Heterogeneous chlorine activation on stratospheric aerosols and clouds in the Arctic polar vortex

Chlorine activation in the Arctic is investigated by examining different parameterizations for uptake coefficients on stratospheric aerosols, high-resolution in-situ measurements and vortex-wide satellite observations. The parameterizations for heterogeneous chemistry on liquid aerosols are most sensitive to temperature with the reaction rates doubling for every 1 K increase in temperature. However, differences between the currently available parameterizations are negligible. For Nitric Acid Trihydrate particles (NAT) the major factors of uncertainty are the number density of nucleated particles and different parameterizations for heterogeneous chemistry. These two factors induce an uncertainty that covers several orders of magnitude on the reaction rate. Nonetheless, since predicted reaction rates on liquid aerosols always exceed those on NAT, the overall uncertainty for chlorine activation is small. In-situ observations of ClO<sub>x</sub> from Arctic winters in 2005 and 2010 are used to evaluate the heterogeneous chemistry parameterizations. The conditions for these measurements proved to be very different between those two winters with HCl being the limiting reacting partner for the 2005 measurements and ClONO<sub>2</sub> for the 2010 measurements. Modeled levels of chlorine activation are in very good agreement with the in-situ observations and the surface area provided by Polar Stratospheric Clouds (PSCs) has only a limited impact on modeled chlorine activation. This indicates that the parameterizations give a good representation of the processes in the atmosphere. Back-trajectories started on the location of the observations in 2005 indicate temperatures on the threshold for PSC formation, hence the surface area is mainly provided by the background aerosol. Still, the model shows additional chlorine activation during this time-frame, providing cautionary evidence for chlorine activation even in the absence of PSCs. Vortex-averaged satellite observations by the MLS instrument also show no definite connection between chlorine activation and PSC formation. The inter -and intra-annual variability of vortex-average HCl and HNO<sub>3</sub> based on MLS observations is examined for the Arctic winters 2004/2005 to 2010/2011. These observations show that removal of HCl and HNO<sub>3</sub> from the gas-phase are not correlated. HNO<sub>3</sub> loss exhibits great inter-annual variability depending on prevailing temperatures while HCl loss is continuous through December without considerable inter- or intra-annual variability. Only the recovery of HCl in late winter depends on the level of denitrification. Hence, the occurrence of HNO<sub>3</sub> containing PSC particles does not seem to have a significant effect on the speed of initial chlorine activation on a vortex-wide scale

Stable carbon isotope ratios of toluene in the boundary layer and the lower free troposphere

During the field campaign ZEPTER-2 in autumn 2008 whole air samples were collected on board a Zeppelin NT airship in the planetary boundary layer (PBL) and the lower free troposphere (LFT) over south-west Germany using the ZEppelin Based Isotope Sampler (ZEBIS). These samples were analysed with respect to volatile organic compound (VOC) mixing ratios and stable carbon isotope ratios using a gas chromatograph combustion isotope ratio mass spectrometer (GC-C-IRMS). In this study we present results for toluene, one of the major anthropogenic pollutants, which emphasise the viability of isotope ratio measurements in VOC for atmospheric research, especially to study VOC sources or to track both dynamical and chemical processes. In situ measurements of CO mixing ratios on board the Zeppelin NT were used to allocate the air samples either to the PBL or the LFT. <br><br> In the PBL we observed rather fresh emissions mixing into the background air. We estimated a toluene source isotope ratio of δ¹³C = −28.2 ± 0.5&permil;. Samples from the PBL and the LFT were clearly distinguishable by means of their mixing ratio and isotope ratio signatures. Using the concept of the effective kinetic isotope effect, we were able to separate the effects of dilution processes and photochemical degradation in the free troposphere. We calculated the photochemical age of toluene in the atmosphere in two different ways using isotope ratios and mixing ratios. The results differ strongly in the PBL, probably due to mixing processes, but are compatible with each other in the LFT. Here, they correlate with a slope of 0.90±0.31

ClOOCl photolysis at high solar zenith angles: analysis of the RECONCILE self-match flight

