induced by the waves even if the synoptic-scale temperatures are too high. However, this formation mechanism is usually missing in global chemistry–climate models because these temperature fluctuations are neither resolved nor parameterised. Here, we investigate in detail the episodic and localised wintertime stratospheric cooling events produced over the Antarctic Peninsula by a parameterisation of mountain-wave-induced temperature fluctuations inserted into a 30-year run of the global chemistry–climate configuration of the UM-UKCA (Unified Model – United Kingdom Chemistry and Aerosol) model. Comparison of the probability distribution of the parameterised cooling phases with those derived from climatologies of satellite-derived AIRS brightness temperature measurements and high-resolution radiosonde temperature soundings from Rothera Research Station on the Antarctic Peninsula shows that they broadly agree with the AIRS observations and agree well with the radiosonde observations, particularly in both cases for the “cold tails” of the distributions. It is further shown that adding the parameterised cooling phase to the resolved and synoptic-scale temperatures in the UM-UKCA model results in a considerable increase in the number of instances when minimum temperatures fall below the formation temperature for PSCs made from ice water during late austral autumn and early austral winter and early austral spring, and without the additional cooling phase the temperature rarely falls below the ice frost point temperature above the Antarctic Peninsula in the model. Similarly, it was found that the formation potential for PSCs made from ice water was many times larger if the additional cooling is included. For PSCs made from nitric acid trihydrate (NAT) particles it was only during October that the additional cooling is required for temperatures to fall below the NAT formation temperature threshold (despite more NAT PSCs occurring during other months). The additional cooling phases also resulted in an increase in the surface area density of NAT particles throughout the winter and early spring, which is important for chlorine activation. The parameterisation scheme was finally shown to make substantial differences to the distribution of total column ozone during October, resulting from a shift in the position of the polar vortex.

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.

Stratospheric Aerosols, Polar Stratospheric Clouds, and Polar Ozone Depletion After the Mount Calbuco Eruption in 2015

AbstractWe investigate the impact of the 2015 Mount Calbuco eruption and previous eruptions on stratospheric aerosols, polar stratospheric clouds, and ozone depletion using the Community Earth System Model coupled with the Community Aerosol and Radiation Model for Atmospheres compared with several satellite and balloon observations. The modeled volcanic sulfate aerosol size distribution agrees with the Light Optical Aerosol Counter observation at the Reunion Island site (21°S, 55°E) on 19 August at 20 km within estimated 0.1‐ to 1‐μm radius error bars. Both the observed and simulated backscatter and extinction show that volcanic sulfate aerosol from the Mount Calbuco eruption was transported from midlatitude toward the Antarctic and slowly descended during transport. They also indicate that the SO2 emission into the stratosphere from Mount Calbuco is 0.2–0.4 Tg. The modeled number density indicates that the volcanic sulfate aerosol from the Mount Calbuco eruption penetrated into the Antarctic polar vortex in May and thereafter and reduced the polar stratospheric clouds effective radius. In the simulations, the Antarctic stratosphere denitrified too early and by too much compared with Microwave Limb Sounder observations. Heterogeneous nucleation of nitric acid trihydrate or sophisticated gravity wave representations may be required to simulate nitric acid trihydrate particles with smaller falling velocity. The volcanic sulfate aerosol increases the ozone depletion in September especially around 100 hPa and 70°S, relative to a case without any volcanic eruptions. The simulated surface area density, earlier ozone loss, and larger area of the ozone hole are consistent with the presence of volcanic sulfate layers observed at 16 km as well as previous studies.

Widespread polar stratospheric ice clouds in the 2015–2016 Arctic winter – implications for ice nucleation

Abstract. Low planetary wave activity led to a stable vortex with exceptionally cold temperatures in the 2015–2016 Arctic winter. Extended areas with temperatures below the ice frost point temperature Tice persisted over weeks in the Arctic stratosphere as derived from the 36-year temperature climatology of the ERA-Interim reanalysis data set of the European Centre for Medium-Range Weather Forecasts (ECMWF). These extreme conditions promoted the formation of widespread polar stratospheric ice clouds (ice PSCs). The space-borne Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) instrument on board the CALIPSO (Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation) satellite continuously measured ice PSCs for about a month with maximum extensions of up to 2×106 km2 in the stratosphere. On 22 January 2016, the WALES (Water Vapor Lidar Experiment in Space – airborne demonstrator) lidar on board the High Altitude and Long Range Research Aircraft HALO detected an ice PSC with a horizontal length of more than 1400 km. The ice PSC extended between 18 and 24 km altitude and was surrounded by nitric acid trihydrate (NAT) particles, supercooled ternary solution (STS) droplets and particle mixtures. The ice PSC occurrence histogram in the backscatter ratio to particle depolarization ratio optical space exhibits two ice modes with high or low particle depolarization ratios. Domain-filling 8-day back-trajectories starting in the high particle depolarization (high-depol) ice mode are continuously below the NAT equilibrium temperature TNAT and decrease below Tice∼10 h prior to the observation. Their matches with CALIPSO PSC curtain plots demonstrate the presence of NAT PSCs prior to high-depol ice, suggesting that the ice had nucleated on NAT. Vice versa, STS or no PSCs were detected by CALIPSO prior to the ice mode with low particle depolarization ratio. In addition to ice nucleation in STS potentially having meteoric inclusions, we find evidence for ice nucleation on NAT in the Arctic winter 2015–2016. The observation of widespread Arctic ice PSCs with high or low particle depolarization ratios advances our understanding of ice nucleation in polar latitudes. It further provides a new observational database for the parameterization of ice nucleation schemes in atmospheric models.

