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Acetylene is a short-lived trace gas produced during combustion of fossil fuels, biomass, and biofuels. Biomass burning is likely the only major source of acetylene in the preindustrial atmosphere, making ice core acetylene a powerful tool for reconstructing paleofire emissions. Here we present a 2,000-year atmospheric record of acetylene reconstructed from analysis of air bubbles trapped in Greenland and Antarctic ice cores and infer pyrogenic acetylene emissions using a chemistry transport model. From 0 to 1500 CE, Antarctic acetylene averages 36 ± 1 pmol mol−1 (mean ± 1 SE), roughly double the annual mean over Antarctica today. Antarctic acetylene declines during the Little Ice Age by over 50% to 17 ± 2 pmol mol−1 from 1650 to 1750 CE. Acetylene over Greenland declines less dramatically over the same period. Modeling results suggest that pyrogenic acetylene emissions during 1000–1500 CE were sustained at rates significantly greater than modern day and declined by over 50% during the 1650–1750 CE period.

The coupled chemistry of methane, carbon monoxide (CO), and hydroxyl radical (OH) can modulate methane's 9-year lifetime. This is often ignored in methane flux inversions, and the impacts of neglecting interactive chemistry have not been quantified. Using a coupled-chemistry box model, we show that neglecting the effect of methane source perturbation on [OH] can lead to a 25% bias in estimating abrupt changes in methane sources after only 10 years. Further, large CO emissions, such as from biomass burning, can increase methane concentrations by extending the methane lifetime through impacts on [OH]. Finally, we quantify the biases of including (or excluding) coupled chemistry in the context of recent methane and CO trends. Decreasing CO concentrations, beginning in the 2000's, have notable impacts on methane flux inversions. Given these nonnegligible errors, decadal methane emissions inversions should incorporate chemical feedbacks for more robust methane trend analyses and source attributions.

We examine the impact of El Niño–Southern Oscillation (ENSO) on surface ozone abundance observed over the continental United States (U.S.) during 1993–2013. The monthly ozone decreases (increases) during El Niño (La Niña) years with amplitude up to 1.8 ppb per standard deviation of Niño 3.4 index. The largest ENSO influences occur over two southern U.S. regions during fall when the ENSO develops and over two western U.S. regions during the winter to spring after the ENSO decays. ENSO affects surface ozone via chemical processes during warm seasons in southern regions, where favorable meteorological conditions occur, but via dynamic transport during cold seasons in western regions, where the ENSO-induced circulation variations are large. The geographic dependence and seasonality of the ENSO impacts imply that regulations regarding air quality and its exceedance need to be adjusted for different seasons and U.S. regions to account for the ENSO-driven patterns in surface ozone.

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.

Stratosphere-troposphere exchange (STE) of ozone (O3) is key in the budget of tropospheric O3, in turn affecting climate forcing and global air quality. We compare three commonly used diagnostics meant to quantify cross-tropopause O3 fluxes with a Chemistry-Transport Model driven by two distinct European Centre forecast fields. Our reference case calculates accurate, geographically resolved net transport across an isosurface in artificial tracer e90 representing the tropopause. Hemispheric fluxes derived from the ozone mass budget of the lowermost stratosphere yield similar results. Use of the Brewer-Dobson residual vertical velocity as a scaled proxy for ozone flux, however, fails to capture the interannual variability. Thus, the common notion that the strength of stratospheric overturning circulation is a good measure for global STE does not apply to O3. Climatic variability in the modeled O3 flux needs to be diagnosed directly rather than indirectly through the overturning circulation. Key Points O3 residual flux by BDC does not sync with cross-tropopause O3 fluxesMore accurate diagnostics of ozone STE are needed in climate-chemistry modelsTC and LS methods are suitable for diagnosing STE of ozone

Knowledge of the atmospheric chemistry of reactive greenhouse gases is needed to accurately quantify the relationship between human activities and climate, and to incorporate uncertainty in our projections of greenhouse gas abundances. We present a method for estimating the fraction of greenhouse gases attributable to human activities, both currently and for future scenarios. Key variables used to calculate the atmospheric chemistry and budgets of major non-CO2greenhouse gases are codified along with their uncertainties, and then used to project budgets and abundances under the new climate-change scenarios. This new approach uses our knowledge of changing abundances and lifetimes to estimate current total anthropogenic emissions, independently and possibly more accurately than inventory-based scenarios. We derive a present-day atmospheric lifetime for methane (CH4) of 9.1 ± 0.9 y and anthropogenic emissions of 352 ± 45 Tg/y (64% of total emissions). For N2O, corresponding values are 131 ± 10 y and 6.5 ± 1.3 TgN/y (41% of total); and for HFC-134a, the lifetime is 14.2 ± 1.5 y.

