Chemical nonlinearities in relating intercontinental ozone pollution to anthropogenic emissions

Model studies typically estimate intercontinental influence on surface ozone by perturbing emissions from a source continent and diagnosing the ozone response in the receptor continent. Since the response to perturbations is non-linear due to chemistry, conclusions drawn from different studies may depend on the magnitude of the applied perturbation. We investigate this issue for intercontinental transport between North America, Europe, and Asia with sensitivity simulations in three global chemical transport models. In each region, we decrease anthropogenic emissions of NOx and nonmethane volatile organic compounds (NMVOCs) by 20% and 100%. We find strong nonlinearity in the response to NOx perturbations outside summer, reflecting transitions in the chemical regime for ozone production. In contrast, we find no significant nonlinearity to NOx perturbations in summer or to NMVOC perturbations year-round. The relative benefit of decreasing NOx vs. NMVOC from current levels to abate intercontinental pollution increases with the magnitude of emission reductions

Chemical nonlinearities in relating intercontinental ozone pollution to anthropogenic emissions

Model studies typically estimate intercontinental influence on surface ozone by perturbing emissions from a source continent and diagnosing the ozone response in the receptor continent. Since the response to perturbations is non-linear due to chemistry, conclusions drawn from different studies may depend on the magnitude of the applied perturbation. We investigate this issue for intercontinental transport between North America, Europe, and Asia with sensitivity simulations in three global chemical transport models. In each region, we decrease anthropogenic emissions of NOx and nonmethane volatile organic compounds (NMVOCs) by 20% and 100%. We find strong nonlinearity in the response to NOx perturbations outside summer, reflecting transitions in the chemical regime for ozone production. In contrast, we find no significant nonlinearity to NOx perturbations in summer or to NMVOC perturbations year-round. The relative benefit of decreasing NOx vs. NMVOC from current levels to abate intercontinental pollution increases with the magnitude of emission reductions

Atmospheric chemistry-climate feedbacks

We extend the theory of climate feedbacks to include atmospheric chemistry. A change in temperature caused by a radiative forcing will include, in general, a contribution from the chemical change that is fed back into the climate system; likewise, the change in atmospheric burdens caused by a chemical forcing will include a contribution from the associated climate change that is fed back into the chemical system. The theory includes two feedback gains, G_(che) and G_(cli). G_(che) is defined as the ratio of the change in equilibrium global mean temperature owing to long-lived greenhouse gas radiative forcing, under full climate-chemistry coupling, to that in the absence of coupling. G_(cli) is defined as the ratio of the change in equilibrium mean aerosol or gas-phase burdens owing to chemical forcing under full coupling, to that in the absence of coupling. We employ a climate-atmospheric chemistry model based on the Goddard Institute for Space Studies (GISS) GCM II', including tropospheric gas-phase chemistry, sulfate, nitrate, ammonium, black carbon, and organic carbon. While the model describes many essential couplings between climate and atmospheric chemistry, not all couplings are accounted for, such as indirect aerosol forcing and the role of natural dust and sea salt aerosols. Guided by the feedback theory, we perform perturbation experiments to quantify G_(che) and G_(cli). We find that G_(che) for surface air temperature is essentially equal to 1.00 on a planetary scale. Regionally, G_(che) is estimated to be 0.80–1.30. The gains are small compared to those of the physical feedbacks in the climate system (e.g., water vapor, and cloud feedbacks). These values for G_(che) are robust for the specific model used, but may change when using more comprehensive climate-atmospheric chemistry models. Our perturbation experiments do not allow one to obtain robust values for G_(cli). Globally averaged, the values range from 0.99 to 1.28, depending on the chemical species, while, in areas of high pollution, G_(cli) can be up to 1.15 for ozone, and as large as 1.40 for total aerosol. These preliminary values indicate a significant role of climate feedbacks in the atmospheric chemistry system

Fresh air in the 21st century?

Ozone is an air quality problem today for much of the world's population. Regions can exceed the ozone air quality standards (AQS) through a combination of local emissions, meteorology favoring pollution episodes, and the clean-air baseline levels of ozone upon which pollution builds. The IPCC 2001 assessment studied a range of global emission scenarios and found that all but one projects increases in global tropospheric ozone during the 21st century. By 2030, near-surface increases over much of the northern hemisphere are estimated to be about 5 ppb (+2 to +7 ppb over the range of scenarios). By 2100 the two more extreme scenarios project baseline ozone increases of >20 ppb, while the other four scenarios give changes of -4 to +10 ppb. Even modest increases in the background abundance of tropospheric ozone might defeat current AQS strategies. The larger increases, however, would gravely threaten both urban and rural air quality over most of the northern hemisphere

Impact of multiscale dynamical processes and mixing on the chemical composition of the upper troposphere and lower stratosphere during the Intercontinental Chemical Transport Experiment–North America

