-
The SLIMCAT three-dimensional chemical transport model (CTM) is used to infer chemical ozone loss from Polar Ozone and Aerosol Measurement (POAM) III observations of stratospheric ozone during the Arctic winter of 2002-2003. Inferring chemical ozone loss from satellite data requires quantifying ozone variations due to dynamical processes. To accomplish this, the SLIMCAT model was run in a "passive" mode from early December until the middle of March. In these runs, ozone is treated as an inert, dynamical tracer. Chemical ozone loss is inferred by subtracting the model passive ozone, evaluated at the time and location of the POAM observations, from the POAM measurements themselves. This "CTM Passive Subtraction" technique relies on accurate initialization of the CTM and a realistic description of vertical/horizontal transport, both of which are explored in this work. The analysis suggests that chemical ozone loss during the 2002-2003 winter began in late December. This loss followed a prolonged period in which many polar stratospheric clouds were detected, and during which vortex air had been transported to sunlit latitudes. A series of stratospheric warming events starting in January hindered chemical ozone loss later in the winter of 2003. Nevertheless, by 15 March, the final date of the analysis, ozone loss maximized at 425K at a value of about 1.2ppmv, a moderate amount of loss compared to loss during the unusually cold winters in the late-1990s. SLIMCAT was also run with a detailed stratospheric chemistry scheme to obtain the model-predicted loss. The SLIMCAT model simulation also shows a maximum ozone loss of 1.2ppmv at 425K, and the morphology of the loss calculated by SLIMCAT was similar to that inferred from the POAM data. These results from the recently updated version of SLIMCAT therefore give a much better quantitative description of polar chemical ozone loss than older versions of the same model. Both the inferred and modeled loss calculations show the early destruction in late December and the region of maximum loss descending in altitude through the remainder of the winter and early spring.
-
The Master Chemical Mechanism has been updated from MCMv3 to MCMv3.1 in order to take into account recent improvements in the understanding of aromatic photo-oxidation. Newly available kinetic and product data from the literature have been incorporated into the mechanism. In particular, the degradation mechanisms for hydroxyarenes have been revised following the observation of high yields of ring-retained products, and product studies of aromatic oxidation under relatively low NO<sub>x</sub> conditions have provided new information on the branching ratios to first generation products. Experiments have been carried out at the European Photoreactor (EUPHORE) to investigate key subsets of the toluene system. These results have been used to test our understanding of toluene oxidation, and, where possible, refine the degradation mechanisms. The evaluation of MCMv3 and MCMv3.1 using data on benzene, toluene, <i>p</i>-xylene and 1,3,5-trimethylbenzene photosmog systems is described in a companion paper, and significant model shortcomings are identified. Ideas for additional modifications to the mechanisms, and for future experiments to further our knowledge of the details of aromatic photo-oxidation are discussed.
-
Direct observation of the Sun at large solar zenith angles during the second SAGE III Ozone Loss and Validation Experiment (SOLVE II)/Validation of International Satellites and study of Ozone Loss (VINTERSOL) campaign by several instruments provided a rich dataset for the retrieval and analysis of line-of-sight column composition, intercomparison, and measurement validation. A flexible, multi-species spectral fitting technique is presented and applied to spectral solar irradiance measurements made by the NCAR Direct beam Irradiance Atmospheric Spectrometer (DIAS) on-board the NASA DC-8. The approach allows for the independent retrieval of O<sub>3</sub>, O<sub>2</sub>·O<sub>2</sub>, and aerosol optical properties, by constraining Rayleigh extinction. We examine the 19 January 2003 and 6 February 2003 flights and find very good agreement of O<sub>3</sub> and O<sub>2</sub>·O<sub>2</sub> retrievals with forward-modeling calculations, even at large solar zenith angles, where refraction is important. Intercomparisons of retrieved ozone and aerosol optical thickness with results from the Ames Airborne Tracking Sunphotometer (AATS-14) are summarized.
