ClONO2 Research Articles

Molecular Insights into the Spontaneous Generation of Cl2O in the Reaction of ClONO2 and HOCl at the Air-Water Interface.

Chemical processes involving chlorine nitrate (ClONO2) at the surface of stratospheric aerosols are crucial to ozone depletion. Herein, we show a reaction route for the formation of Cl2O, which is a source of stratospheric chlorine, in the ClONO2 + HOCl reaction at the air-water interface. Our ab initio molecular dynamics (AIMD) simulations show that the (ClONO2)Cl···O(HOCl) halogen bond plays a key role in the reaction and is the main interaction between ClONO2 and HOCl both at the air-water interface and in the bulk liquid water. Furthermore, metadynamics-based AIMD simulations reveal two pathways: (i) The OCl fragment of HOCl binds to the Cl atom in ClONO2, resulting in the formation of Cl2O and NO3-. Simultaneously, the remaining hydrogen atom is transferred to a water molecule to form H3O+. (ii) HOCl acts as a bridge for Cl atom transfer from ClONO2 to the O atom of a water molecule, and this water molecule transfers one of its H atoms to another water molecule, forming two HOCl molecules, NO3-, and H3O+. Free-energy calculations show that the former is the energetically more favorable process. More importantly, the free-energy barrier for Cl2O formation at the air-water interface is only ∼0.8 kcal/mol, and the reaction is exothermic. These findings provide insights into the importance of fundamental chlorine chemistry and the broader implications of the aerosol air-water interface for atmospheric chemistry.

Chlorine activation and enhanced ozone depletion induced by wildfire aerosol.

Remarkable perturbations in the stratospheric abundances of chlorine species and ozone were observed over Southern Hemisphere mid-latitudes following the 2020 Australian wildfires1,2. These changes in atmospheric chemical composition suggest that wildfire aerosols affect stratospheric chlorine and ozone depletion chemistry. Here we propose that wildfire aerosol containing a mixture of oxidized organics and sulfate3-7 increases hydrochloric acid solubility8-11 and associated heterogeneous reaction rates, activating reactive chlorine species and enhancing ozone loss rates at relatively warm stratospheric temperatures. We test our hypothesis by comparing atmospheric observations to model simulations that include the proposed mechanism. Modelled changes in 2020 hydrochloric acid, chlorine nitrate and hypochlorous acid abundances are in good agreement with observations1,2. Our results indicate that wildfire aerosol chemistry, although not accounting for the record duration of the 2020 Antarctic ozone hole, does yield an increase in its area and a 3-5% depletion of southern mid-latitude total column ozone. These findings increase concern2,12,13 that more frequent and intense wildfires could delay ozone recovery in a warming world.

Mechanistic Insights into the Reactive Uptake of Chlorine Nitrate at the Air-Water Interface.

It is well-known that the aqueous-phase processing of chlorine nitrate (ClONO2) plays a crucial role in ozone depletion. However, many of the physical and chemical properties of ClONO2 at the air-water interface or in bulk water are unknown or not understood on a microscopic scale. Here, the solvation and hydrolysis of ClONO2 at the air-water interface and in bulk water at 300 K were investigated by classical and ab initio molecular dynamics (AIMD) simulations combined with free energy methods. Our results revealed that ClONO2 prefers to accumulate at the air-water interface rather than in the bulk phase. Specifically, halogen bonding interactions (ClONO2)Cl···O(H2O) were found to be the predominant interactions between ClONO2 and H2O. Moreover, metadynamics-biased AIMD simulations revealed that ClONO2 hydrolysis is catalyzed at the air-water interface with an activation barrier of only ∼0.2 kcal/mol; additionally, the difference in free energy between the product and reactant is only ∼0.1 kcal/mol. Surprisingly, the near-barrierless reaction and the comparable free energies of the reactant and product suggested that the ClONO2 hydrolysis at the air-water interface is reversible. When the temperature is lowered from 300 to 200 K, the activation barrier for the ClONO2 hydrolysis at the air-water interface is increased to ∼5.4 kcal/mol. These findings have important implications for the interpretation of experiments.

