Nitric Acid Trihydrate Nucleation Research Articles

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.

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.

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.

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.

Free energy of formation of a crystal nucleus in incongruent solidification: Implication for modeling the crystallization of aqueous nitric acid droplets in polar stratospheric clouds.

Using the formalism of classical thermodynamics in the framework of the classical nucleation theory, we derive an expression for the reversible work W* of formation of a binary crystal nucleus in a liquid binary solution of non-stoichiometric composition (incongruent crystallization). Applied to the crystallization of aqueous nitric acid droplets, the new expression more adequately takes account of the effects of nitric acid vapor compared to the conventional expression of MacKenzie, Kulmala, Laaksonen, and Vesala (MKLV) [J. Geophys. Res.: Atmos. 102, 19729 (1997)]. The predictions of both MKLV and modified expressions for the average liquid-solid interfacial tension σls of nitric acid dihydrate (NAD) crystals are compared by using existing experimental data on the incongruent crystallization of aqueous nitric acid droplets of composition relevant to polar stratospheric clouds (PSCs). The predictions for σls based on the MKLV expression are higher by about 5% compared to predictions based on our modified expression. This results in similar differences between the predictions of both expressions for the solid-vapor interfacial tension σsv of NAD crystal nuclei. The latter can be obtained by using the method based on the analysis of experimental data on crystal nucleation rates in aqueous nitric acid droplets; it exploits the dominance of the surface-stimulated mode of crystal nucleation in small droplets and its negligibility in large ones. Applying that method to existing experimental data, our expression for the free energy of formation provides an estimate for σsv of NAD in the range ≈92 dyn/cm to ≈100 dyn/cm, while the MKLV expression predicts it in the range ≈95 dyn/cm to ≈105 dyn/cm. The predictions of both expressions for W* become identical for the case of congruent crystallization; this was also demonstrated by applying our method for determining σsv to the nucleation of nitric acid trihydrate crystals in PSC droplets of stoichiometric composition.

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.

Arctic stratospheric dehydration – Part 2: Microphysical modeling

Abstract. Large areas of synoptic-scale ice PSCs (polar stratospheric clouds) distinguished the Arctic winter 2009/2010 from other years and revealed unprecedented evidence of water redistribution in the stratosphere. A unique snapshot of water vapor repartitioning into ice particles was obtained under extremely cold Arctic conditions with temperatures around 183 K. Balloon-borne, aircraft and satellite-based measurements suggest that synoptic-scale ice PSCs and concurrent reductions and enhancements in water vapor are tightly linked with the observed de- and rehydration signatures, respectively. In a companion paper (Part 1), water vapor and aerosol backscatter measurements from the RECONCILE (Reconciliation of essential process parameters for an enhanced predictability of Arctic stratospheric ozone loss and its climate interactions) and LAPBIAT-II (Lapland Atmosphere–Biosphere Facility) field campaigns have been analyzed in detail. This paper uses a column version of the Zurich Optical and Microphysical box Model (ZOMM) including newly developed NAT (nitric acid trihydrate) and ice nucleation parameterizations. Particle sedimentation is calculated in order to simulate the vertical redistribution of chemical species such as water and nitric acid. Despite limitations given by wind shear and uncertainties in the initial water vapor profile, the column modeling unequivocally shows that (1) accounting for small-scale temperature fluctuations along the trajectories is essential in order to reach agreement between simulated optical cloud properties and observations, and (2) the use of recently developed heterogeneous ice nucleation parameterizations allows the reproduction of the observed signatures of de- and rehydration. Conversely, the vertical redistribution of water measured cannot be explained in terms of homogeneous nucleation of ice clouds, whose particle radii remain too small to cause significant dehydration.

Nitric acid trihydrate nucleation and denitrification in the Arctic stratosphere

Abstract. Nitric acid trihydrate (NAT) particles in the polar stratosphere have been shown to be responsible for vertical redistribution of reactive nitrogen (NOy). Recent observations by Cloud–Aerosol Lidar with Orthogonal Polarization (CALIOP) aboard the CALIPSO satellite have been explained in terms of heterogeneous nucleation of NAT on foreign nuclei, revealing this to be an important formation pathway for the NAT particles. In state of the art global- or regional-scale models, heterogeneous NAT nucleation is currently simulated in a very coarse manner using a constant, saturation-independent nucleation rate. Here we present first simulations for the Arctic winter 2009/2010 applying a new saturation-dependent parametrisation of heterogeneous NAT nucleation rates within the Chemical Lagrangian Model of the Stratosphere (CLaMS). The simulation shows good agreement of chemical trace species with in situ and remote sensing observations. The simulated polar stratospheric cloud (PSC) optical properties agree much better with CALIOP observations than those simulated with a constant nucleation rate model. A comparison of the simulated particle size distributions with observations made using the Forward Scattering Spectrometer Probe (FSSP) aboard the high altitude research aircraft Geophysica, shows that the model reproduces the observed size distribution, except for the very largest particles above 15 μm diameter. The vertical NOy redistribution caused by the sedimentation of the NAT particles, in particular the denitrification and nitrification signals observed by the ACE-FTS satellite instrument and the in situ SIOUX instrument aboard the Geophysica, are reproduced by the improved model, and a small improvement with respect to the constant nucleation rate model is found.

