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The impacts of climate change on tropospheric transport, diagnosed from a carbon monoxide (CO)-like tracer species emitted from global CO sources, are evaluated from an ensemble of four chemistry-climate model (CCMs) contributing to the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP). Model time-slice simulations for present-day and end of the 21st century conditions were performed under the Representative Concentrations Pathways (RCP) climate scenario RCP 8.5. All simulations reveal a strong seasonality in transport, especially over the tropics. The highest CO-tracer mixing ratios aloft occur during boreal winter when strong vertical transport is co-located with biomass burning emission source regions. A consistent and robust decrease in future CO-tracer mixing ratios throughout most of the troposphere, especially in the tropics, and an increase around the tropopause is found across the four CCMs in both winter and summer. Decreases in CO-tracer mixing ratios in the tropical troposphere are associated with reduced convective mass fluxes in this region, which in turn may reflect a weaker Hadley Cell circulation in the future climate. Increases in CO-tracer mixing ratios near the tropopause are largely attributable to a rise in tropopause height enabling lofting to higher altitudes, although a poleward shift in the mid-latitude jets may also play a minor role in the extra-tropical upper troposphere. An increase in CO-tracer mixing ratios also occurs near the Equator, centred over equatorial and Central Africa, extending from the surface to the mid-troposphere. This is most likely related to localised decreases in convection in the vicinity of the Intertropical Convergence Zone (ITCZ), resulting in larger CO-tracer mixing ratios over biomass burning regions and smaller mixing ratios downwind.

Delineating the boundary between troposphere and stratosphere in a chemistry transport model requires a state variable for each air mass that maps out the ever shifting, overlapping three-dimensional (3-D) boundary at each time step. Using an artificial tracer, e90, with surface sources and 90 day decay time, the model e90 tropopause matches the 1-D temperature lapse rate definition of the tropopause as well as the seasonal variation of ozone at this boundary. This approach works from equator to pole, over all seasons, unlike methods based on potential vorticity or ozone. By focusing on the time scales that separate stratosphere from troposphere, we examine the cause of ozone seasonality at the midlatitude tropopause, the oldest air in the troposphere (winter descent in the subtropics), and a north-south bias in the age of air of the lowermost stratosphere as evaluated using a northern tracer. The tracer e90 is invaluable in 3-D modeling, readily separating stratosphere from troposphere and a giving quantitative measure of the effective distance from the tropopause.

Nitrous oxide (N(2)O) and methane (CH(4)) are chemically reactive greenhouse gases with well-documented atmospheric concentration increases that are attributable to anthropogenic activities. We quantified the link between N(2)O and CH(4) emissions through the coupled chemistries of the stratosphere and troposphere. Specifically, we simulated the coupled perturbations of increased N(2)O abundance, leading to stratospheric ozone (O(3)) depletion, altered solar ultraviolet radiation, altered stratosphere-to-troposphere O(3) flux, increased tropospheric hydroxyl radical concentration, and finally lower concentrations of CH(4). The ratio of CH(4) per N(2)O change, -36% by mole fraction, offsets a fraction of the greenhouse effect attributable to N(2)O emissions. These CH(4) decreases are tied to the 108-year chemical mode of N(2)O, which is nine times longer than the residence time of direct CH(4) emissions.

Photolytic dissociation of molecular oxygen (O2) at wavelengths about 205 nm produces ozone (O3) in the upper tropical troposphere. In tropospheric chemistry models that ignore this process, the O3 abundance above 14 km in the tropics (a.k.a. Tropopause Transition Layer) is underestimated by 5 to 20 ppb. Even for models including O2 photolysis, uncertainty in the O2 cross sections yields similar uncertainty in TTL O3. The related impact on global atmospheric chemistry is small, i.e., ±0.2% in CO and CH4 budgets, but the change in the O3 column, ±1.6 DU in the tropics, may be important in calculating heating rates and climate forcing.