A deep learning system to transform cross-section spectra to varying environmental conditions

Absorption cross-sections provide a basis for many gas sensing applications. Therefore, any error in molecular cross-sections caused by varying environmental conditions propagates to spectroscopic applications. Original molecular cross-sections in varying environmental conditions can only be simulated for some molecules, whereas for most multi-atom molecules, one must rely on high-precision measurements at certain environmental configurations. In this study, a deep learning system trained with simulated absorption cross-sections for predicting cross-sections at a different pressure configuration is presented. The system’s capability to transfer to measured, multi-atom cross-sections is demonstrated. Thus, it provides an alternative to (pseudo-) line lists whenever the required information for simulation is unavailable. The predictive performance of the system was evaluated on validation data via simulation, and its transfer learning capabilities were demonstrated on actual measurement chlorine nitrate data. From the comparison between the system and line lists, the system shows slightly worse performance than pseudo-line lists but its predictive quality is still deemed acceptable with less than 5 % relative integral change with a highly localized error around the peak center. This opens a promising way for further research to use deep learning to simulate the effect of varying environmental conditions on absorption cross-sections.

The influence of energetic particle precipitation on Antarctic stratospheric chlorine and ozone over the 20th century

Abstract. Chlorofluorocarbon (CFC) emissions in the latter part of the 20th century reduced stratospheric ozone abundance substantially, especially in the Antarctic region. Simultaneously, polar stratospheric ozone is also destroyed catalytically by nitrogen oxides (NOx = NO + NO2) descending from the mesosphere and the lower thermosphere during winter. These are produced by energetic particle precipitation (EPP) linked to solar activity and space weather. Active chlorine (ClOx = Cl + ClO) can also react mutually with EPP-produced NOx or hydrogen oxides (HOx) and transform both reactive agents into reservoir gases, chlorine nitrate or hydrogen chloride, which buffer ozone destruction by all these agents. We study the interaction between EPP-produced NOx, ClO and ozone over the 20th century by using free-running climate simulations of the chemistry–climate model SOCOL3-MPIOM. A substantial increase of NOx descending to the polar stratosphere is found during winter, which causes ozone depletion in the upper and mid-stratosphere. However, in the Antarctic mid-stratosphere, the EPP-induced ozone depletion became less efficient after the 1960s, especially during springtime. Simultaneously, a significant decrease in stratospheric ClO and an increase in hydrogen chloride – and partly chlorine nitrate between 10–30 hPa – can be ascribed to EPP forcing. Hence, the interaction between EPP-produced NOx/HOx and ClO likely suppressed the ozone depletion, due to both EPP and ClO at these altitudes. Furthermore, at the end of the century, a significant ClO increase and ozone decrease were obtained at 100 hPa altitude during winter and spring. This lower stratosphere response shows that EPP can influence the activation of chlorine from reservoir gases on polar stratospheric clouds, thus modulating chemical processes important for ozone hole formation. Our results show that EPP has been a significant modulator of reactive chlorine in the Antarctic stratosphere during the CFC era. With the implementation of the Montreal Protocol, stratospheric chlorine is estimated to return to pre-CFC era levels after 2050. Thus, we expect increased efficiency of chemical ozone destruction by EPP-NOx in the Antarctic upper and mid-stratosphere over coming decades. The future lower stratosphere ozone response by EPP is more uncertain.

Wildfire smoke destroys stratospheric ozone.

Large wildfires inject smoke and biomass-burning products into the mid-latitude stratosphere, where they destroy ozone, which protects us from ultraviolet radiation. The infrared spectrometer on the Atmospheric Chemistry Experiment satellite measured the spectra of smoke particles from the "Black Summer" fires in Australia in late 2019 and early 2020, revealing that they contain oxygenated organic functional groups and water adsorption on the surfaces. These injected smoke particles have produced unexpected and extreme perturbations in stratospheric gases beyond any seen in the previous 15 years of measurements, including increases in formaldehyde, chlorine nitrate, chlorine monoxide, and hypochlorous acid and decreases in ozone, nitrogen dioxide, and hydrochloric acid. These perturbations in stratospheric composition have the potential to affect ozone chemistry in unexpected ways.