Quasi‐Lagrangian measurements of nitric acid trihydrate formation over Antarctica

AbstractIn 2010, the joint French‐United States Concordiasi project released 19 long‐duration superpressure balloons from McMurdo Station, Antarctica. Four of these balloons carried a gondola with particle counters and temperature sensors to measure polar stratospheric clouds. One gondola spent 5 days at stable temperatures between equilibrium temperatures for nitric acid trihydrate (NAT) and for supercooled ternary solution droplets. Sporadic particles with radii between 0.46 µm and 4.5 µm were measured in a small fraction of the measurements. At these times the corresponding size distributions and total particle volumes were consistent with NAT. Although the fraction of these observations was less than 3%, their frequency increased with time over the 5 days. From this frequency the NAT nucleation rate at 3°C below TNAT was estimated to be 2 × 10−4 m−3 s−1 ± 60% for these late winter austral NAT observations at a potential temperature of 410–415 K. Interspersed with these measurements of polar stratospheric cloud particles consistent with NAT were many more measurements of particles consistent with background stratospheric aerosol indicating that the polar stratospheric clouds sampled were highly discontinuous.

Heterogeneous formation of polar stratospheric clouds – Part 2: Nucleation of ice on synoptic scales

Abstract. This paper provides compelling evidence for the importance of heterogeneous nucleation, likely on solid particles of meteoritic origin, and of small-scale temperature fluctuations, for the formation of ice particles in the Arctic stratosphere. During January 2010, ice PSCs (polar stratospheric clouds) were shown by CALIPSO (Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations) to have occurred on a synoptic scale (~1000 km dimension). CALIPSO observations also showed widespread PSCs containing NAT (nitric acid trihydrate) particles in December 2009, prior to the occurrence of synoptic-scale regions of ice PSCs during mid-January 2010. We demonstrate by means of detailed microphysical modeling along air parcel trajectories that the formation of these PSCs is not readily reconciled with expectations from the conventional understanding of PSC nucleation mechanisms. The measurements are at odds with the previous laboratory-based understanding of PSC formation, which deemed direct heterogeneous nucleation of NAT and ice on preexisting solid particles unlikely. While a companion paper (Part 1) addresses the heterogeneous nucleation of NAT during December 2009, before the existence of ice PSCs, this paper shows that also the large-scale occurrence of stratospheric ice in January 2010 cannot be explained merely by homogeneous ice nucleation but requires the heterogeneous nucleation of ice, e.g. on meteoritic dust or preexisting NAT particles. The required efficiency of the ice nuclei is surprisingly high, namely comparable to that of known tropospheric ice nuclei such as mineral dust particles. To gain model agreement with the ice number densities inferred from observations, the presence of small-scale temperature fluctuations, with wavelengths unresolved by the numerical weather prediction models, is required. With the derived rate parameterization for heterogeneous ice nucleation we are able to explain and reproduce CALIPSO observations throughout the entire Arctic winter 2009/2010.

Heterogeneous formation of polar stratospheric clouds – Part 1: Nucleation of nitric acid trihydrate (NAT)

Abstract. Satellite-based observations during the Arctic winter of 2009/2010 provide firm evidence that, in contrast to the current understanding, the nucleation of nitric acid trihydrate (NAT) in the polar stratosphere does not only occur on preexisting ice particles. In order to explain the NAT clouds observed over the Arctic in mid-December 2009, a heterogeneous nucleation mechanism is required, occurring via immersion freezing on the surface of solid particles, likely of meteoritic origin. For the first time, a detailed microphysical modelling of this NAT formation pathway has been carried out. Heterogeneous NAT formation was calculated along more than sixty thousand trajectories, ending at Cloud Aerosol Lidar with Orthogonal Polarization (CALIOP) observation points. Comparing the optical properties of the modelled NAT with these observations enabled a thorough validation of a newly developed NAT nucleation parameterisation, which has been built into the Zurich Optical and Microphysical box Model (ZOMM). The parameterisation is based on active site theory, is simple to implement in models and provides substantial advantages over previous approaches which involved a constant rate of NAT nucleation in a given volume of air. It is shown that the new method is capable of reproducing observed polar stratospheric clouds (PSCs) very well, despite the varied conditions experienced by air parcels travelling along the different trajectories. In a companion paper, ZOMM is applied to a later period of the winter, when ice PSCs are also present, and it is shown that the observed PSCs are also represented extremely well under these conditions.

