J.-F. Müller

Nitrogen and sulfur deposition on regional and global scales: A multimodel evaluation

We use 23 atmospheric chemistry transport models to calculate current and future (2030) deposition of reactive nitrogen (NOy, NHx) and sulfate (SOx) to land and ocean surfaces. The models are driven by three emission scenarios: (1) current air quality legislation (CLE); (2) an optimistic case of the maximum emissions reductions currently technologically feasible (MFR); and (3) the contrasting pessimistic IPCC SRES A2 scenario. An extensive evaluation of the present-day deposition using nearly all information on wet deposition available worldwide shows a good agreement with observations in Europe and North America, where 60–70% of the model-calculated wet deposition rates agree to within ±50% with quality-controlled measurements. Models systematically overestimate NHx deposition in South Asia, and underestimate NOy deposition in East Asia. We show that there are substantial differences among models for the removal mechanisms of NOy, NHx, and SOx, leading to ±1 σ variance in total deposition fluxes of about 30% in the anthropogenic emissions regions, and up to a factor of 2 outside. In all cases the mean model constructed from the ensemble calculations is among the best when comparing to measurements. Currently, 36–51% of all NOy, NHx, and SOx is deposited over the ocean, and 50–80% of the fraction of deposition on land falls on natural (nonagricultural) vegetation. Currently, 11% of the worlds natural vegetation receives nitrogen deposition in excess of the “critical load” threshold of 1000 mg(N) m−2 yr−1. The regions most affected are the United States (20% of vegetation), western Europe (30%), eastern Europe (80%), South Asia (60%), East Asia (40%), southeast Asia (30%), and Japan (50%). Future deposition fluxes are mainly driven by changes in emissions, and less importantly by changes in atmospheric chemistry and climate. The global fraction of vegetation exposed to nitrogen loads in excess of 1000 mg(N) m−2 yr−1 increases globally to 17% for CLE and 25% for A2. In MFR, the reductions in NOy are offset by further increases for NHx deposition. The regions most affected by exceedingly high nitrogen loads for CLE and A2 are Europe and Asia, but also parts of Africa.

Radiative forcing in the 21st century due to ozone changes in the troposphere and the lower stratosphere

ranging from 0.40 to 0.78 W m 2 on a global and annual average. The lower stratosphere contributes an additional 7.5–9.3 DU to the calculated increase in the ozone column, increasing radiative forcing by 0.15–0.17 W m 2 . The modeled radiative forcing depends on the height distribution and geographical pattern of predicted ozone changes and shows a distinct seasonal variation. Despite the large variations between the 11 participating models, the calculated range for normalized radiative forcing is within 25%, indicating the ability to scale radiative forcing to global-mean ozone column change. INDEX TERMS: 0365 Atmospheric Composition and Structure: Troposphere—composition and chemistry; 0341 Atmospheric Composition and Structure: Middle atmosphere—constituent transport and chemistry (3334) Citation: Gauss, M., et al., Radiative forcing in the 21st century due to ozone changes in the troposphere and the lower stratosphere, J. Geophys. Res., 108(D9), 4292, doi:10.1029/2002JD002624, 2003.

Grid‐based versus big region approach for inverting CO emissions using Measurement of Pollution in the Troposphere (MOPITT) data

The CO columns retrieved by the Measurement of Pollution in the Troposphere (MOPITT) satellite instrument between May 2000 and April 2001 are used together with the Intermediate Model for the Annual and Global Evolution of Species (IMAGES) global chemistry transport model and its adjoint to provide top-down estimates for anthropogenic, biomass burning, and biogenic CO emissions on the global scale, as well as for the biogenic volatile organic compounds (VOC) fluxes, whose oxidation constitutes a major indirect CO source. For this purpose, the big region and grid-based Bayesian inversion methods are presented and compared. In the former setup, the monthly emissions over large geographical regions are quantified. In the grid-based setup, the fluxes are optimized at the spatial resolution of the model and on a monthly basis. Source-specific spatiotemporal correlations among errors on the prior emissions are introduced in order to better constrain the inversion problem. Both inversion techniques bring the model columns much closer to the measurements at all latitudes, but the grid-based analysis achieves a higher reduction of the overall model/data bias. Further comparisons with observed mixing ratios at NOAA Climate Monitoring and Diagnostics Laboratory and Global Atmosphere Watch sites, as well as with airborne measurements are also presented. The inferred emission estimates are weakly dependent on the prior errors and correlations. Our best estimate for the global CO source amounts to 2900 Tg CO/yr in both inversion approaches, about 5% higher than the prior. The global anthropogenic emission estimate is 18% larger than the prior, with the biggest increase for east Asia and a substantial decrease in south Asia. The vegetation fire emission estimates decrease as well, from the prior 467 Tg CO/yr to 450 Tg CO/yr in the grid-based solution and 434 Tg CO/yr in the monthly big region setup, mainly due to a significant reduction of African savanna fire emissions. The biogenic CO/VOC flux estimates are found to be enhanced by about 15% on the global scale. The most significant error reductions concern the biogenic emissions in the tropics, the Asian anthropogenic emissions, and the vegetation fire source over Africa. Our inversion results are further compared with previously reported emission estimates.