Attribution of climate change to individual countries is a part of ongoing policy discussions, e.g., the Brazil proposal, and requires a quantifiable link between emissions and climate change. We present a constrained propagation of errors that tracks uncertainties from human activities to greenhouse gas emissions, to increasing abundances of greenhouse gases, to radiative forcing of climate, and finally to climate change, thus following the causal chain for greenhouse gases emitted by developed nations since national reporting began in 1990. Errors combine uncertainties in the forward modeling at each step with top-down constraints on the observed changes in greenhouse gases and temperatures. Global surface temperature increased by +0.11 °C in 2003 due to the developed nations' emissions of Kyoto greenhouse gases from 1990 to 2002. The uncertainty range, +0.08 °C to +0.14 °C (68% confidence), is large considering that the developed countries emissions are well known for this period and climate system modeling uncertainties are constrained by observations.

The rapid rise of global temperature that began about 1975 continues at a mean rate of about 0.18 °C/decade, with the current annual temperature exceeding +1.25 °C relative to 1880–1920. Global temperature has just reached a level similar to the mean level in the prior interglacial (Eemian) period, when sea level was several meters higher than today, and, if it long remains at this level, slow amplifying feedbacks will lead to greater climate change and consequences. The growth rate of climate forcing due to human-caused greenhouse gases (GHGs) increased over 20 % in the past decade mainly due to resurging growth of atmospheric CH4, thus making it increasingly difficult to achieve targets such as limiting global warming to 1.5 °C or reducing atmospheric CO2 below 350 ppm. Such targets now require "negative emissions", i.e., extraction of CO2 from the atmosphere. If rapid phasedown of fossil fuel emissions begins soon, most of the necessary CO2 extraction can take place via improved agricultural and forestry practices, including reforestation and steps to improve soil fertility and increase its carbon content. In this case, the magnitude and duration of global temperature excursion above the natural range of the current interglacial (Holocene) could be limited and irreversible climate impacts could be minimized. In contrast, continued high fossil fuel emissions by the current generation would place a burden on young people to undertake massive technological CO2 extraction, if they are to limit climate change. Proposed methods of extraction such as bioenergy with carbon capture and storage (BECCS) or air capture of CO2 imply minimal estimated costs of 104–570 trillion dollars this century, with large risks and uncertain feasibility. Continued high fossil fuel emissions unarguably sentences young people to either a massive, possibly implausible cleanup or growing deleterious climate impacts or both, scenarios that should provide both incentive and obligation

The effect of future climate change on surface ozone over North America, Europe, and East Asia is evaluated using present-day (2000s) and future (2100s) hourly surface ozone simulated by four global models. Future climate follows RCP8.5, while methane and anthropogenic ozone precursors are fixed at year-2000 levels. Climate change shifts the seasonal surface ozone peak to earlier in the year and increases the amplitude of the annual cycle. Increases in mean summertime and high-percentile ozone are generally found in polluted environments, while decreases are found in clean environments. We propose climate change augments the efficiency of precursor emissions to generate surface ozone in polluted regions, thus reducing precursor export to neighboring downwind locations. Even with constant biogenic emissions, climate change causes the largest ozone increases at high percentiles. In most cases, air quality extreme episodes become larger and contain higher ozone levels relative to the rest of the distribution.

Nitrogen trifluoride (NF3) can be called the missing greenhouse gas: It is a synthetic chemical produced in industrial quantities; it is not included in the Kyoto basket of greenhouse gases or in national reporting under the United Nations Framework Convention on Climate Change (UNFCCC); and there are no observations documenting its atmospheric abundance. Current publications report a long lifetime of 740 yr and a global warming potential (GWP), which in the Kyoto basket is second only to SF6. We re-examine the atmospheric chemistry of NF3 and calculate a shorter lifetime of 550 yr, but still far beyond any societal time frames. With 2008 production equivalent to 67 million metric tons of CO2, NF3 has a potential greenhouse impact larger than that of the industrialized nations' emissions of PFCs or SF6, or even that of the world's largest coal-fired power plants. If released, annual production would increase the lower atmospheric abundance by 0.4 ppt, and it is urgent to document NF3 emissions through atmospheric observations.