We use high-frequency in situ observations made from the DC8 to examine fine-scale tracer structure and correlations observed in the upper troposphere and lower stratosphere during INTEX-NA. Two flights of the NASA DC-8 are compared and contrasted. Chemical data from the DC-8 flight on 18 July show evidence for interleaving and mixing of polluted and stratospheric air masses in the vicinity of the subtropical jet in the upper troposphere, while on 2 August the DC-8 flew through a polluted upper troposphere and a lowermost stratosphere that showed evidence of an intrusion of polluted air. We compare data from both flights with RAQMS 3-D global meteorological and chemical model fields to establish dynamical context and to diagnose processes regulating the degree of mixing on each day. We also use trajectory mapping of the model fields to show that filamentary structure due to upstream strain deformation contributes to tracer variability observed in the upper troposphere. An Eulerian measure of strain versus rotation in the large-scale flow is found useful in predicting filamentary structure in the vicinity of the jet. Higher-frequency (6–24 km) tracer variability is attributed to buoyancy wave oscillations in the vicinity of the jet, whose turbulent dissipation leads to efficient mixing across tracer gradients

The impact of air pollutant and methane emission controls on tropospheric ozone and radiative forcing: CTM calculations for the period 1990-2030

To explore the relationship between tropospheric ozone and radiative forcing with changing emissions, we compiled two sets of global scenarios for the emissions of the ozone precursors methane (CH₄), carbon monoxide (CO), non-methane volatile organic compounds (NMVOC) and nitrogen oxides (NO_x) up to the year 2030 and implemented them in two global Chemistry Transport Models. The 'Current Legislation' (CLE) scenario reflects the current perspectives of individual countries on future economic development and takes the anticipated effects of presently decided emission control legislation in the individual countries into account. In addition, we developed a 'Maximum technically Feasible Reduction' (MFR) scenario that outlines the scope for emission reductions offered by full implementation of the presently available emission control technologies, while maintaining the projected levels of anthropogenic activities. Whereas the resulting projections of methane emissions lie within the range suggested by other greenhouse gas projections, the recent pollution control legislation of many Asian countries, requiring introduction of catalytic converters for vehicles, leads to significantly lower growth in emissions of the air pollutants NO_x, NMVOC and CO than was suggested by the widely used and more pessimistic IPCC (Intergovernmental Panel on Climate Change) SRES (Special Report on Emission Scenarios) scenarios (Nakicenovic et al., 2000), which made Business-as-Usual assumptions regarding emission control technology. With the TM3 and STOCHEM models we performed several long-term integrations (1990-2030) to assess global, hemispheric and regional changes in CH₄, CO, hydroxyl radicals, ozone and the radiative climate forcings resulting from these two emission scenarios. Both models reproduce broadly the observed trends in CO, and CH₄ concentrations from 1990 to 2002. <P style='line-height: 20px;'> For the 'current legislation' case, both models indicate an increase of the annual average ozone levels in the Northern Hemisphere by 5ppbv, and up to 15ppbv over the Indian sub-continent, comparing the 2020s (2020-2030) with the 1990s (1990-2000). The corresponding higher ozone and methane burdens in the atmosphere increase radiative forcing by approximately 0.2 Wm^-2. Full application of today's emissions control technologies, however, would bring down ozone below the levels experienced in the 1990s and would reduce the radiative forcing of ozone and methane to approximately -0.1 Wm^-2. This can be compared to the 0.14-0.47 Wm^-2 increase of methane and ozone radiative forcings associated with the SRES scenarios. While methane reductions lead to lower ozone burdens and to less radiative forcing, further reductions of the air pollutants NO_x and NMVOC result in lower ozone, but at the same time increase the lifetime of methane. Control of methane emissions appears an efficient option to reduce tropospheric ozone as well as radiative forcing

Chemical transport model ozone simulations for spring 2001 over the western Pacific: Regional ozone production and its global impacts

The spatial and temporal variation in ozone production over major source regions in East Asia during the NASA Transport and Chemical Evolution over the Pacific (TRACE-P) measurement campaign in spring 2001 is assessed using a global chemical transport model. There is a strong latitudinal gradient in ozone production in springtime, driven by regional photochemistry, which rapidly diminishes as the season progresses. The great variability in meteorological conditions characteristic of East Asia in springtime leads to large daily variability in regional ozone formation, but we find that it has relatively little impact on the total global production. We note that transport processes effectively modulate and thus stabilize total ozone production through their influence over its location. However, the impact on the global ozone burden, important for assessing the effects of precursor emissions on tropospheric oxidizing capacity and climate, is sensitive to local meteorology through the effects of location on chemical lifetime. Stagnant, anticyclonic conditions conducive to substantial boundary layer ozone production typically allow little lifting of precursors into the free troposphere where greater ozone production could occur, and the consequent shorter chemical lifetime for ozone leads to relatively small impacts on global ozone. Conversely, cyclonic conditions with heavy cloud cover suppressing regional ozone production are often associated with substantial cloud convection, enhancing subsequent production in the free troposphere where chemical lifetimes are longer, and the impacts on global ozone are correspondingly greater. We find that ozone formation in the boundary layer and free troposphere outside the region of precursor emissions dominates total gross production from these sources in springtime, and that it makes a big contribution to the long range transport of ozone, which is greatest in this season