Optimization of Procedure for Determining Chlorine Nitrate in the Atmosphere from Ground-Based Spectroscopic Measurements

The procedure for determining the total content of chlorine nitrate (ClONO2) from ground-based measurements of the solar radiation spectra on a Bruker 125HR Fourier spectrometer at the St. Petersburg station (59.88oN, 29.82oE, 20 m above sea level) of the international observational network NDACC is examined. The method was applied to spectra measured in the period from 2009 to 2019, and the results were compared with calculations by the EMAC chemistry-climate model. Good qualitative and quantitative agreement was obtained between the experimental data and the results of numerical modeling. For the period 2009–2017 the average mismatch between model and experiment was 3%, the standard deviation was 43%, and the correlation coefficient was 0.79 ± 0.02, which indicates an adequate description of the variability of the total ClONO2 content by the model. Assessment of the linear trend of the total ClONO2 content showed a significant decrease in the total chlorine nitrate content in the atmosphere over St. Petersburg according both to the ground-based measurements (–2.3 ± 1.9% per year) and to the model (–1.2 ± 0.4% per year).

Technical note: Determination of binary gas-phase diffusion coefficients of unstable and adsorbing atmospheric trace gases at low temperature – arrested flow and twin tube method

Abstract. Gas-phase diffusion is the first step for all heterogeneous reactions under atmospheric conditions. Knowledge of binary diffusion coefficients is important for the interpretation of laboratory studies regarding heterogeneous trace gas uptake and reactions. Only for stable, nonreactive and nonpolar gases do well-established models for the estimation of diffusion coefficients from viscosity data exist. Therefore, we have used two complementary methods for the measurement of binary diffusion coefficients in the temperature range of 200 to 300 K: the arrested flow method is best suited for unstable gases, and the twin tube method is best suited for stable but adsorbing trace gases. Both methods were validated by the measurement of the diffusion coefficients of methane and ethane in helium and air as well as nitric oxide in helium. Using the arrested flow method the diffusion coefficients of ozone in air, dinitrogen pentoxide and chlorine nitrate in helium, and nitrogen were measured. The twin tube method was used for the measurement of the diffusion coefficient of nitrogen dioxide and dinitrogen tetroxide in helium and nitrogen.

Unusual chlorine partitioning in the 2015/16 Arctic winter lowermost stratosphere: observations and simulations

Abstract. The Arctic winter 2015/16 was characterized by cold stratospheric temperatures. Here we present a comprehensive view of the temporal evolution of chlorine in the lowermost stratosphere over the course of the studied winter. We utilize two-dimensional vertical cross sections of ozone (O3) and chlorine nitrate (ClONO2), measured by the airborne limb imager GLORIA (Gimballed Limb Observer for Radiance Imaging of the Atmosphere) during the POLSTRACC/GW-LCYCLE II/GWEX/SALSA campaigns, to investigate the tropopause region in detail. Observations from three long-distance flights in January, February, and March 2016 are discussed. ClONO2 volume mixing ratios up to 1100 pptv were measured at 380 K potential temperature in mesoscale structures. Similar mesoscale structures are also visible in O3 measurements. Both trace gas measurements are applied to evaluate simulation results from the chemistry transport model CLaMS (Chemical Lagrangian Model of the Stratosphere) and the chemistry–climate model EMAC (ECHAM5/MESSy Atmospheric Chemistry). These comparisons show agreement within the expected performance of these models. Satellite measurements from Aura/MLS (Microwave Limb Sounder) and SCISAT/ACE-FTS (Atmospheric Chemistry Experiment – Fourier Transform Spectrometer) provide an overview over the whole winter and information about the stratospheric situation above the flight altitude. Time series of these satellite measurements reveal unusually low hydrochloric acid (HCl) and ClONO2 at 380 K from the beginning of January to the end of February 2016, while chlorine monoxide (ClO) is strongly enhanced. In March 2016, unusually rapid chlorine deactivation into HCl is observed instead of deactivation into ClONO2, the more typical pathway for deactivation in the Arctic. Chlorine deactivation observed in the satellite time series is well reproduced by CLaMS. Sensitivity simulations with CLaMS demonstrate the influence of low abundances of O3 and reactive nitrogen (NOy) due to ozone depletion and sedimentation of NOy-containing particles, respectively. On the basis of the different altitude and time ranges of these effects, we conclude that the substantial chlorine deactivation into HCl at 380 K arose as a result of very low ozone abundances together with low temperatures. Additionally, CLaMS estimates ozone depletion of at least 0.4 ppmv at 380 K and 1.75 ppmv at 490 K, which is comparable to other extremely cold Arctic winters. We have used CLaMS trajectories to analyze the history of enhanced ClONO2 measured by GLORIA. In February, most of the enhanced ClONO2 is traced back to chlorine deactivation that had occurred within the past few days prior to the GLORIA measurement. In March, after the final warming, air masses in which chlorine has previously been deactivated into ClONO2 have been transported in the remnants of the polar vortex towards the location of measurement for at least 11 d.