Development of a Polar Stratospheric Cloud Model Within the Community Earth System Model: Assessment of 2010 Antarctic Winter

AbstractTo simulate polar stratospheric clouds (PSCs) during the Antarctic winter of 2010, we have developed a PSC model within the Community Earth System Model framework that includes detailed microphysics of sulfuric aerosols and three types of PSCs: supercooled ternary solution (STS), nitric acid trihydrate (NAT), and ice. Our model includes two major NAT formation mechanisms, both of which are essential to reproduce the PSC and gas phase chemical features in the 2010 Antarctic winter. Homogeneous nucleation of NAT from STS produces NAT particles with sizes near 8 μm, which are important to properly simulate denitrification and the gas phase HNO3 observed by the Microwave Limb Sounder (MLS). Heterogeneous nucleation of NAT on ice particles or ice particles on NAT and subsequent evaporation of the ice produces NAT particles with sizes from submicrometers to a few micrometers. These particles account for the large backscattering ratio from NAT observed by the Cloud‐Aerosol Lidar and Infrared Pathfinder Satellite Observations satellite, especially in the midwinter season. Adding temperature fluctuations from gravity waves is important to produce larger number density and higher backscattering ratio from ice and NAT particles. However, our model needs a better representation of waves to improve the backscattering ratio and gas phase HNO3 compared with observations. Our model also includes homogeneous nucleation of ice from STS and heterogeneous nucleation of ice on NAT. The model reproduces the gas phase H2O during the winter within the uncertainty of the MLS observations.

Comparing simulated PSC optical properties with CALIPSO observations during the 2010 Antarctic winter

AbstractWe simulate polar stratospheric clouds (PSCs) during the Antarctic winter of 2010 using the Specified Dynamics version of the Whole Atmosphere Community Climate Model/Community Aerosol and Radiation Model for Atmospheres (SD‐WACCM/CARMA) model. The current PSC model contains microphysical schemes for supercooled ternary solutions (STS) and nitric acid trihydrate (NAT) particles, as well as a prognostic treatment for PSC ice particles and dehydration. Our simulations and CALIPSO satellite data suggest two major NAT particle formation mechanisms. The first mechanism is the nucleation of NAT from STS. Our model, with homogeneous nucleation rates of NAT from STS constrained by observations from the Arctic winter of 2010–2011, reproduces optical properties observed by CALIPSO over Antarctica in May and the timing of denitrification observed by the Microwave Limb Sounder within their uncertainties. On the other hand, the CALIPSO data indicate that our simulations are missing clouds containing small NAT particles with large number densities. We suggest these particles are most likely to form from ice clouds or STS in gravity waves, as found by previous investigations. The simulated cloud coverage agrees with the CALIPSO cloud coverage within a few percent on average with a correlation coefficient of 0.83. However, using the CALIPSO classification algorithm, simulated ice clouds often fall into Mix categories under the denitrified and dehydrated conditions. The model needs an improved ice microphysical representation, not only to allow ice particles to be a source of NAT but also to provide information on ice cloud particle number and size so that ice cloud optical properties can be more precisely calculated for comparison with CALIPSO data.

Interannual variations of early winter Antarctic polar stratospheric cloud formation and nitric acid observed by CALIOP and MLS

Abstract. We use satellite-borne measurements collected over the last decade (2006–2015) from the Aura Microwave Limb Sounder (MLS) and the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) to investigate the nitric acid distribution and the properties of polar stratospheric clouds (PSCs) in the early winter Antarctic vortex. Frequently, at the very start of the winter, we find that synoptic-scale depletion of HNO3 can be detected in the inner vortex before the first lidar detection of geophysically associated PSCs. The generation of "sub-visible" PSCs can be explained as arising from the development of a solid particle population with low number densities and large particle sizes. Assumed to be composed of nitric acid trihydrate (NAT), the sub-visible PSCs form at ambient temperatures well above the ice frost point, but also above the temperature at which supercooled ternary solution (STS) grows out of the background supercooled binary solution (SBS) distribution. The temperature regime of their formation, inferred from the simultaneous uptake of ambient HNO3 into NAT and their Lagrangian temperature histories, is at a depression of a few kelvin with respect to the NAT existence threshold, TNAT. Therefore, their nucleation requires a considerable supersaturation of HNO3 over NAT, and is consistent with a recently described heterogeneous nucleation process on solid foreign nuclei immersed in liquid aerosol. We make a detailed investigation of the comparative limits of detection of PSCs and the resulting sequestration of HNO3 imposed by lidar, mid-infrared, and microwave techniques. We find that the temperature history of air parcels, in addition to the local ambient temperature, is an important factor in the relative frequency of formation of liquid/solid PSCs. We conclude that the initiation of NAT nucleation and the subsequent development of large NAT particles capable of sedimentation and denitrification in the early winter do not emanate from an ice-seeding process. Finally, we investigate the patterns of interannual variability and compare the relative formation frequency of liquid and solid PSCs in the Antarctic lower polar stratosphere using the results of a cluster analysis to synthesize the combined CALIOP and MLS measurements into a relatively small number of interrelated categories.

