understood/captured by meteorological models (e.g., over Europe). However, in the upper troposphere and lower stratosphere, models often fail to capture sharp gradients across the tropopause and from the subtropics to the tropics. In some models, this is related to deficiencies in model transport schemes and upper boundary conditions. Also, regions of the globe where our understanding of meteorology is poorer and emissions are less well known (e.g., tropics, continental Africa, Asia, and South America) are not simulated as well by all models. At particular measurement locations, it is apparent that emission inventories used by some global models underestimate emissions in certain regions (e.g., over southern Asia) or have incorrect seasonal variations (e.g., biomass burning over South America). Deficiencies in chemical schemes may also explain differences between models and the data.

Abstract. Within ACCENT, a European Network of Excellence, eighteen atmospheric models from the U.S., Europe, and Japan calculated present (2000) and future (2030) concentrations of ozone at the Earth's surface with hourly temporal resolution. Comparison of model results with surface ozone measurements in 14 world regions indicates that levels and seasonality of surface ozone in North America and Europe are characterized well by global models, with annual average biases typically within 5–10 nmol/mol. However, comparison with rather sparse observations over some regions suggest that most models overestimate annual ozone by 15–20 nmol/mol in some locations. Two scenarios from the International Institute for Applied Systems Analysis (IIASA) and one from the Intergovernmental Panel on Climate Change Special Report on Emissions Scenarios (IPCC SRES) have been implemented in the models. This study focuses on changes in near-surface ozone and their effects on human health and vegetation. Different indices and air quality standards are used to characterise air quality. We show that often the calculated changes in the different indices are closely inter-related. Indices using lower thresholds are more consistent between the models, and are recommended for global model analysis. Our analysis indicates that currently about two-thirds of the regions considered do not meet health air quality standards, whereas only 2–4 regions remain below the threshold. Calculated air quality exceedances show moderate deterioration by 2030 if current emissions legislation is followed and slight improvements if current emissions reduction technology is used optimally. For the "business as usual" scenario severe air quality problems are predicted. We show that model simulations of air quality indices are particularly sensitive to how well ozone is represented, and improved accuracy is needed for future projections. Additional measurements are needed to allow a more quantitative assessment of the risks to human health and vegetation from changing levels of surface ozone.

A fundamental difficulty in 3-D models is addressed which can arise due to inconsistencies between advection schemes and winds. It is shown that a model will fail to meet certain basic criteria, desired of 3-D transport models, when the density field computed by the advection scheme from the winds differs from the implied density field based on the surface pressure and the sigma (or hybrid) coordinates. To allow a rigorous mathematical formulation, the focus is on the example of a mass flux advection scheme in a model where the winds and surface pressure are derived from different advection schemes (e.g. a spectral scheme in a climate model or a weather centre model); however, in principle the discussion applies to nearly any situation in which the pressure levels change in a model. To illustrate the potential seventy of such problems, a mass conserving gridto-grid transformation scheme is constructed which only uses the current tracer mass mixing-ratio distribution. It is shown that only one solution exists that is comprehensively valid for any arbitrary tracer distribution, and that this type of correction introduces an additional undesired artificial vertical diffusion component into the model transport that increases with increasing tracer mass mixing-ratio gradients and may exceed the physical vertical transport itself. It is demonstrated that the results of any supplementary fix, either mass fixer or grid-togrid transformation, are generally unacceptable for global modelling applications. From this, it is concluded that the only alternative which can produce reliable results for any arbitrary tracer is to maintain a consistent grid throughout the entire model time step, where all changes in pressure levels due to modelled advection exactly match the changes implied by the surface pressure at the next time step. Although this is already done in some models, this would require significant changes in the structure of the advection scheme or its input wind fields in several other contemporary general circulation and chemistry transport models.

Recently several field campaigns and satellite observations have found strong indications for the presence of bromine oxide (BrO) in the free troposphere. Using a global atmospheric chemistry transport model we show that BrO mixing ratios of a few tenths to 2 pmol mol −1 lead to a reduction in the zonal mean O 3 mixing ratio of up to 18% in widespread areas and regionally up to 40% compared to a model run without bromine chemistry. A lower limit approach for the marine boundary layer, that does not explicitly include the release of halogens from sea salt aerosol, shows that for dimethyl sulfide (DMS) the effect is even larger, with up to 60% reduction of its tropospheric column. This is accompanied by dramatic changes in DMS oxidation pathways, reducing its cooling effect on climate. In addition there are changes in the HO 2 : OH ratio that also affect NO x and PAN. These results imply that potentially significant strong sinks for O 3 and DMS have so far been ignored in many studies of the chemistry of the troposphere.

Abstract. The potential impact of the uptake of HNO3 on ice on the distribution of NOy species, ozone and OH has been assessed using the global scale chemistry-transport model MATCH-MPIC. Assuming equilibrium uptake according to dissociative Langmuir theory results in significant reductions of gas phase HNO3. Comparison to a large set of observations provides support that significant uptake of HNO3 on ice is occurring, but the degree of the uptake cannot be inferred from this comparison alone. Sensitivity simulations show that the uncertainties in the total amount of ice formation in the atmosphere and the actual expression of the settling velocity of ice particles only result in small changes in our results. The largest uncertainty is likely to be linked to the actual theory describing the uptake process and the value of the initial uptake coefficient. The inclusion of non-methane hydrocarbon chemistry partially compensates for the absence of HNO3 uptake on ice when this is neglected in the model. The calculated overall effect on upper tropospheric ozone concentrations and the tropospheric methane lifetime are moderate to low. These results support a shift in the motivation for future experimental and theoretical studies of HNO3-ice interaction towards the role of HNO3 in hydrometeor surface physics.