High-resolution analysis of the 12.6 µm spectral region of the nitryl chloride ClNO2 molecule

The 12.6 µm region of nitryl chloride (ClNO2) has been recorded at high resolution (0.00102 cm−1) using a Fourier transform spectrometer and the SOLEIL synchrotron light source. ClNO2 was found during our studies of chlorine nitrate and, after fractional distillations it was introduced into a multipass White cell made of inert materials, with an optical path length of 5.4 m. 320 scans were recorded for the range 600–980 cm−1 at a total pressure of 0.23 hPa and a temperature of 250 K. A thorough analysis of the ν2, 2ν6 and 2ν3 bands of 35ClNO2 and of the ν2 band of 37ClNO2 falling in this region has been carried out using a Hamiltonian model which takes explicitly into account the numerous resonances affecting the ro-vibrational energy levels; especially the C-type Coriolis resonance between the ν2 and the ν3 + ν6 modes. These two modes are only separated by less than 20 cm−1 and are thoroughly mixed. From the fittings, the following band centers were derived: νo(ν2) = 792.761264(60) cm−1, νo(ν3 + ν6) = 775.8923(20) cm−1, νo(2ν3) = 734.183576(20) cm−1 and νo(2ν6) = 819.836727(90) cm−1 for 35ClNO2 and νo(ν2) = 792.258284(30) cm−1 and νo(ν3 + ν6) = 774.6826(30) cm−1 for 37ClNO2 where the uncertainties are one standard deviation. Due to their sharp Q branches falling into an atmospheric “window”, the detection of the ν2 bands might be an advantageous route for future attempts to quantify atmospheric ClNO2, using infrared techniques.

Chlorine nitrate in the atmosphere

Abstract. This review article compiles the characteristics of the gas chlorine nitrate and discusses its role in atmospheric chemistry. Chlorine nitrate is a reservoir of both stratospheric chlorine and nitrogen. It is formed by a termolecular reaction of ClO and NO2. Sink processes include gas-phase chemistry, photo-dissociation, and heterogeneous chemistry on aerosols. The latter sink is particularly important in the context of polar spring stratospheric chlorine activation. ClONO2 has vibrational–rotational bands in the infrared, notably at 779, 809, 1293, and 1735 cm−1, which are used for remote sensing of ClONO2 in the atmosphere. Mid-infrared emission and absorption spectroscopy have long been the only concepts for atmospheric ClONO2 measurements. More recently, fluorescence and mass spectroscopic in situ techniques have been developed. Global ClONO2 distributions have a maximum at polar winter latitudes at about 20–30 km altitude, where mixing ratios can exceed 2 ppbv. The annual cycle is most pronounced in the polar stratosphere, where ClONO2 concentrations are an indicator of chlorine activation and de-activation.

Monsoon circulations and tropical heterogeneous chlorine chemistry in the stratosphere

AbstractModel simulations presented in this paper suggest that transport processes associated with the summer monsoons bring increased abundances of hydrochloric acid into contact with liquid sulfate aerosols in the cold tropical lowermost stratosphere, leading to heterogeneous chemical activation of chlorine species. The calculations indicate that the spatial and seasonal distributions of chlorine monoxide and chlorine nitrate near the monsoon regions of the northern hemisphere tropical and subtropical lowermost stratosphere could provide indicators of heterogeneous chlorine processing. In the model, these processes impact the local ozone budget and decrease ozone abundances, implying a chemical contribution to longer‐term northern tropical ozone profile changes at 16–19 km.

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.

