Items

Advanced search

An evolution strategy to estimate emission source distributions on a regional scale from atmospheric observations

In this paper we present an Evolution Strategy (ES) approach towards the estimation of the location and strength of surface emissions of trace gases based on atmospheric concentration measurements and back-trajectory analyses. The details of the ES developed are outlined. The ES is tested using artificial emission maps at different grid resolutions and the results compared to those obtained on the same problems using Singular Value Decomposition (SVD). In almost all cases, the ES improves on SVD at equivalent resolutions. In addition, a number of insights, which the ES approach brings to the problem of source location and emission strength, are discussed, particularly the limitations on the use of measurement and meteorological data in the determination of emission source distribution.
Numerical simulations of homogeneous freezing processes in the aerosol chamber AIDA

The homogeneous freezing of supercooled H2SO4/H2O aerosols in an aerosol chamber is investigated with a microphysical box model using the activity parameterization of the nucleation rate by Koop et al. (2000). The simulations are constrained by measurements of pressure, temperature, total water mixing ratio, and the initial aerosol size distribution, described in a companion paper Möhler et al. (2003). Model results are compared to measurements conducted in the temperature range between 194 and 235 K, with cooling rates in the range between 0.5 and 2.6 K min-1, and at air pressures between 170 and 1000 hPa. The simulations focus on the time history of relative humidity with respect to ice, aerosol size distribution, partitioning of water between gas and particle phase, onset times of freezing, freezing threshold relative humidities, aerosol chemical composition at the onset of freezing, and the number of nucleated ice crystals. The latter four parameters can be inferred from the experiments, the former three aid in interpreting the measurements. Sensitivity studies are carried out to address the relative importance of uncertainties of basic quantities such as temperature, total H2O mixing ratio, aerosol size spectrum, and deposition coefficient of H2O molecules on ice. The ability of the numerical simulations to provide detailed explanations of the observations greatly increases confidence in attempts to model this process under real atmospheric conditions, for instance with regard to the formation of cirrus clouds or polar stratospheric ice clouds, provided that accurate temperature and humidity measurements are available.
The H Lyman-a actinic flux in the middle atmosphere

The penetration of solar H Lyman-a radiation into the terrestrial middle atmosphere is studied in detail. The Lyman-a actinic flux is calculated with a Monte Carlo approach including multiple resonance scattering of Lyman-a photons within the terrestrial atmosphere and a temperature dependent absorption cross section of molecular oxygen. The dependence of the actinic flux on the temperature profile is significant for O2 column densities greater than about 1024 m-2. For column densities greater than about 5 · 1024 m-2 resonance scattering becomes important at solar zenith angles > 60°. The O(1D) quantum yield of the O2 dissociation by Lyman-a photons is found to decrease from 0.58 in the lower thermosphere to 0.48 in the lower mesosphere. Parameterisations for Lyman-a actinic flux, mean O2 absorption cross section and O(1D) quantum yield including temperature dependence and resonance scattering are given valid up to a O2 column density of about 1025 m-2.
Experimental investigation of homogeneous freezing of sulphuric acid particles in the aerosol chamber AIDA

The homogeneous freezing of supercooled H2SO4/H2O solution droplets was investigated in the aerosol chamber AIDA (Aerosol Interactions and Dynamics in the Atmosphere) of Forschungszentrum Karlsruhe. 24 freezing experiments were performed at temperatures between 189 and 235 K with aerosol particles in the diameter range 0.05 to 1 µm. Individual experiments started at homogeneous temperatures and ice saturation ratios between 0.9 and 0.95. Cloud cooling rates up to -2.8 K min-1 were simulated dynamically in the chamber by expansion cooling using a mechanical pump. Depending on the cooling rate and starting temperature, freezing threshold relative humidities were exceeded after expansion time periods between about 1 and 10 min. The onset of ice formation was measured with three independent methods showing good agreement among each other. Ice saturation ratios measured at the onset of ice formation increased from about 1.4 at 231 K  to about 1.75 at 189 K. The experimental data set including thermodynamic parameters as well as physical and chemical aerosol analysis provides a good basis for microphysical model applications.
A model for particle formation and growth in the atmosphere with molecular resolution in size

The formation and growth of atmospheric aerosol particles is considered using an exact discrete method with molecular resolution in size space. The method is immune to numerical diffusion problems that are a nuisance for typical simulation methods using a sectional representation for the particle size distribution. For condensational growth, a slight modification is proposed for the Fuchs-Sutugin expression, which improves the prediction of the growth rate of nano-sized particles by as much as a factor of two. The presented method is applied to particle formation in a Finnish Boreal forest and is shown to capture the essential features of the dynamics quite nicely. Furthermore, it is shown that the growth of the particles is roughly linear, which means that the amount of condensable vapour is constant (of the order 1013 1/m3).
Modeling the chemical effects of ship exhaust in the cloud-free marine boundary layer

The chemical evolution of the exhaust plumes of ocean-going ships in the cloud-free marine boundary layer is examined with a box model. Dilution of the ship plume via entrainment of background air was treated as in studies of aircraft emissions and was found to be a very important process that significantly alters model results. We estimated the chemical lifetime (defined as the time when differences between plume and background air are reduced to 5% or less) of the exhaust plume of a single ship to be 2 days. Increased concentrations of NOx (= NO + NO2) in the plume air lead to higher catalytical photochemical production rates of O3 and also of OH. Due to increased OH concentrations in the plume, the lifetime of many species (especially NOx) is significantly reduced in plume air. The chemistry on background aerosols has a significant effect on gas phase chemistry in the ship plume, while partly soluble ship-produced aerosols are computed to only have a very small effect. Soot particles emitted by ships showed no effect on gas phase chemistry. Halogen species that are released from sea salt aerosols are slightly increased in plume air. In the early plume stages, however, the mixing ratio of BrO is decreased because it reacts rapidly with NO. To study the global effects of ship emissions we used a simple upscaling approach which suggested that the parameterization of ship emissions in global chemistry models as a constant source at the sea surface leads to an overestimation of the effects of ship emissions on O3 of about 50% and on OH of roughly a factor of 2. The differences are mainly caused by a strongly reduced lifetime (compared to background air) of NOxin the early stages of a ship plume.
Strategies for measuring canonical tracer relationships in the stratosphere

