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The UV-visible absorption cross-sections of IONO2

The UV-visible absorption spectrum of gaseous IONO2 has been measured over the wavelength range 245--415 nm using the technique of laser photolysis with time-resolved UV-visible absorption spectroscopy. IONO2 was produced in situ in the gas phase by laser flash photolysis of NO2/CF3I/N2 mixtures. Post flash spectra were deconvolved to remove contributions to the observed absorption from other reactant and product species. The resulting spectrum attributed to IONO2 consists of several overlapping broad absorption bands. Assuming a quantum yield of unity for IONO2 photolysis, model calculations show that during sunlit hours at noon, 53° N, the first order solar photolysis rate coefficient (J value) for IONO2 is 4.0 x 10-2 s-1.
Atmospheric deposition of toxics onto the Seine Estuary, France: example of polycyclic aromatic hydrocarbons

Concentrations of Polycyclic Aromatic Hydrocarbons (PAH) were measured in precipitation samples on a weekly basis between March and October 2001, at four sites in the Seine Estuary (France). Mean concentrations of total PAHs (S 14 PAHs) ranged from 38 to 141 ng L-1. Fluoranthene, phenanthrene and pyrene were the dominant PAH compounds and were detected in each sample. The six potential carcinogenic PAHs accounted for 20 to 25% of the total PAH concentration in bulk deposition. The PAH signatures in bulk (wet and dry) deposition and surface water were also compared to investigate source/sink relationships. Seasonal patterns were observed with maximum loading occurring during the colder months of the studied period (March and April). Mean values of daily flux reported for S 14 PAHs ranged from 108 to 267 ng m-2 d-1. Spatial influences were also observed, indicating both localized and long-range atmospheric source inputs (controlled by hydroclimatic parameters).
The adsorption of nitrogen oxides on crystalline ice

The partitioning of nitrogen oxides between ice and air is of importance to the ozone budget in the upper troposphere. In the present study, adsorption of nitrogen oxides on ice was investigated at atmospheric pressure using a chromatographic technique with radioactively labelled nitrogen oxides at low concentrations. The measured retentions solely depended on molecular adsorption and were not influenced by dimerisation, formation of encapsulated hydrates on the ice surface, dissociation of the acids, nor by migration into a quasi-liquid layer or grain boundaries. Based on the chromatographic retention and the model of thermo-chromatography, the standard adsorption enthalpy of -20 kJ mol-1 for NO, -22kJ mol-1 for NO2, -30kJ mol-1 for peroxyacetyl nitrate, -32kJ mol-1 for HON} and -44 kJ mol-1 for HNO3 was calculated. To perform those calculations within the model of thermo-chromatography, the standard adsorption entropy was calculated based on statistical thermodynamics. In this work, two different choices of standard states were applied, and consequently different values of the standard adsorption entropy, of either between -39 kJ mol-1 and -45kJ mol-1, or -164 kJ mol-1 and -169 kJ mol-1 for each nitrogen oxide were derived. The standard adsorption enthalpy was identical for both standard adsorption entropies and thus shown to be independent of the choice of standard state. A brief outlook on environmental implications of our findings indicates that adsorption on ice might be an important removal process of HNO3. In addition, it might be of some importance for HONO and peroxyacetyl nitrate and irrelevant for NO and NO2.
Uptake of HNO3 to deliquescent sea-salt particles: a study using the short-lived radioactive isotope tracer 13N

The uptake of HNO3 to deliquescent airborne sea-salt particles (RH = 55%, P = 760 torr, T = 300 K) at concentrations from 2 to 575 ppbv is measured in an aerosol flow tube using 13N as a tracer. Small particles (<approx> 70 nm diameter) are used in order to minimize the effect of diffusion in the gas phase on the mass transfer. Below 100 ppbv, an uptake coefficient (gupt) of 0.50 ± 0.20 is derived. At higher concentrations, the uptake coefficient decreases along with the consumption of aerosol chloride. Data interpretation is further supported by using the North American Aerosol Inorganics Model (AIM), which predicts the aqueous phase activities of ions and the gas-phase partial pressures of H2O, HNO3, and HCl at equilibrium for the NaCl/HNO3/H2O system. These simulations show that the low concentration data are obtained far from equilibrium, which implies that the uptake coefficient derived is equal to the mass accommodation coefficient under these conditions. The observed uptake coefficient can serve as input to modeling studies of atmospheric sea-salt aerosol chemistry. The main sea-salt aerosol burden in the marine atmosphere is represented by coarse mode particles (> 1 µm diameter). This implies that diffusion in the gas-phase is the limiting step to HNO3 uptake until the sea-salt has been completely processed.
Analysis of a summer smog episode in the Berlin-Brandenburg region with a nested atmosphere -- chemistry model

An analysis of a pollution episode in an urban atmosphere, using a complex model system is presented. The nested atmosphere-chemistry model system simulates the atmospheric conditions during a one week measurement campaign, called FLUMOB, in July 1994 in Berlin-Brandenburg, Germany. The analysis shows that naturally emitted hydrocarbons played the dominant role in the ozone formation in the investigated area. The composition of non-methane volatile organic compounds was made up to 70--80% by biogenically emitted hydrocarbons. During the analysed case, ozone formation was sensitive to hydrocarbon concentrations so that the ozone production was limited by the availability of hydrocarbons and thus especially by the amount which was biogenically emitted. Furthermore, it is shown that the FLUMOB episode was influenced by elevated concentrations of ozone in the free troposphere. In contrast to previous analyses, the importance of ozone produced outside of Europe is emphasized. In spite of the stagnant high pressure situation which occurred during the FLUMOB episode Germany was significantly influenced by long-range transport of ozone. This transport also influenced near surface ozone concentrations.
Global ozone forecasting based on ERS-2 GOME observations