Chlorine Nitrate in the Atmosphere over St. Petersburg

Chlorine Nitrate in the Atmosphere over St. Petersburg

Chlorine nitrate in the atmosphere over St. Petersburg

Ground-based measurements of the total chlorine nitrate (ClONO2) in the atmosphere have been taken for the first time in Russia using the Bruker IFS-125HR infrared (IR) Fourier spectrometer (FS). The average error of the total ClONO2 measurements, performed in 2009–2012 in Peterhof, is (25 ± 10)%. The results have been compared with measurements performed using similar devices at the NDACC network, Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) satellite measurements, and the total ClONO2 numerical simulation (performed using the EMAC chemical climatic model). The total ClONO2 seasonal variations are similar for three considered observation stations (Peterhof, Kiruna, and Eureka) with the maximum in February-March, which is more pronounced at higher latitudes. High correlations (R = 0.7–0.9) between the MIPAS satellite data, ground-based measurements near St. Petersburg, and the values calculated using the EMAC model have been revealed. The modeling data are on average smaller than the data of the ground-based and satellite measurements. An analysis of the seasonal variations in the total ClONO2 monthly average values in the St. Petersburg region indicated that this difference is caused by the fact that the model underestimated the maximal total ClONO2 values in the atmosphere.

Technical Note: SWIFT – a fast semi-empirical model for polar stratospheric ozone loss

Abstract. An extremely fast model to estimate the degree of stratospheric ozone depletion during polar winters is described. It is based on a set of coupled differential equations that simulate the seasonal evolution of vortex-averaged hydrogen chloride (HCl), nitric acid (HNO3), chlorine nitrate (ClONO2), active forms of chlorine (ClOx = Cl + ClO + 2 ClOOCl) and ozone (O3) on isentropic levels within the polar vortices. Terms in these equations account for the chemical and physical processes driving the time rate of change of these species. Eight empirical fit coefficients associated with these terms are derived by iteratively fitting the equations to vortex-averaged satellite-based measurements of HCl, HNO3 and ClONO2 and observationally derived ozone loss rates. The system of differential equations is not stiff and can be solved with a time step of one day, allowing many years to be processed per second on a standard PC. The inputs required are the daily fractions of the vortex area covered by polar stratospheric clouds and the fractions of the vortex area exposed to sunlight. The resultant model, SWIFT (Semi-empirical Weighted Iterative Fit Technique), provides a fast yet accurate method to simulate ozone loss rates in polar regions. SWIFT's capabilities are demonstrated by comparing measured and modeled total ozone loss outside of the training period.

The uptake of ClNO3 on film coatings of natural sea salt

Using a coated-insert flow tube reactor coupled to a high-resolution low-energy electron impact mass spectrometer, the uptake of chlorine nitrate on a salt film coating of natural sea salt (NSS) was studied under variation in the reactant concentration ([ClNO3] = (1–15) · 1012 cm−3), humidity ([H2O] = (0.01–2.2) · 1015 cm−3), and reactor temperatures of 295 and 423 K. The time-dependent character of the uptake coefficient γ(t) = γ ini exp(−t/τ) + γ ss [1 − exp(−t/τ)] with parameters of the initial (γ ini ) and steady-state (γ ss ) uptake and characteristic time dependent on [ClNO3] was established. The only detected gas phase uptake product was Cl2. The absence of the dependence of the steady-state uptake coefficent γ ss on humidity in the aforementioned [H2O] range was established. Based on the model description of experimental dependences in terms of the modified Langmuir adsorption model, the adsorption heat of chlorine nitrate on NSS and the constant of unimolecular decay rate of the ClNO3…Z surface complex with the formation of the Cl2 product were estimated. It follows from the comparison of these parameters for the initial and steady-state uptake that their adsorption heats are similar within the experimental error and the difference between the coefficients γ ini and γ ss is caused by the difference in activation energies of unimolecular decay. The coefficients γ ini , γ ss , and τ were estimated under tropospheric chlorine nitrate concentrations that are unavailable in laboratory conditions.

HCl and ClO profiles inside the Antarctic vortex as observed by SMILES in November 2009: comparisons with MLS and ACE-FTS instruments