The environmental damage caused by atmospheric pollutants is proportional to the duration of their effects. The global impacts of greenhouse gases (as measured by global warming potential) and ozone depleting substances (as measured by ozone depletion potential) have traditionally been calculated using the atmospheric lifetime of the source gas as a quantitative measure of the impact's duration, assuming that the gas quickly reaches a steady-state pattern which decays exponentially according to the lifetime. This assumed behavior obviously does not match the true rise and fall of impacts, particularly secondary ones like ozone depletion, that can be seen in numerical integrations or chemical mode decomposition. Here, the modes decomposition is used to prove that: (a) the steady-state pattern of impacts caused by specified emissions, multiplied by (b) the steady-state lifetime of the source gas for that emission pattern, is exactly equal to (c) the integral of all impacts - independent of the number and atmospheric residence times of secondary impacts.

Results from simulations performed for the Atmospheric Chemistry and Climate Modeling Intercomparison Project (ACCMIP) are analysed to examine how OH and methane lifetime may change from present day to the future, under different climate and emissions scenarios. Present day (2000) mean tropospheric chemical lifetime derived from the ACCMIP multi-model mean is 9.8±1.6 yr (9.3±0.9 yr when only including selected models), lower than a recent observationally-based estimate but with a similar range to previous multi-model estimates. Future model projections are based on the four Representative Concentration Pathways (RCPs), and the results also exhibit a large range. Decreases in global methane lifetime of 4.5±9.1% are simulated for the scenario with lowest radiative forcing by 2100 (RCP 2.6), while increases of 8.5±10.4% are simulated for the scenario with highest radiative forcing (RCP 8.5). In this scenario, the key driver of the evolution of OH and methane lifetime is methane itself, since its concentration more than doubles by 2100 and it consumes much of the OH that exists in the troposphere. Stratospheric ozone recovery, which drives tropospheric OH decreases through photolysis modifications, also plays a partial role. In the other scenarios, where methane changes are less drastic, the interplay between various competing drivers leads to smaller and more diverse OH and methane lifetime responses, which are difficult to attribute. For all scenarios, regional OH changes are even more variable, with the most robust feature being the large decreases over the remote oceans in RCP8.5. Through a regression analysis, we suggest that differences in emissions of non-methane volatile organic compounds and in the simulation of photolysis rates may be the main factors causing the differences in simulated present day OH and methane lifetime. Diversity in predicted changes between present day and future OH was found to be associated more strongly with differences in modelled tempe

We have analysed time-slice simulations from 17 global models, participating in the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP), to explore changes in present-day (2000) hydroxyl radical (OH) concentration and methane (CH4) lifetime relative to preindustrial times (1850) and to 1980. A comparison of modeled and observation-derived methane and methyl chloroform lifetimes suggests that the present-day global multi-model mean OH concentration is overestimated by 5 to 10% but is within the range of uncertainties. The models consistently simulate higher OH concentrations in the Northern Hemisphere (NH) compared with the Southern Hemisphere (SH) for the present-day (2000; inter-hemispheric ratios of 1.13 to 1.42), in contrast to observation-based approaches which generally indicate higher OH in the SH although uncertainties are large. Evaluation of simulated carbon monoxide (CO) concentrations, the primary sink for OH, against ground-based and satellite observations suggests low biases in the NH that may contribute to the high north–south OH asymmetry in the models. The models vary widely in their regional distribution of present-day OH concentrations (up to 34%). Despite large regional changes, the multi-model global mean (mass-weighted) OH concentration changes little over the past 150 yr, due to concurrent increases in factors that enhance OH (humidity, tropospheric ozone, nitrogen oxide (NOx) emissions, and UV radiation due to decreases in stratospheric ozone), compensated by increases in OH sinks (methane abundance, carbon monoxide and non-methane volatile organic carbon (NMVOC) emissions). The large inter-model diversity in the sign and magnitude of preindustrial to present-day OH changes (ranging from a decrease of 12.7% to an increase of 14.6%) indicate that uncertainty remains in our understanding of the long-term trends in OH and methane lifetime. We show that this diversity is largely explained by the different ratio of the change i

