D. Poppe

Intercomparison of the gas-phase chemistry in several chemistry and transport models

An intercomparison of nine chemical mechanisms (e.g. ADOM, CBM-IV, EMEP, RADM2) as used by 12 contributing groups was conducted. The results for three scenarios are presented covering remote situations with a net O3 loss of around 2.7 ppb (LAND and FREE) and a moderately polluted situation with O3 formation of around 100 ppb (PLUME1) over a 5 day simulation period. The overall tendencies (i.e. the total net production/loss over 5 days) for O3 show a r.m.s. error of 38, 15 and 16%; for H2O2 the errors are 76, 23 and 30% (for LAND, FREE, PLUME1). In terms of ozone production in PLUME1, the most productive mechanisms are EMEP and IVL, the RADM-type mechanisms lie in the mid-range and the CBM-IV type mechanisms fall at the bottom of the range. The differences in H2O2 can partly be explained by an incorrect use of the HO2 + HO2 rate constant and by differences in the treatment of the peroxy radical interactions. In the PLUME1 case the r.m.s. error of the PAN tendency was found to be 29%. Differences between mechanisms for the HO radical are 10, 15 and 19% and for the NO3 radical 35, 16 and 40% (for LAND, FREE, PLUME1) in terms of the r.m.s. error of the results for a 12 h time period centred around the last noon (HO), respectively, a 8 h time period centred around the last midnight (NO3) of simulation. Especially for NO3 some differences are due to different numerical treatment of photolytic processes in the models. Large differences between mechanisms are observed for higher organic peroxides and higher aldehydes with a r.m.s. error of around 50% for the final concentration in PLUME1. The protocol of the intercomparison is given in the appendix, so that the comparison could be repeated for the purpose of mechanism development and sensitivity studies.

The dependence of the concentration of OH on its precursors under moderately polluted conditions: A model study

Oxidation of trace gases emitted into the atmosphere is frequently promoted by free radicals. During daytime, the most important radical is the hydroxyl radical, since it reacts with almost all pollutants thereby initializing their ultimate removal from the atmosphere. Since the reaction with OH is in many cases the rate-determining step, the ambient OH concentration is a measure for the atmospheres oxidation capacity. This paper investigates the influence of the chemical precursors and the photolysis frequencies on the atmospheric OH abundance under moderately polluted and rural conditions. The dominant controlling parameter are the photolysis of ozone and the concentrations of the nitrogen oxides.

Nonlinear chemical couplings in the tropospheric NO x -HO x gas phase chemistry

A bifurcation phenomenon with relevance to atmospheric chemistry is discussed. The gasphase reactions in the troposphere exhibit two types of temporal evolution which are controlled by the strength of the source,Q, of nitric oxide, NO, via the nonlinear chemical coupling between the hydrogen oxides and nitrogen oxides chemistry. IfQ remains below a threshold value, all short-lived species, including NO, approach steady-state concentrations, while above the threshold bifurcation to another state with increasing (nonstationary) NO concentrations accompanied by a depletion of the OH and HO2 abundances takes place.

A Database for Volatile Organic Compounds

The database for volatile organic compounds (VOC data base) was created with the aim of providing an overview of tropospheric hydrocarbon measurements. The data base contains 202 substances, for which atmospheric and useful kinetic data such as rate coefficients, photolysis frequencies, mixing ratios, emission data and ozone formation potentials are compiled from available literature. The database file can be downloaded without charge from http://www.physchem.uni-wuppertal.de/voc-database. Registered users will be informed about the appearance of updates.

Nonlinear Dynamics in Atmospheric Chemistry Rate Equations

Nonlinear terms in the gas-phase rate equations of atmospheric trace constituents give rise to unexpected oscillations in the concentrations. For a simplified chemical scheme of the troposphere that contains only the generic reaction paths, the underlying dynamical structure is investigated. It is shown that the source strengths of CO and NO are the controlling parameters of the system. A linear stability analysis reveals that the steady state solutions lose stability due to the occurrence of two Hopf bifurcations. Furthermore, it appears that the dynamical behaviour of the oscillatory solutions is dominated by O3 and CO. Based on the two-variable system (CO–O3) it is shown that the oscillatory solution involves an autocatalytic ozone production phase which is followed by a phase in which CO is oxidised quickly. A simple expression is presented from which the period of the oscillation can be obtained. The implications for the present troposphere are unclear, since other hydrocarbons are present and transport is taking place. Nevertheless, the system nicely shows the general nonlinear mechanisms that operate in the tropospheric chemistry equations.

Chemical Mechanism Development: Laboratory Studies and Model Applications

Within the German Tropospheric Research Programme (TFS) numerous kinetic and mechanistic studies on the tropospheric reaction/degradation of the following reactants were carried out:• oxygenated VOC, • aromatic VOC, • biogenic VOC, •short-lived intermediates, such as alkoxy and alkylperoxy radicals.At the conception of the projects these selected groups were classes of VOC or intermediates for which the atmospheric oxidation mechanisms were either poorly characterised or totally unknown. The motivation for these studies was the attainment of significant improvements in our understanding of the atmospheric chemical oxidation processes of these compounds, particularly with respect to their involvement in photooxidant formation in the troposphere. In the present paper the types of experimental investigations performed and the results obtained within the various projects are briefly summarised. The major achievements are highlighted and discussed in terms of their contribution to improving our understanding of the chemical processes controlling photosmog formation in the troposphere.

Scenarios for Modeling Multiphase Tropospheric Chemistry

Besides observational data model calculations are a very importanttool for improving our understanding of multiphase chemistryin the troposphere. Before a chemical model can be used for that purposeit is necessary to show that the model does what it is intendedto do. A protocol has been developed thatcan be used as a basis for the verification of the numericsand the correct implementation of thechemical balance equations.The protocol defines meteorological parameters and initial conditionsfor a zerodimensional (box) model. Several scenarios cover the pollutedas well as the remote marine and continental boundary layer and also thefree troposphere. Calculations by different groupswith different modelsand numerical solvers demonstrate that the protocol is clear and complete.The excellent agreement between the results of all groups are a major step of verification of the participating models.The scenarios may also serve as well documented base cases forsensitivity studies.

The Tropospheric Gas-Phase Degradation of NH3 and Its Impact on the Formation of N2O and NOx

The gas-phase degradation of NH3 in the atmosphere still has many uncertainties. One of them is the possible isomerisation of NH2O to NHOH, as indicated by kinetic studies. Since NH2O is formed during the gas-phase oxidation of ammonia in the troposphere, this reaction can potentially influence the subsequent production of N2O and NOx. So far, the isomerisation has never been implemented into current chemical schemes describing the atmospheric gas-phase degradation of NH3 and its atmospheric relevance has never been assessed. The N2O yield from NH3 degradation is calculated to be in the range of 10–43 %. It depends on the NO2 and O3 concentrations, but is independent of the NH3 concentration. Compared with the results from recent literature, the N2O yield derived from the new mechanism is 20–80% lower, implying a smaller global N2O source strength of 0.4 Tg yr- 1. The production of NH2SO2 seems to be less important for the atmospheric degradation of NH3. NH3 oxidation is a sink for NOx at NOx mixing ratios of more than about 1 ppb and a source at lower NOx burdens.