Reconciliation of essential process parameters for an enhanced predictability of Arctic stratospheric ozone loss and its climate interactions (RECONCILE): activities and results

Abstract. The international research project RECONCILE has addressed central questions regarding polar ozone depletion, with the objective to quantify some of the most relevant yet still uncertain physical and chemical processes and thereby improve prognostic modelling capabilities to realistically predict the response of the ozone layer to climate change. This overview paper outlines the scope and the general approach of RECONCILE, and it provides a summary of observations and modelling in 2010 and 2011 that have generated an in many respects unprecedented dataset to study processes in the Arctic winter stratosphere. Principally, it summarises important outcomes of RECONCILE including (i) better constraints and enhanced consistency on the set of parameters governing catalytic ozone destruction cycles, (ii) a better understanding of the role of cold binary aerosols in heterogeneous chlorine activation, (iii) an improved scheme of polar stratospheric cloud (PSC) processes that includes heterogeneous nucleation of nitric acid trihydrate (NAT) and ice on non-volatile background aerosol leading to better model parameterisations with respect to denitrification, and (iv) long transient simulations with a chemistry-climate model (CCM) updated based on the results of RECONCILE that better reproduce past ozone trends in Antarctica and are deemed to produce more reliable predictions of future ozone trends. The process studies and the global simulations conducted in RECONCILE show that in the Arctic, ozone depletion uncertainties in the chemical and microphysical processes are now clearly smaller than the sensitivity to dynamic variability.

Antarctic NAT PSC belt of June 2003: Observational validation of the mountain wave seeding hypothesis

[1] Satellite observations of polar stratospheric clouds (PSCs) over Antarctica in June 2003 revealed small nitric acid trihydrate (NAT) particles forming suddenly along the vortex edge. Models suggest the trigger was mountain waves over the Antarctic Peninsula (AP) forming ice for NAT nucleation. We test this hypothesis by analyzing perturbations in stratospheric radiances from the Atmospheric Infrared Sounder (AIRS). AIRS data show mountain waves over the AP on 10–14 June, with no resolved wave activity before or after. Peak wave temperature amplitudes derived from independent 40 hPa channels all return values of 10–12 K, in agreement with values used to model this NAT event. These observations support a NAT wake from a small region of mountain wave activity over the AP as the source of this circumpolar NAT outbreak.

Heterogeneous Nucleation of Nitric Acid Trihydrate on Clay Minerals: Relevance to Type Ia Polar Stratospheric Clouds

Although critical to atmospheric modeling of stratospheric ozone depletion, selective heterogeneous nuclei that promote the formation of Type Ia polar stratospheric clouds (PSCs) are largely unknown. While mineral particles are known to be good ice nuclei, it is currently not clear whether they are also good nuclei for PSCs. In the present study, a high-vacuum chamber equipped with transmission Fourier transform infrared spectroscopy and a quadrupole mass spectrometer was used to study heterogeneous nucleation of nitric acid trihydrate (NAT) on two clay minerals-Na-montmorillonite and kaolinite-as analogs of atmospheric terrestrial and extraterrestrial minerals. The minerals are first coated with a 3:1 supercooled H2O/HNO3 solution prior to the observed nucleation of crystalline NAT. At 220 K, NAT formation was observed at low SNAT values of 12 and 7 on kaolinite and montmorillonite clays, respectively. These are the lowest SNAT values reported in the literature on any substrate. However, NAT nucleation exhibited significant temperature dependence. At lower temperatures, representative of typical polar stratospheric conditions, much higher supersaturations were required before nucleation was observed. Our results suggest that NAT nucleation on mineral particles, not previously treated with sulfuric acid, may not be an important nucleation platform for Type Ia PSCs under normal polar stratospheric conditions.

Reply to “Comment on ‘Do NAD and NAT Form in Liquid Stratospheric Aerosols by Pseudoheterogeneous Nucleation?'”