-
A high quality dataset on the photo-oxidation of benzene, toluene, <i>p</i>-xylene and 1,3,5-trimethylbenzene has been obtained from experiments in the European Photoreactor (EUPHORE), a large outdoor environmental reaction chamber. The experiments were designed to test sensitive features of detailed aromatic mechanisms, and the dataset has been used to evaluate the performance of the Master Chemical Mechanism Version 3 (MCMv3). An updated version (MCMv3.1) was constructed based on recent experimental data, and details of its development are described in a companion paper. The MCMv3.1 aromatic mechanisms have also been evaluated using the EUPHORE dataset. Significant deficiencies have been identified in the mechanisms, in particular: 1) an over-estimation of the ozone concentration, 2) an under-estimation of the NO oxidation rate, 3) an under-estimation of OH. The use of MCMv3.1 improves the model-measurement agreement in some areas but significant discrepancies remain.
-
In-situ measurements of ClO and its dimer carried out during the SOLVE II/VINTERSOL-EUPLEX and ENVISAT Validation campaigns in the Arctic winter 2003 suggest that the thermal equilibrium between the dimer formation and dissociation is shifted significantly towards the monomer compared to the current JPL 2002 recommendation. Detailed analysis of observations made in thermal equilibrium allowed to re-evaluate the magnitude and temperature dependence of the equilibrium constant. A fit of the JPL format for equilibrium constants yields <i>K<sub>EQ</sub></i>=3.61x10<sup>-27</sup>exp(8167/<i>T</i>), but to reconcile the observations made at low temperatures with the existing laboratory studies at room temperature, a modified equation, <i>K<sub>EQ</sub></i>=5.47x10<sup>-25</sup>(<i>T</i>/300)<sup>-2.29</sup>exp(6969/<i>T</i>), is required. This format can be rationalised by a strong temperature dependence of the reaction enthalpy possibly induced by Cl<sub>2</sub>O<sub>2</sub> isomerism effects. At stratospheric temperatures, both equations are practically equivalent. Using the equilibrium constant reported here rather than the JPL 2002 recommendation in atmospheric models does not have a large impact on simulated ozone loss. Solely at large zenith angles after sunrise, a small decrease of the ozone loss rate due to the ClO dimer cycle and an increase due to the ClO-BrO cycle (attributed to the enhanced equilibrium ClO concentrations) is observed, the net effect being a slightly stronger ozone loss rate.
-
Ozone loss during the winter 2002/2003 has been evaluated from comparisons between total ozone reported by the SAOZ network and simulated in passive mode by both REPROBUS and SLIMCAT. Despite the fact that the two models have a different approach to calculate the descent inside vortex, both evaluations provide similar results 18±4% using REPROBUS and 20±4% using SLIMCAT and show that the loss started around mid-December, at least ten to twenty days earlier than during any of the previous eleven winters, except 1993/1994. This unusual behaviour is consistent with the low temperatures reported in the stratosphere as well to the signature of early chlorine activation indicated by ground-based, balloon and satellite observations. <P style="line-height: 20px;"> A significant ozone loss is also simulated by the current versions of two models, but of lesser amplitude compared to SAOZ, 13±2% for REPROBUS and 16±2% for SLIMCAT, the underestimation being already observed by mid-January. The early ozone depletion captured by both model show that chemical depletion did indeed take place in December, predominantly at the illuminated edge of the distorted vortex, but the reason for the underestimation compared to the observations and the differences among the models have still to be investigated.
