ALBERT

Beschreibung: 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.

Beschreibung: 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.

Beschreibung: A `virtual' disjunct eddy covariance (vDEC) device was tested with field measurements of biogenic VOC fluxes at a subalpine forest site in the Rocky Mountains of the USA. A PTR-MS instrument was used as the VOC sensor. Daily peak emission fluxes of 2-methyl-3-buten-2-ol (MBO), methanol, acetone and acetaldehyde were around 1.5, 1, 0.8 and 0.4 mg m-2 h-1, respectively. High pass filtering due to long sampling lines was investigated in laboratory experiments, and suggested that VOC losses in PTFA lines are generally governed by diffusion laws. Memory effects and surface reactions did not seem to play a dominant role. Model estimates of MBO fluxes compared well with measured fluxes. The results also suggest that latent heat and sensible heat fluxes are reasonably well correlated with VOC fluxes and could be used to predict variations in VOC emissions. The release of MBO, methanol, acetone and acetaldehyde resulted in significant change of tropospheric oxidant levels and a 10--40% increase in ozone levels, as inferred from a photochemical box model. We conclude that vDEC with a PTR-MS instrument is a versatile tool for simultaneous field analysis of multiple VOC fluxes.

Beschreibung: The impact of multiphase reactions involving nitrogen dioxide (NO2) and aromatic compounds was simulated in this study. A mechanism (CAPRAM 2.4, MODAC Mechanism) was applied for the aqueous phase reactions, whereas RACM was applied for the gas phase chemistry. Liquid droplets were considered as monodispersed with a mean radius of 0.1 µm and a liquid content (LC) of 50 µg m-3. The multiphase mechanism has been further extended to the chemistry of aromatics, i.e. reactions involving benzene, toluene, xylene, phenol and cresol have been added. In addition, reaction of NO2 with dissociated hydroxyl substituted aromatic compounds has also been implemented. These reactions proceed through charge exchange leading to nitrite ions and therefore to nitrous acid formation. The strength of this source was explored under urban polluted conditions. It was shown that it may increase gas phase HONO levels under some conditions and that the extent of this effect is strongly pH dependent. Especially under moderate acidic conditions (i.e. pH above 4) this source may represent more than 75% of the total HONO/NO2 - production rate, but this contribution drops down close to zero in acidic droplets (as those often encountered in urban environments).

Beschreibung: 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.

Beschreibung: The nucleation of NAD and NAT from HNO3/H2O and HNO3/H2SO4/H2O solution droplets is investigated both theoretically and experimentally with respect to the formation of polar stratospheric clouds (PSCs). Our analysis shows that homogeneous NAD and NAT nucleation from liquid aerosols is insufficient to explain the number densities of large nitric acid containing particles recently observed in the Arctic stratosphere. This conclusion is based on new droplet freezing experiments employing optical microscopy combined with Raman spectroscopy. The homogeneous nucleation rate coefficients of NAD and NAT in liquid aerosols under polar stratospheric conditions derived from the experiments are 〈 2 x 10-5 cm-3 s-1 and 〈 8 x 10-2 cm-3 s-1, respectively. These nucleation rate coefficients are smaller by orders of magnitude than the value of ~103 cm-3 s-1 used in a recent denitrification modelling study that is based on a linear extrapolation of laboratory nucleation data to stratospheric conditions (Tabazadeh et al., Science, 291, 2591--2594, 2001). We show that this linear extrapolation is in disagreement with thermodynamics and with experimental data and, therefore, must not be used in microphysical models of PSCs. Our analysis of the experimental data yields maximum hourly production rates of nitric acid hydrate particles per cm3 of air of about 3 x 10-10 cm-3 (air) h-1 under polar stratospheric conditions. Assuming PSC particle production to proceed at this rate for two months we arrive at particle number densities of 〈 5 x 10-7 cm-3, much smaller than the value of ~10-4 cm-3 reported in recent field observations. In addition, the nitric acid hydrate production rate inferred from our data is much smaller than that required to reproduce the observed denitrification in the modelling study mentioned above. This clearly shows that homogeneous nucleation of NAD and NAT from liquid supercooled ternary solution aerosols cannot explain the observed polar denitrification.

Beschreibung: 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.

Beschreibung: 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.

Beschreibung: A tracer model, DREAM (the Danish Rimpuff and Eulerian Accidental release Model), has been developed for modelling transport, dispersion and deposition (wet and dry) of radioactive material from accidental releases, as the Chernobyl accident. The model is a combination of a Lagrangian model, that includes the near source dispersion, and an Eulerian model describing the long-range transport. The performance of the transport model has previously been tested within the European Tracer Experiment, ETEX, which included transport and dispersion of an inert, non-depositing tracer from a controlled release. The focus of this paper is the model performance with respect to the total deposition of  137Cs, 134Cs and 131I from the Chernobyl accident, using different relatively simple and comprehensive parameterizations for dry- and wet deposition. The performance, compared to measurements, of using different combinations of two different wet deposition parameterizations and three different parameterizations of dry deposition has been evaluated, using different statistical tests. The best model performance, compared to measurements, is obtained when parameterizing the total deposition combined of a simple method for dry deposition and a subgrid-scale averaging scheme for wet deposition based on relative humidities. The same major conclusion is obtained for all the three different radioactive isotopes and using two different deposition measurement databases. Large differences are seen in the results obtained by using the two different parameterizations of wet deposition based on precipitation rates and relative humidities, respectively. The parameterization based on subgrid-scale averaging is, in all cases, performing better than the parameterization based on precipitation rates. This indicates that the in-cloud scavenging process is more important than the below cloud scavenging process for the submicron particles and that the precipitation rates are relatively uncertain in the meteorological model compared to the relative humidity. Relatively small differences are, however, seen in the statistical tests between the three different parameterizations of dry deposition.

Beschreibung: The relationship between nucleation events and spectral solar irradiance was analysed using two years of data collected at the Station for Measuring Forest Ecosystem-Atmosphere Relations (SMEAR II) in Hyytiälä, Finland. We analysed the data in two different ways. In the first step we calculated ten nanometer average values from the irradiance measurements between 280 and 580 nm and explored if any special wavelengths groups showed higher values on event days compared to a spectral reference curve for all the days for 2 years or to reference curves for every month. The results indicated that short wavelength irradiance between 300 and 340 nm is higher on event days in winter (February and March) compared to the monthly reference graph but quantitative much smaller than in spring or summer. By building the ratio between the average values of different event classes and the yearly reference graph we obtained peaks between 1.17 and 1.6 in the short wavelength range (300--340 nm). In the next step we included number concentrations of particles between 3 and 10 nm and calculated correlation coefficients between the different wavelengths groups and the particles. The results were quite similar to those obtained previously; the highest correlation coefficients were reached for the spectral irradiance groups 3--5 (300--330 nm) with average values for the single event classes around 0.6 and a nearly linear decrease towards higher wavelengths groups by 30%. Both analyses indicate quite clearly that short wavelength irradiance between 300 and 330 or 340 nm is the most important solar spectral radiation for the formation of newly formed aerosols. In the end we introduce a photochemical mechanism as one possible pathway how short wavelength irradiance can influence the formation of SOA by calculating the production rate of excited oxygen. This mechanism shows in which way short wavelength irradiance can influence the formation of new particles even though the absolute values are one to two magnitudes smaller compared to irradiance between 400 and 500 nm.