Spectroscopic evidence of large aspherical <i>β</i>-NAT particles involved in denitrification in the December 2011 Arctic stratosphere

Abstract. We analyze polar stratospheric cloud (PSC) signatures in airborne MIPAS-STR (Michelson Interferometer for Passive Atmospheric Sounding – STRatospheric aircraft) observations in the spectral regions from 725 to 990 and 1150 to 1350 cm−1 under conditions suitable for the existence of nitric acid trihydrate (NAT) above northern Scandinavia on 11 December 2011. The high-resolution infrared limb emission spectra of MIPAS-STR show a characteristic “shoulder-like” signature in the spectral region around 820 cm−1, which is attributed to the ν2 symmetric deformation mode of NO3− in β-NAT. Using radiative transfer calculations involving Mie and T-Matrix methods, the spectral signatures of spherical and aspherical particles are simulated. The simulations are constrained using collocated in situ particle measurements. Simulations assuming highly aspherical spheroids with aspect ratios (AR) of 0.1 or 10.0 and a lognormal particle mode with a mode radius of 4.8 µm reproduce the observed spectra to a high degree. A smaller lognormal mode with a mode radius of 2.0 µm, which is also taken into account, plays only a minor role. Within the scenarios analyzed, the best overall agreement is found for elongated spheroids with AR = 0.1. Simulations of spherical particles and spheroids with AR = 0.5 and 2.0 return results very similar to each other and do not allow us to reproduce the signature around 820 cm−1. The observed “shoulder-like” signature is explained by the combination of the absorption/emission and scattering characteristics of large highly aspherical β-NAT particles. The size distribution supported by our results corresponds to ∼ 9 ppbv of gas-phase equivalent HNO3 at the flight altitude of ∼ 18.5 km. The results are compared with the size distributions derived from the in situ observations, a corresponding Chemical Lagrangian Model of the Stratosphere (CLaMS) simulation, and excess gas-phase HNO3 observed in a nitrification layer directly below the observed PSC. The presented results suggest that large highly aspherical β-NAT particles involved in denitrification of the polar stratosphere can be identified by means of passive infrared limb emission measurements.

Solid‐state photochemistry as a formation mechanism for Titan's stratospheric C4N2 ice clouds

AbstractWe propose that C4N2 ice clouds observed in Titan's springtime polar stratosphere arise due to solid‐state photochemistry occurring within extant ice cloud particles of HCN‐HC3N mixtures. This formation process resembles the halogen‐induced ice particle surface chemistry that leads to condensed nitric acid trihydrate (NAT) particles and ozone depletion in Earth's polar stratosphere. As our analysis of the Cassini Composite Infrared Spectrometer 478 cm−1 ice emission feature demonstrates, this solid‐state photochemistry mechanism eliminates the need for the relatively high C4N2 saturation vapor pressures required (even though they are not observed) when the ice is produced through the usual procedure of direct condensation from the vapor.

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.

Development of a Polar Stratospheric Cloud Model within the Community Earth System Model using constraints on Type I PSCs from the 2010–2011 Arctic winter

AbstractPolar stratospheric clouds (PSCs) are critical elements of Arctic and Antarctic ozone depletion. We establish a PSC microphysics model using coupled chemistry, climate, and microphysics models driven by specific dynamics. We explore the microphysical formation and evolution of STS (Supercooled Ternary Solution) and NAT (Nitric Acid Trihydrate). Characteristics of STS particles dominated by thermodynamics compare well with observations. For example, the mass of STS is close to the thermodynamic equilibrium assumption when the particle surface area is >4 µm2/cm3. We derive a new nucleation rate equation for NAT based on observed denitrification in the 2010–2011 Arctic winter. The homogeneous nucleation scheme leads to supermicron NAT particles as observed. We also find that as the number density of NAT particles increases, the denitrification also increases. Simulations of the PSC lidar backscatter, denitrification, and gas phase species are generally within error bars of the observations. However, the simulations are very sensitive to temperature, which limits our ability to fully constrain some parameters (e.g., denitrification, ozone amount) based on observations.

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.