In her comment, Tabazadeh1 raises several points of criticism on the work by Knopf:2 (1) the paper does not provide new experimental and theoretical studies to debate the main conclusion of Tabazadeh et al.,3 i.e., the possibility of a pseudoheterogeneous nucleation process occurring in polar stratospheric clouds (PSCs) to form NAD (nitric acid dihydrate) and NAT (nitric acid trihydrate), (2) Knopf2 ignores experimental and theoretical studies supporting pseudoheterogeneous nucleation, (3) nucleation rates are not expected to equal zero at the melting points of NAD and NAT using the framework of classical nucleation theory (CNT), (4) adjustment of the activation energies in the parametrization3 yields suitable pseudoheterogeneous nucleation rates (PNR), (5) Knopf2 lacks the treatment of atmospheric disequilibrium processes as encountered, e.g., in mountain lee waves. Here Knopf responds to these points. (1) As mentioned in Knopf,2 a possible pseudoheterogeneous nucleation mechanism is not ruled out, but it is shown, that the upper limits of the PNRs of NAD are too small to explain observations of large nitric acid containing particles (LNACP) in number densities of about 10-4 cm-3 in synoptic PSCs.4 These findings are in agreement with two more recent studies.5,6 Knopf2 follows a similar analysis of Tabazadeh et al.3 but uses a more extensive NAD and NAT nucleation data set compared to Tabazadeh et al.’s3 that also includes nucleation in supercooled HNO3/H2SO4/H2O solution droplets. Tabazadeh et al.3 neglected data sets of Koop et al.7,8 and Bertram et al.9 without further discussion, and those have been shown2 to disagree with the PNR parametrization.3 For these reasons, Knopf’s new analysis provides more conservative upper limits of the PNRs under relevant stratospheric conditions.2 (2) Knopf2 investigates pseudoheterogeneous nucleation occurring in aqueous HNO3 and aqueous HNO3/H2SO4 solution droplets. The general idea of pseudoheterogeneous nucleation may be supported by recent experimental and theoretical studies applying pure water droplets,10-15 as mentioned by Tabazadeh.1 However, one should proceed with caution when transferring nucleation characteristics obtained from pure water droplets to droplets containing aqueous electrolytic solutions. It is wellknown that nucleation characteristics such as nucleation temperature and phase change significantly when electrolytes are added to pure water.16,17 (3) Tabazadeh et al.3 fit the activation energies linearly as a function of S. This is in disagreement with classical nucleation theory (CNT)18 and results in finite PNR values, J, at the melting point of the crystal. Correct employment of the CNT framework would result in a logarithmic dependency between the activation energy and S, which leads to the correct thermodynamic behavior of limSf1 J ) 0, i.e., the PNR approaches 0 as the melting point of the crystal is reached.18 As shown in Knopf,2 employing all available nucleation data sets, which cover S < 10, the PNRs behave according to CNT. (4) A change in the activation energy by 1 kcal mol-1 changes the PNR by a factor of 14. A 10% adjustment of the activation energy could lead to changes of 3 kcal mol-1 in the activation energy under stratospheric conditions. Such an arbitrary adjustment of the pseudoheterogeneous activation energy may result in the correct representation of the observed particle numbers but does not provide evidence that the particles indeed formed by pseudoheterogeneous nucleation. Additionally, decreasing the activation energy by 10% may result in disagreement with laboratory data used to derive the concept of pseudoheterogeneous nucleation.3 (5) The nucleation rates derived by Knopf et al.19 and Knopf2 are discussed for equilibrium conditions typically encountered in synoptic scale PSCs, as has been done by Tabazadeh et al., and others.7-9,21-23 Knopf et al.19 and Knopf2 found that neither homogeneous nucleation nor pseudoheterogeneous nucleation, respectively, are sufficient to explain LNACP (10-4 particles cm-3). Tabazadeh1 addresses other atmospheric scenarios in which particles and gas phase may be in disequilibrium. Such disequilibrium events may be encountered in mountain lee waves with particle number densities much higher than 0.1 cm-3. To address these points, the reader is referred to the work of Meilinger et al.,24 Tsias et al.,25 and Luo et al.,26 the last discussing various nucleation scenarios for S values up to 500. Although Tabazadeh et al.3 mention caveats within their analysis, many modeling studies are using this parametrization to deduce if pseudoheterogeneous nucleation occurred under atmospherically conditions. These include two very recent studies of Tabazadeh,27,28 although the author is aware of the problematic extrapolation of PNRs to stratospheric conditions.1 Knopf points out that a PNR parametrization that is thermodynamically not sound and that is in disagreement with laboratory data cannot be used to determine nonambiguously if pseudoheterogeneous nucleation of NAD occurred in synoptic PSCs.2 An adjusted PNR parametrization1,27 may be used as a first approximation to describe the atmospheric particle observations, but from this it cannot be concluded that LNACP were formed by a pseudoheterogeneous nucleation mechanism.