The two longest-lived, major chemical response patterns (eigenmodes) of the atmosphere, coupling N2O and CH4, are identified with the UCI chemistry-transport model using a linearized (N2O, NO y, O3, CH4, H2O)-system for stratospheric chemistry and specified tropospheric losses. As in previous 1D and 2D studies, these century-long 3D simulations show that the e-folding decay time of a N2O perturbation (mode-1: 108.4 y) caused by a pulse emission of N2O is 10-years shorter than the N2O atmospheric lifetime (118.2 y). This mode-1 can also be excited by CH4emissions due to CH4-O3 stratospheric chemistry: a pulse emission of 100 Tg CH4 creates a +0.1 Tg N2O perturbation in mode-1 with a 108-yr e-folding decay time, thus increasing the CH4 global warming potential by 1.2%. Almost all of the 100 Tg CH4 appears in mode-2 (10.1 y).

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.

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.

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.

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.

Satellite observations of CO2 abundance in the upper troposphere can provide a major constraint for deriving the net carbon fluxes from tropical landmasses that is unavailable from current surface observations. Such global CO2 profiling with an uncertainty of about 1% (3 ppm) contains key longitudinal information needed to derive surface fluxes in a standard Bayesian inversion. Upper-tropospheric data available from flight-proven FTIR solar occultation measurements could provide comparable information to that from yet-to-be-demonstrated column CO2 observations, which have heretofore been the focus of carbon cycle studies. A strategy for improving CO2source inversions with either type of satellite data should focus on tropical observations and on careful evaluation of possible sampling biases affecting the observational uncertainties.

Anthropogenic emissions of short-lived, chemically reactive gases, such as NOx and CO, are known to influence climate by altering the chemistry of the global troposphere and thereby the abundance of the greenhouse gases O3, CH4 and the HFCs. This study uses the characteristics of the natural modes of the tropospheric chemical system to decompose the greenhouse effect of NOx and CO emissions into (i) short-lived modes involving predominantly tropospheric O3 and (ii) the long-lived mode involving a global coupled CH4-CO-O3perturbation. Combining these two classes of greenhouse perturbations—large, short-lived, regional O3 increases and smaller, long-lived, global decreases in CH4 and O3—we find that most types of anthropogenic NOx emissions lead to a negative radiative forcing and an overall cooling of the earth.

A new approach is needed for calculating the ozone depletion potential (ODP) of short-lived gases with mean lifetimes less than 100 days. Clearly, the ozone loss from such gases depends strongly on the location and season of emissions. It is proposed that delivery to the tropical tropopause is a surrogate for the amount of halogen entering the stratosphere. Thus 3-D global models, with accurate simulation of tropospheric chemistry and transport, can calculate the ODP specific to tropical sources (high) and high-latitude sources (low). The ODP of CH2BrCH2CH3  from this analysis ranges from 0.0002 to 0.06 depending on the location and season of emissions.

Convection in the tropics turns over the upper troposphere at rates (0.08 d−1) comparable to photochemical processes controlling the absolute abundance of HOx (OH + HO2) and the abundance of NOx (NO + NO2) relative to HNO3. Here we identify convection of boundary-layer CH3OOH as a primary source of HOx to the upper troposphere. Turnover of NOx leads to NO/HNO3 ratios much higher than predicted for local photochemical steady-state. Through convective transport the upper troposphere is more photochemically active in producing O3, an important greenhouse gas.

Atmospheric CH4 perturbations, caused directly by CH4 emissions or indirectly by those of CO are enhanced by chemical feedbacks. They can be diagnosed in terms of the natural modes of atmospheric chemistry that are general solutions of the continuity equations. Each mode is a pattern in the global distribution of all chemical species, and each has a single time-constant that accurately describes its exponential decay about a given atmospheric state. This mathematical theory extends earlier work and is general for 2-D and 3-D chemistry-transport models. A formal proof relates the steady-state distribution and its lifetime to the integral of the true time-dependent response (properly included in the recent IPCC assessment). Changes in CO are also known to perturb CH4; however, the impact of CO emissions on climate has not been formally assessed in part because the short lifetime of CO (months) relative to that of CH4 (decade) was believed to limit the integrated impact. Using the IPCC model studies, this theory predicts that adding 5 CO molecules to today's atmosphere is equivalent to adding 1 CH4 molecule with the same decadal duration as direct CH4 addition. Extrapolating these results, CH4 sources would have to triple before runaway growth, wherein CH4 emissions exceed the oxidizing capacity of the troposphere. Copyright 1996 by the American Geophysical Union.