The photolysis rate constant of dichlorine peroxide (ClOOCl, ClO dimer) JClOOCl is a critical parameter in catalytic cycles destroying ozone (O3) in the polar stratosphere. In the atmospherically relevant wavelength region (λ > 310 nm), significant discrepancies between laboratory measurements of ClOOCl absorption cross sections and spectra cause a large uncertainty in JClOOCl. Previous investigations of the consistency of published JClOOCl with atmospheric observations of chlorine monoxide (ClO) and ClOOCl have focused on the photochemical equilibrium between ClOOCl formation and photolysis, and thus could only constrain the ratio of JClOOCl over the ClOOCl formation rate constant krec. Here, we constrain the atmospherically effective JClOOCl independent of krec, using ClO measured in the same air masses before and directly after sunrise during an aircraft flight that was part of the RECONCILE field campaign in the winter 2010 from Kiruna, Sweden. Over sunrise, when the ClO/ClOOCl system comes out of thermal equilibrium and the influence of the ClO recombination reaction is negligible, the increase in ClO concentrations is significantly faster than expected from JClOOCl based on the absorption spectrum proposed by Pope et al. (2007), but does not warrant cross sections larger than recently published values by Papanastasiou et al. (2009). In particular, the existence of a significant ClOOCl absorption band longwards of 420 nm is not supported by our observations. The observed night-time ClO would not be consistent with a ClO/ClOOCl thermal equilibrium constant significantly higher than the one proposed by Plenge et al. (2005)

Chlorine activation on stratospheric aerosols:uncertainties in parameterizations and surface area

Abstract. Chlorine activation in the Arctic is evaluated by examining the different parameterizations for uptake coefficients on stratospheric aerosols, high-resolution in-situ measurements and vortex-wide satellite observations. The parameterizations for heterogeneous chemistry on liquid aerosols are most sensitive to temperature with the reaction rates doubling for each Kelvin increase in temperature. However, differences between the parameterizations are negligible. For Nitric Acid Trihydrate particles (NAT) the major factors of uncertainty are the number density of nucleated particles and different parameterization choices. These two factors induce an uncertainty that covers several orders of magnitude on the reaction rate. But as predicted reaction rates on liquid aerosols always exceed those on NAT the overall uncertainty is small. In-situ observations of ClOx from Arctic winters in 2005 and 2010 are used to validate the heterogeneous chemistry parameterizations. The ambient conditions for these measurements proved to be very different between those two winters with HCl being the limiting reacting partner for the 2005 measurements and ClONO2 for the 2010 measurements. Modeled levels of chlorine activation are in very good agreement with the in-situ observations and the surface area provided by Polar Stratospheric Clouds (PSCs) has only a limited impact on modeled chlorine activation. This indicates that the parameterizations give a good representation of the processes in the atmosphere. Back-trajectories started on the location of the observations in 2005 indicate temperatures on the threshold for PSC formation, hence the surface area is mainly provided by the background aerosol. Still, the model shows additional chlorine activation during this time-frame, providing cautionary evidence for chlorine activation even in the absence of PSCs. Vortex-averaged satellite observations also show no definite connection between chlorine activation and PSC formation. The inter- and intra-annual variability of vortex-average HCl and HNO3 based on MLS observations is examined for the Arctic winters 2004/2005 to 2010/2011. These observations show that removal of HCl and HNO3 from the gas-phase are not correlated. HNO3 loss exhibits great inter-annual variability depending on prevailing temperatures while HCl loss is continuous through December without considerable inter- or intra-annual variability. Only the recovery of HCl in late in winter depends on the level of denitrification. Hence, the occurrence of HNO3 containing PSC particles does not seem to have a significant effect on the speed of initial chlorine activation on a vortex-wide scale. </jats:p

CRISTA-NF measurements with unprecedented vertical resolution during the RECONCILE aircraft campaign