-
The Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on ENVISAT has made extensive measurements of polar stratospheric clouds (PSCs) in the northern hemisphere winter 2002/2003. A PSC detection method based on a ratio of radiances (the cloud index) has been implemented for MIPAS and is validated in this study with respect to ground-based lidar and space borne occultation measurements. A very good correspondence in PSC sighting and cloud altitude between MIPAS detections and those of other instruments is found for cloud index values of less than four. Comparisons with data from the Stratospheric Aerosol and Gas Experiment (SAGE) III are used to further show that the sensitivity of the MIPAS detection method for this threshold value of cloud index is approximately equivalent to an extinction limit of 10<sup>-3</sup>km<sup>-1</sup> at 1022nm, a wavelength used by solar occultation experiments. The MIPAS cloud index data are subsequently used to examine, for the first time with any technique, the evolution of PSCs throughout the Arctic polar vortex up to a latitude close to 90° north on a near-daily basis. We find that the winter of 2002/2003 is characterised by three phases of very different PSC activity. First, an unusual, extremely cold phase in the first three weeks of December resulted in high PSC occurrence rates. This was followed by a second phase of only moderate PSC activity from 5-13 January, separated from the first phase by a minor warming event. Finally there was a third phase from February to the end of March where only sporadic and mostly weak PSC events took place. The composition of PSCs during the winter period has also been examined, exploiting in particular an infra-red spectral signature which is probably characteristic of NAT. The MIPAS observations show the presence of these particles on a number of occasions in December but very rarely in January. The PSC type differentiation from MIPAS indicates that future comparisons of PSC observations with microphysical and denitrification models might be revealing about aspects of solid particle existence and location.
-
Aerosols affect the climate system by changing cloud characteristics in many ways. They act as cloud condensation and ice nuclei, they may inhibit freezing and they could have an influence on the hydrological cycle. While the cloud albedo enhancement (Twomey effect) of warm clouds received most attention so far and traditionally is the only indirect aerosol forcing considered in transient climate simulations, here we discuss the multitude of effects. Different approaches how the climatic implications of these aerosol effects can be estimated globally as well as improvements that are needed in global climate models in order to better represent indirect aerosol effects are discussed in this paper.
-
Recent field observations suggest that the fraction of organic-containing aerosol particles in ice cloud particles is diminished when compared to the background aerosol prior to freezing. In this work, we use model calculations to investigate possible causes for the observed behavior. In particular, homogeneous freezing processes in cooling air parcels containing aqueous inorganic particles and organic particles are studied with a detailed microphysical model. A disparate water uptake and resulting size differences that occur between organic and inorganic particles prior to freezing are identified as the most likely reason for the poor partitioning of organic aerosols into the ice phase. The differences in water uptake can be caused by changes in the relationship between solute mass fraction and water activity of the supercooled liquid phase, by modifications of the accommodation coefficient for water molecules, or by a combination thereof. The behavior of peak ice saturation ratios and total ice crystal number concentrations is examined, and the dependence of the results on cooling rate is investigated. Finally, processes are discussed that could possibly modify the homogeneous freezing behavior of organic particles.
-
Owing to their extensive spatial coverage, stratocumulus clouds play a crucial role in the radiation budget of the earth. Climate models need an accurate characterisation of stratocumulus in order to provide an accurate forecast. However, remote sensing as well as in-situ observations reveal that on several occasions, cumulus clouds present below the stratocumulus, often have a significant impact on the main stratocumulus microphysical properties. This was observed during the ACE-2 (Aerosol Characterisation Experiment-2) campaign designed to study the impact of polluted continental air on stratocumulus formation. In this paper we used a detailed micro-physical chemical parcel model to quantify the extent of this cumulus-stratocumuls coupling. In addition, we made extensive use of microphysical observations from the C-130 aircraft that was operated during ACE-2. For the ACE-2 case studies considered in this paper, our analysis revealed that the chemical, microphysical and optical characteristics of the main stratocumulus cloud deck had significant contributions from cumulus clouds that often penetrated the stratocumulus deck. The amount of fine mode ionic species, the average droplet number concentrations, the effective radii and the optical depths during the flight A562 (when cumulus clouds interacted with the main stratocumulus) were estimated and model runs that included this effect yielded microphysical and optical properties which compared more favourably with the observations than the runs which did not. This study highlights the importance of including these cumulus effects in stratocumulus related modelling studies.