Atmospheric CH4 perturbations, caused directly by CH4 emissions or indirectly by those of CO are enhanced by chemical feedbacks. They can be diagnosed in terms of the natural modes of atmospheric chemistry that are general solutions of the continuity equations. Each mode is a pattern in the global distribution of all chemical species, and each has a single time-constant that accurately describes its exponential decay about a given atmospheric state. This mathematical theory extends earlier work and is general for 2-D and 3-D chemistry-transport models. A formal proof relates the steady-state distribution and its lifetime to the integral of the true time-dependent response (properly included in the recent IPCC assessment). Changes in CO are also known to perturb CH4; however, the impact of CO emissions on climate has not been formally assessed in part because the short lifetime of CO (months) relative to that of CH4 (decade) was believed to limit the integrated impact. Using the IPCC model studies, this theory predicts that adding 5 CO molecules to today's atmosphere is equivalent to adding 1 CH4 molecule with the same decadal duration as direct CH4 addition. Extrapolating these results, CH4 sources would have to triple before runaway growth, wherein CH4 emissions exceed the oxidizing capacity of the troposphere.

The contribution from the chlorine and bromine species in the formation of the Antarctic ozone hole is evaluated. Since chlorine and bromine compounds are of different industrial origin, it is desirable, from a policy point of view, to be able to attribute chlorine-catalyzed loss of ozone with those reactions directly involving chlorine species, and likewise for bromine-catalyzed loss. In the stratosphere, however, most of the chemical families are highly coupled, and, for example, changes in the chlorine abundance will alter the partitioning in other families and thus the rate of ozone loss. This modeling study examines formation of the Antarctic ozone hole for a wide range of bromine concentrations (5–25 pptv) and for chlorine concentrations typical of the last two decades (1.5, 2.5 and 3.5 ppbv). We follow the photochemical evolution of a single parcel of air, typical of the inner Antarctic vortex (50 mbar, 70°S, NOy=2 ppbv, with polar stratospheric clouds(PSC)) from August 1 to November 1. For all of these ranges of chlorine and bromine loading, we would predict a substantial ozone hole (local depletion greater than 90%) within the de-nitrified, PSC-perturbed vortex. The contributions of the different catalytic cycles responsible for ozone loss are tabulated. The deep minimum in ozone is driven primarily by the chlorine abundance. As bromine levels decrease, the magnitude of the chlorine-catalyzed ozone loss increases to take up the slack. This is because bromine suppresses ClO by accelerating the conversion of ClO and Cl2O2 back to HCl. For this range of conditions, the local relative efficiency of ozone destruction per bromine atom to that per chlorine atom (α-factor) ranges from 33 to 55, decreasing with increase of bromine.

The time scales and mode of the atmosphere's response to chemical perturbations are defined by the eigenvalues and eigenvectors of the system. The eigenstates of a simplified one-box CH4-CO-OH system are analyzed. The longest time constant (smallest eigenvalue) always exceeds the lifetime defined by the steady-state loss frequency for CH4, the longest lived gas. Thus, the extent of a CH4perturbation—the methane response time—is always longer than predicted by the steady-state lifetime and is independent of size of the perturbation in the linear limit. This lengthening of the atmospheric recovery time can be diagnosed by how close we are to a chemically unstable troposphere, i.e., how much OH production exceeds that minimum needed to oxidize just the global emissions of CH4, CO, and other hydrocarbons and species.

Atmospheric circulation leads to an accumulation of debris from meteors in the Antarctic stratosphere at the beginning of austral spring. The major component of meteoric material is alkaline, comprised predominantly of the oxides of magnesium and iron. These metals may neutralize the natural acidity of stratospheric aerosols, remove nitric acid from the gas phase, and bond it as metal nitrates in the aerosol phase. Removal of nitric acid vapor has been previously shown to be a critical link in the photochemical depletion of ozone in the Antarctic spring, by allowing for increased catalytic loss from chlorine and bromine.