Methane and ethane are the most abundant hydrocarbons in the atmosphere and they affect both atmospheric chemistry and climate. Both gases are emitted from fossil fuels and biomass burning, whereas methane (CH(4)) alone has large sources from wetlands, agriculture, landfills and waste water. Here we use measurements in firn (perennial snowpack) air from Greenland and Antarctica to reconstruct the atmospheric variability of ethane (C(2)H(6)) during the twentieth century. Ethane levels rose from early in the century until the 1980s, when the trend reversed, with a period of decline over the next 20 years. We find that this variability was primarily driven by changes in ethane emissions from fossil fuels; these emissions peaked in the 1960s and 1970s at 14-16 teragrams per year (1 Tg = 10(12) g) and dropped to 8-10 Tg yr(-1) by the turn of the century. The reduction in fossil-fuel sources is probably related to changes in light hydrocarbon emissions associated with petroleum production and use. The ethane-based fossil-fuel emission history is strikingly different from bottom-up estimates of methane emissions from fossil-fuel use, and implies that the fossil-fuel source of methane started to decline in the 1980s and probably caused the late twentieth century slow-down in the growth rate of atmospheric methane.

Changes in the stratosphere-troposphere exchange (STE) of ozone over the last few decades have altered the tropospheric ozone abundance and are likely to continue doing so in the coming century as climate changes. Combining an updated linearized stratospheric ozone chemistry (Linoz v2) with parameterized polar stratospheric clouds (PSCs) chemistry, a 5-year (2001–2005) sequence of the European Centre for Medium-Range Weather Forecasts (ECMWF) meteorology data, and the University of California, Irvine (UCI) chemistry transport model (CTM), we examined variations in STE O3 flux and how it perturbs tropospheric O3. Our estimate for the current STE ozone flux is 290 Tg/a in the Northern Hemisphere (NH) and 225 Tg/a in the Southern Hemisphere (SH). The 2001–2005 interannual root-mean-square (RMS) variability is 25 Tg/a for the NH and 30 Tg/a for the SH. STE drives a seasonal peak-to-peak NH variability in tropospheric ozone of about 7–8 Dobson unit (DU). Of the interannual STE variance, 20% and 45% can be explained by the quasi-biennial oscillation (QBO) in the NH and SH, respectively. The CTM matches the observed QBO variations in total column ozone, and the STE O3 flux shows negative anomalies over the midlatitudes during the easterly phases of the QBO. When the observed column ozone depletion from 1979 to 2004 is modeled with Linoz v2, we predicted STE reductions of at most 10% in the NH, corresponding to a mean decrease of 1 ppb in tropospheric O3.

Ozone exposure is associated with negative health impacts, including premature mortality. Observations and modeling studies demonstrate that emissions from one continent influence ozone air quality over other continents. We estimate the premature mortalities avoided from surface ozone decreases obtained via combined 20% reductions of anthropogenic nitrogen oxide, non-methane volatile organic compound, and carbon monoxide emissions in North America (NA), East Asia (EA), South Asia (SA), and Europe (EU). We use estimates of ozone responses to these emission changes from several atmospheric chemical transport models combined with a health impact function. Foreign emission reductions contribute approximately 30%, 30%, 20%, and >50% of the mortalities avoided by reducing precursor emissions in all regions together in NA, EA, SA, and EU, respectively. Reducing emissions in NA and EU avoids more mortalities outside the source region than within, owing in part to larger populations in foreign regions. Lowering the global methane abundance by 20% reduces mortality most in SA, followed by EU, EA, and NA. For some source−receptor pairs, there is greater uncertainty in our estimated avoided mortalities associated with the modeled ozone responses to emission changes than with the health impact function parameters.

Observations have revealed widespread emissions of alkyl nitrates from the tropical and Southern Oceans. We present the first chemical transport model simulations to examine the global impact of these emissions. Matching observed atmospheric abundances, we derive a total oceanic flux of methyl nitrate (MeONO2) and ethyl nitrate (EtONO2) equivalent to 0.35 Tg of N per year, which contributes as much as 1 DU to the tropospheric ozone column in the Western Pacific and is responsible for about 3% of the global oxidative capacity of the troposphere.