Abstract. We present vertical profiles of hydrogen chloride (HCl) and chlorine monoxide (ClO) as observed by the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) on the International Space Station (ISS) inside the Antarctic vortex on 19–24 November 2009. The SMILES HCl value reveals 2.8–3.1 ppbv between 450 K and 500 K levels in potential temperature (PT). The high value of HCl is highlighted since it is suggested that HCl is a main component of the total inorganic chlorine (Cly), defined as Cly ≃ HCl + ClO + chlorine nitrate (ClONO2), inside the Antarctic vortex in spring, owing to low ozone values. To confirm the quality of two SMILES level 2 (L2) data products provided by the Japan Aerospace Exploration Agency (JAXA) and Japan's National Institute of Information and Communications Technology (NICT), vis-à-vis the partitioning of Cly, comparisons are made using other satellite data from the Aura Microwave Limb Sounder (MLS) and Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS). HCl values from the SMILES NICT L2 product agree to within 10% (0.3 ppbv) with the MLS HCl data between 450 and 575 K levels in PT and with the ACE-FTS HCl data between 425 and 575 K. The SMILES JAXA L2 product is 10 to 20% (0.2–0.5 ppbv) lower than that from MLS between 400 and 700 K and from ACE-FTS between 500 and 700 K. For ClO in daytime, the difference between SMILES (JAXA and NICT) and MLS is less than ±0.05 ppbv (100 %) between 500 K and 650 K with the ClO values less than 0.2 ppbv. ClONO2 values as measured by ACE-FTS also reveal 0.2 ppbv at 475–500 K level, resulting in the HCl / Cly ratios of 0.91–0.95. The HCl / Cly ratios derived from each retrieval agree to within −5 to 8 % with regard to their averages. The high HCl values and HCl / Cly ratios observed by the three instruments in the lower stratospheric Antarctic vortex are consistent with previous observations in late Austral spring.

Theoretical Investigation of the Reaction Mechanism of ClONO2 + HCl → HNO3 + Cl2 on (H2O)n (n = 0–3) Cluster

Hydrated chlorine nitrate and hydrogen chloride ClONO2·HCl·(H2O)n (n = 0-3) clusters were investigated by using the MP2/aug-cc-pVTZ level of theory to clarify the reaction mechanism of Cl2 production. Isomeric stable structures found in n = 2 and 3 clusters have equivalent binding energies and the reaction barrier drastically decreases to be 2.1 kcal/mol at n = 3. The plausible reaction pathways were proposed according to calculated structures and energies, where the zero-point-energy corrections are important to determine the energy profiles of reactions especially for the n = 3 cluster. The kinetic analysis using the transition state theory suggested that the reaction rate constant from the original reactants to the product of n = 3 is 1.8 × 10(5) times larger than that of n = 2 cluster. Even though the small amount of the molar concentration of HCl(H2O)3 is obtained, the overall reaction rate of the trihydrate reaction is still 35 times faster than that of the dihydrate.

Diurnal variations of reactive chlorine and nitrogen oxides observed by MIPAS-B inside the January 2010 Arctic vortex

Abstract. The winter 2009/2010 was characterized by a strong Arctic vortex with extremely cold mid-winter temperatures in the lower stratosphere associated with an intense activation of reactive chlorine compounds (ClOx) from reservoir species. Stratospheric limb emission spectra were recorded during a flight of the balloon version of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS-B) from Kiruna (Sweden) on 24 January 2010 inside the Arctic vortex. Several fast limb sequences of spectra (in time steps of about 10 min) were measured from nighttime photochemical equilibrium to local noon allowing the retrieval of chlorine- and nitrogen-containing species which change rapidly their concentration around the terminator between night and day. Mixing ratios of species like ClO, NO2, and N2O5 show significant changes around sunrise, which are temporally delayed due to polar stratospheric clouds reducing the direct radiative flux from the sun. ClO variations were derived for the first time from MIPAS-B spectra. Daytime ClO values of up to 1.6 ppbv are visible in a broad chlorine activated layer below 26 km correlated with low values (below 0.1 ppbv) of the chlorine reservoir species ClONO2. Observations are compared and discussed with calculations performed with the 3-dimensional Chemistry Climate Model EMAC (ECHAM5/MESSy Atmospheric Chemistry). Mixing ratios of the species ClO, NO2, and N2O5 are well reproduced by the model during night and noon. However, the onset of ClO production and NO2 loss around the terminator in the model is not consistent with the measurements. The MIPAS-B observations along with Tropospheric Ultraviolet-Visible (TUV) radiation model calculations suggest that polar stratospheric clouds lead to a delayed start followed by a faster increase of the photodissoziation of ClOOCl and NO2 near the morning terminator since stratospheric clouds alter the direct and the diffuse flux of solar radiation. These effects are not considered in the EMAC model simulations which assume a cloudless atmosphere.