Modeling aerosol formation in alpha-pinene photo-oxidation experiments

[1]xa0We present BOREAM (Biogenic hydrocarbon Oxidation and Related Aerosol formation Model), a detailed model for the oxidation of α-pinene and the resulting formation of secondary organic aerosol (SOA). It is based on a quasi-explicit gas phase mechanism for the formation of primary products, developed on objective grounds using advanced theoretical methods, and on a simplified representation for the further oxidation of the products. The partitioning of the products follows a kinetic representation with coefficients estimated from vapor pressures calculated using a dedicated group contribution method. Particle phase and heterogeneous reactions are generally neglected, but the impact of peroxyhemiacetal formation in the aerosol is tested on the basis of laboratory estimates of the reaction rates. The model is evaluated against 28 laboratory experiments from 6 studies of α-pinene photo-oxidation covering a wide range of photochemical conditions. In contrast with previous modeling studies, the modeled and measured SOA yields agree to within a factor of 2 in most cases. The SOA yields are underestimated for the ozonolysis experiments of Presto et al. (2005a) when the standard version of the ozonolysis mechanism is used, presumably because of the lack of credible pathways for the formation of pinic and hydroxy pinonic acid. The underestimation is drastically reduced when the mechanism is modified to account for the formation of these compounds. Accounting for peroxyhemiacetal formation in the particle phase is found to further increase the SOA yields by about one third in high VOC ozonolysis experiments and to have a much smaller impact in all other cases. The model calculates that ozonolysis contributes about twice more to SOA formation than oxidation by OH, whereas NO3-initiated oxidation is negligible. In agreement with previous studies, low NOx conditions and low temperatures are calculated to favor aerosol formation, but the estimated temperature dependence is stronger than found in recent laboratory experiments.

Can a "state of the art" chemistry transport model simulate Amazonian tropospheric chemistry?

We present an evaluation of a nested high-resolution Goddard Earth Observing System (GEOS)-Chem chemistry transport model simulation of tropospheric chemistry over tropical South America. The model has been constrained with two isoprene emission inventories: (1) the canopy-scale Model of Emissions of Gases and Aerosols from Nature (MEGAN) and (2) a leaf-scale algorithm coupled to the Lund-Potsdam-Jena General Ecosystem Simulator (LPJ-GUESS) dynamic vegetation model, and the model has been run using two different chemical mechanisms that contain alternative treatments of isoprene photo-oxidation. Large differences of up to 100 Tg C yr^(−1) exist between the isoprene emissions predicted by each inventory, with MEGAN emissions generally higher. Based on our simulations we estimate that tropical South America (30–85°W, 14°N–25°S) contributes about 15–35% of total global isoprene emissions. We have quantified the model sensitivity to changes in isoprene emissions, chemistry, boundary layer mixing, and soil NO_x emissions using ground-based and airborne observations. We find GEOS-Chem has difficulty reproducing several observed chemical species; typically hydroxyl concentrations are underestimated, whilst mixing ratios of isoprene and its oxidation products are overestimated. The magnitude of model formaldehyde (HCHO) columns are most sensitive to the choice of chemical mechanism and isoprene emission inventory. We find GEOS-Chem exhibits a significant positive bias (10–100%) when compared with HCHO columns from the Scanning Imaging Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY) and Ozone Monitoring Instrument (OMI) for the study year 2006. Simulations that use the more detailed chemical mechanism and/or lowest isoprene emissions provide the best agreement to the satellite data, since they result in lower-HCHO columns.