3-D microphysical model studies of Arctic denitrification: comparison with observations

Abstract. Simulations of Arctic denitrification using a 3-D chemistry-microphysics transport model are compared with observations for the winters 1994/95, 1996/97 and 1999/2000. The model of Denitrification by Lagrangian Particle Sedimentation (DLAPSE) couples the full chemical scheme of the 3-D chemical transport model, SLIMCAT, with a nitric acid trihydrate (NAT) growth and sedimentation scheme. We use observations from the Microwave Limb Sounder (MLS) and Improved Limb Atmospheric Sounder (ILAS) satellite instruments, the balloon-borne Michelsen Interferometer for Passive Atmospheric Sounding (MIPAS-B), and the in situ NOy instrument on-board the ER-2. As well as directly comparing model results with observations, we also assess the extent to which these observations are able to validate the modelling approach taken. For instance, in 1999/2000 the model captures the temporal development of denitrification observed by the ER-2 from late January into March. However, in this winter the vortex was already highly denitrified by late January so the observations do not provide a strong constraint on the modelled rate of denitrification. The model also reproduces the MLS observations of denitrification in early February 2000. In 1996/97 the model captures the timing and magnitude of denitrification as observed by ILAS, although the lack of observations north of ~67° N in the beginning of February make it difficult to constrain the actual timing of onset. The comparison for this winter does not support previous conclusions that denitrification must be caused by an ice-mediated process. In 1994/95 the model notably underestimates the magnitude of denitrification observed during a single balloon flight of the MIPAS-B instrument. Agreement between model and MLS HNO3 at 68 hPa in mid-February 1995 is significantly better. Sensitivity tests show that a 1.5 K overall decrease in vortex temperatures, or a factor 4 increase in assumed NAT nucleation rates, produce the best statistical fit to MLS observations. Both adjustments would be required to bring the model into agreement with the MIPAS-B observations. The agreement between the model and observations suggests that a NAT-only denitrification scheme (without ice), which was discounted by previous studies, must now be considered as one mechanism for the observed Arctic denitrification. The timing of onset and the rate of denitrification remain poorly constrained by the available observations.

Nitric Acid Trihydrate (NAT) formation at low NAT supersaturation in Polar Stratospheric Clouds (PSCs)

Abstract. A PSC was detected on 6 February 2003 in the Arctic stratosphere by in-situ measurements onboard the high-altitude research aircraft Geophysica. Low number densities (~10-4cm-3) of small nitric acid (HNO3) containing particles (d&lt;6µm) were observed at altitudes between 18 and 20km. Provided the temperatures remain below the NAT equilibrium temperature TNAT, these NAT particles have the potential to grow further and to remove HNO3 from the stratosphere, thereby enhancing polar ozone loss. Interestingly, the NAT particles formed in less than a day at temperatures just slightly below TNAT (T&gt;TNAT-3.1K). This unique measurement of PSC formation at extremely low NAT saturation ratios (SNAT≤10) constrains current NAT nucleation theories. We suggest, that the NAT particles have formed heterogeneously, but for certain not on ice. Conversely, meteoritic particles may be favorable candidates for triggering NAT nucleation at the observed low number densities.

Extreme NAT supersaturations in mountain wave ice PSCs: A clue to NAT formation

There is evidence for the existence of nitric acid trihydrate (NAT) in polar stratospheric clouds (PSCs) and for its role in sedimentary denitrification enhancing chlorine‐catalyzed ozone reduction. However, the scientific understanding of NAT formation mechanisms is vague. We show that high cooling rates in mountain waves, though causing only moderate NAT saturation ratios (SNAT ≲ 30) within supercooled ternary solution (STS) droplets, lead to SNAT ≳ 500 within the gas phase. Evidence from previous laboratory measurements suggests that such extreme supersaturations promote NAT deposition nucleation on ice or other solid surfaces, as long as they are not coated by STS. On the basis of airborne lidar PSC observations in three Arctic winters and a combined microphysical/optical model, we derive a simple parameterization for a NAT deposition nucleation rate which depends only on NAT supersaturation and temperature. The results indicate that deposition nucleation of NAT on ice surfaces exposed directly to the gas phase driven by extreme NAT supersaturations is able to explain the formation of NAT particle number densities up to ∼10 cm−3.