A high-resolution simulation of stratospheric long-lived trace gases is subsampled in ways resembling various commonly used measurement platforms. The resulting measurements are analyzed with respect to whether they allow an accurate determination of stratospheric tracer relationships, as a prerequisite for a quantification of mixing processes from them. By varying the simulated locations, frequencies, and, in the case of satellite data, accuracies of the measurements we determine minimal requirements that the measurements need to satisfy in order to be suitable for a derivation of tracer relationships.
Global chemical weather forecasts for field campaign planning: predictions and observations of large-scale features during MINOS, CONTRACE, and INDOEX

The first global tropospheric forecasts of O3 and its precursors have been used in the daily flight planning of field measurement campaigns. The 3-D chemistry-transport model MATCH-MPIC is driven by meteorological data from a weather center (NCEP) to produce daily 3-day forecasts of the global distributions of O3 and related gases, as well as regional CO tracers. This paper describes the forecast system and its use in three field campaigns, MINOS, CONTRACE and INDOEX. An overview is given of the forecasts by MATCH-MPIC and by three other chemical weather forecast models (EURAD, ECHAM, and FLEXPART), focusing on O3 and CO. Total CO and regional CO tracers were found to be the most valuable gases for flight planning, due to their relatively well-defined anthropogenic source regions and lifetimes of one to a few months. CO was in good agreement with the observations on nearly all the flights (generally  r > 0.7, and the relative RMS differences for the deviations from the means was less than 20%). In every case in which the chemical weather forecasts were primarily responsible for the flight plans, the targeted features were observed. Three forecasted phenomena are discussed in detail: outflow from Asia observed in the Mediterranean upper troposphere during MINOS, outflow from North America observed in the middle troposphere over northern Europe during CONTRACE, and the location of the "chemical ITCZ' over the Indian Ocean during INDOEX. In particular it is shown that although intercontinental pollution plumes such as those observed during MINOS and CONTRACE occur repeatedly during the months around the campaigns, their frequency is sufficiently low (~10--30% of the time) that global chemical weather forecasts are important for enabling them to be observed during limited-duration field campaigns. The MATCH-MPIC chemical weather forecasts, including an interface for making customized figures from the output, are available for community use via <a href="http://www.mpch-mainz.mpg.de/~lawrence/forecasts.html">http://www.mpch-mainz.mpg.de/~lawrence/forecasts.html</a>.
Aerosol sources and their contribution to the chemical composition of aerosols in the Eastern Mediterranean Sea during summertime

A detailed study on the temporal variability of compounds important in controlling aerosol chemical composition was performed during a one-month experiment conducted during summer 2000 at a background site on Crete, in the Eastern Mediterranean Sea. Contribution of different aerosol sources in the Eastern Mediterranean Basin could be investigated at this location since the site is influenced by a wide range of air masses originating mainly in Europe and Africa. Chemical apportionment was performed for various air mass origins and showed a strong impact of anthropogenic emissions in the Turkey and Central Europe sectors, with black carbon (BC) and non-sea-salt sulfate (nss-SO4) concentrations higher than observed in the Eastern and Western Europe sectors. High levels of non-sea-salt calcium (nss-Ca) were associated with air masses from Africa but also from Central Turkey. Evidence was found that BC calculation based on light absorbance during dust events was biased. This quality-controlled high temporal resolution dataset allowed to investigate in detail the source-receptor relationships responsible for the levels of BC, nss-SO4 and sulfur dioxide (SO2), observed in Crete. Among the results obtained from this model, the major contribution of Turkey and Central Europe was confirmed in terms of anthropogenic emissions. Comparisons with remote optical properties obtained from Satellite observations (SEAWIFS) north of Crete indicates that our ground based aerosol characterization was suitable for describing aerosol properties in the atmospheric column for most of the time during the campaign.
The isotopic fingerprint of the pre-industrial and the anthropogenic N2O source

We have performed high-precision measurements of the 18O and position dependent 15N isotopic composition of N2O from Antarctic firn air samples. By comparing these data to simulations carried out with a firn air diffusion model, we have reconstructed the temporal evolution of the N2O isotope signatures since pre-industrial times. The heavy isotope content of atmospheric N2O is presently decreasing for all signatures at rates of about -0.038 %o yr -1 for 1d15N, -0.046 %o yr -1 for 2d 15N and -0.025 %o yr -1 for d18O. The total decrease since pre-industrial times is estimated to be about -1.8%o for 1d15N at both positions and -2.2%o for 2d15N. Isotope budget calculations using these trends and recent stratospheric measurements allow to isotopically characterize the present and the pre-industrial global average N2O source, as well as the additional N2O emissions that have caused the global N2O increase since pre-industrial times. The increased fluxes from the depleted surface sources alone are insufficient to explain the inferred temporal isotope changes. In addition, the global average N2O source signature is calculated to be significantly depleted today relative to the pre-industrial value, in agreement with recent indications from soil emission measurements.