The Cryogenic Infrared Spectrometers and Telescope for the Atmosphere - New Frontiers (CRISTA-NF), an airborne infrared limb-sounder, was operated aboard the high-flying Russian research aircraft M55-Geophysica during the Arctic RECONCILE campaign from January to March 2010. This paper describes the calibration process of the instrument and the retrieval algorithm employed and then proceeds to present retrieved trace gas volume mixing ratio cross-sections for one specific flight in this campaign. We are able to resolve the uppermost troposphere/lower stratosphere for several trace gas species for several kilometres below the flight altitude (16 to 19 km) with an unprecedented vertical resolution of 400 to 500 m for the limb-sounding technique. The instrument points sideways with respect to the flight direction. Therefore, the observations are also characterised by a rather high horizontal sampling along the flight track, which provides a full vertical profile every approximate to 15 km. Assembling the vertical trace gas profiles derived from CRISTA-NF measurements to cross-sections shows filaments of vortex and extra-vortex air masses in the vicinity of the polar vortex.During this campaign, the M55-Geophysica carried further instruments enabling trace gas volume mixing ratios derived from CRISTA-NF to be validated by comparing them with measurements by the in situ instruments HAGAR and FOZAN and observations by MIPAS-STR. This validation suggests that the retrieved trace gas volume mixing ratios are both qualitatively and quantitatively reliable

Uncertainties in modeling heterogeneous chemistry and Arctic ozone depletion in the winter 2009/2010

Stratospheric chemistry and denitrification are simulated for the Arctic winter 2009/2010 with the Lagrangian Chemistry and Transport Model ATLAS. A number of sensitivity runs is used to explore the impact of uncertainties in chlorine activation and denitrification on the model results. In particular, the efficiency of chlorine activation on different types of liquid aerosol versus activation on nitric acid trihydrate clouds is examined. Additionally, the impact of changes in reaction rate coefficients, in the particle number density of polar stratospheric clouds, in supersaturation, temperature or the extent of denitrification is investigated. Results are compared to satellite measurements of MLS and ACE-FTS and to in-situ measurements onboard the Geophysica aircraft during the RECONCILE measurement campaign. It is shown that even large changes in the underlying assumptions have only a small impact on the modelled ozone loss, even though they can cause considerable differences in chemical evolution of other species and in denitrification. Differences in column ozone between the sensitivity runs stay below 10% at the end of the winter. Chlorine activation on liquid aerosols alone is able to explain the observed magnitude and morphology of the mixing ratios of active chlorine, reservoir gases and ozone. This is even true for binary aerosols (no uptake of HNO3 from the gas-phase allowed in the model). Differences in chlorine activation between sensitivity runs are within 30%. Current estimates of nitric acid trihydrate (NAT) number density and supersaturation imply that, at least for this winter, NAT clouds play a relatively small role compared to liquid clouds in chlorine activation. The change between different reaction rate coefficients for liquid or solid clouds has only a minor impact on ozone loss and chlorine activation in our sensitivity runs

Uncertainties in modelling heterogeneous chemistry and Arctic ozone depletion in the winter 2009/2010

Stratospheric chemistry and denitrification are simulated for the Arctic winter 2009/2010 with the Lagrangian Chemistry and Transport Model ATLAS. A number of sensitivity runs is used to explore the impact of uncertainties in chlorine activation and denitrification on the model results. In particular, the efficiency of chlorine activation on different types of liquid aerosol versus activation on nitric acid trihydrate clouds is examined. Additionally, the impact of changes in reaction rate coefficients, in the particle number density of polar stratospheric clouds, in supersaturation, temperature or the extent of denitrification is investigated. Results are compared to satellite measurements of MLS and ACE-FTS and to in-situ measurements onboard the Geophysica aircraft during the RECONCILE measurement campaign. It is shown that even large changes in the underlying assumptions have only a small impact on the modelled ozone loss, even though they can cause considerable differences in chemical evolution of other species and in denitrification. Differences in column ozone between the sensitivity runs stay below 10% at the end of the winter. Chlorine activation on liquid aerosols alone is able to explain the observed magnitude and morphology of the mixing ratios of active chlorine, reservoir gases and ozone. This is even true for binary aerosols (no uptake of HNO3 from the gas-phase allowed in the model). Differences in chlorine activation between sensitivity runs are within 30%. Current estimates of nitric acid trihydrate (NAT) number density and supersaturation imply that, at least for this winter, NAT clouds play a relatively small role compared to liquid clouds in chlorine activation. The change between different reaction rate coefficients for liquid or solid clouds has only a minor impact on ozone loss and chlorine activation in our sensitivity runs