The availability of near-real time ozone observations from satellite instruments has recently initiated the development of ozone data assimilation systems. In this paper we present the results of an ozone assimilation and forecasting system, in use since Autumn 2000. The forecasts are produced by an ozone transport and chemistry model, driven by the operational medium range forecasts of ECMWF. The forecasts are initialised with realistic ozone distributions, obtained by the assimilation of near-real time total column observations of the GOME spectrometer on ERS-2. The forecast error diagnostics demonstrate that the system produces meaningful total ozone forecasts for up to 6 days in the extratropics. In the tropics meaningful forecasts of the small anomalies are restricted to shorter periods of about two days with the present model setup. It is demonstrated that important events, such as the breakup of the South Pole ozone hole and mini-hole events above Europe can be successfully predicted 4--5 days in advance.
Redistribution of trace gases by convective clouds - mixed-phase processes

The efficiency of gas transport to the free and upper troposphere in convective clouds is investigated in an axisymmetric dynamic cloud model with detailed microphysics. In particular, we examine the sensitivity of gas transport to the treatment of gas uptake by different ice hydrometeors. Two parameters are used to describe this uptake. The gas retention coefficient defines the fraction of dissolved gas that is retained in an ice particle upon freezing, which includes also the riming process. We also define a gas burial efficiency defining the amount of gas entrapped in ice crystals growing by vapour diffusion. Model calculations are performed for continental and maritime clouds using a complete range of gas solubilities, retention coefficients and burial efficiencies. The results show that the magnitude of the gas retention coefficient is much more important for gas transport in maritime clouds than in continental clouds. The cause of this difference lies in the different microphysical processes dominating the formation and evolution of hydrometeors in the two cloud types. For highly soluble gases, the amount of gas transported to the free troposphere in maritime clouds falls approximately linearly by a factor of 12 as the retention coefficient is varied between 0 and 1. Gas transport is relatively insensitive to the magnitude of the gas burial efficiency. However, the burial efficiency strongly controls the concentration of trace gases inside anvil ice crystals, which subsequently form cirrus clouds.
Suppression of chlorine activation on aviation-produced volatile particles

We examine the effect of nanometer-sized aircraft-induced aqueous sulfuric acid (H2SO4/H2O) particles on atmospheric ozone as a function of temperature. Our calculations are based on a previously derived parameterization for the regional-scale perturbations of the sulfate surface area density due to air traffic in the North Atlantic Flight Corridor (NAFC) and a chemical box model. We confirm large scale model results that at temperatures T>210 K additional ozone loss -- mainly caused by hydrolysis of BrONO2 and N2O5 -- scales in proportion with the aviation-produced increase of the background aerosol surface area. However, at lower temperatures (< 210 K) we isolate two effects which efficiently reduce the aircraft-induced perturbation: (1) background particles growth due to H2O and HNO3 uptake enhance scavenging losses of aviation-produced liquid particles and (2) the Kelvin effect efficiently limits chlorine activation on the small aircraft-induced droplets by reducing the solubility of chemically reacting species. These two effects lead to a substantial reduction of heterogeneous chemistry on aircraft-induced volatile aerosols under cold conditions. In contrast we find contrail ice particles to be potentially important for heterogeneous chlorine activation and reductions in ozone levels. These features have not been taken into consideration in previous global studies of the atmospheric impact of aviation. Therefore, to parameterize them in global chemistry and transport models, we propose the following parameterisation: scale the hydrolysis reactions by the aircraft-induced surface area increase, and neglect heterogeneous chlorine reactions on liquid plume particles but not on ice contrails and aircraft induced ice clouds.
Modelling studies of wind field on urban environment

Increasing load of air pollution in urban environment emphasises the need for detailed evaluation of wind characteristics that significantly affect the air quality of urban areas, especially, in large agglomerations. This paper includes analysis of urban wind climatology and estimation of wind profiles based on measurements of the new urban climate station located at the Eötvös University, observations of the meteorological station network of the Budapest agglomeration area, and multi-level wind measurements near Hegyhátsál. Furthermore, wind field modelling (using the WAsP linear spectral wind flow model) is presented over selected representative complex areas that demonstrates strong dependence between wind, height, topography, and roughness.
On the origin of tropospheric O3 over the Indian Ocean during the winter monsoon: African biomass burning vs. stratosphere-troposphere exchange

This study investigates the origin of a commonly observed feature in the O3 profiles: mid tropospheric O3 maxima (300--500 hPa) over the tropical Indian Ocean. A comparison and analysis of model simulations, using a 3-D global climate-chemistry model, and measured O3 profiles from the INDOEX campaign is presented. European Centre for Medium-Range Weather Forecast (ECMWF) meteorological analyses have been assimilated into the 3-D model to represent actual meteorology. The model realistically simulates the observed mid-tropospheric O3 maxima. The analysis of the model simulations shows that the major source of the mid-tropospheric O3 maxima is advection of polluted air masses from continental biomass burning areas over Africa, with generally only a small contribution of stratospheric O3. Previous studies hinted at stratosphere-troposphere exchange (STE) along the subtropical jet (STJ) as the primary source of the mid-tropospheric O3 maxima over the Indian Ocean. Analysis of the model simulations shows that the mechanism causing the mid-tropospheric transport of African biomass burning pollution and stratospheric air masses are frontal zones or waves passing along the subtropical jets, causing advection of tropical air masses in the prefrontal (equatorward) zone. Furthermore, the frontal zones or waves also cause STE at the poleward side of the STJ. The model simulations also indicate that the contribution of STE in general is minor compared to advection and in situ tropospheric production of O3 for the mid-tropospheric O3 budget over the Indian Ocean region.