[1] 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-CO 2 greenhouse 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 inventorybased scenarios. We derive a present-day atmospheric lifetime for methane (CH 4 ) of 9.1 AE 0.9 y and anthropogenic emissions of 352 AE 45 Tg/y (64% of total emissions). For N 2 O, corresponding values are 131 AE 10 y and 6.5 AE 1.3 TgN/y (41% of total); and for HFC-134a, the lifetime is 14.2 AE 1.5 y. Citation: Prather, M. J., C. D. Holmes, and J. Hsu (2012), Reactive greenhouse gas scenarios: Systematic exploration of uncertainties and the role of atmospheric chemistry, Geophys.

[1] 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)(2002)(2003)(2004)(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 O 3 flux and how it perturbs tropospheric O 3 . 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 O 3 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 O 3 .

The lifetime of nitrous oxide, the third‐most‐important human‐emitted greenhouse gas, is based to date primarily on model studies or scaling to other gases. This work calculates a semiempirical lifetime based on Microwave Limb Sounder satellite measurements of stratospheric profiles of nitrous oxide, ozone, and temperature; laboratory cross‐section data for ozone and molecular oxygen plus kinetics for O(1D); the observed solar spectrum; and a simple radiative transfer model. The result is 116 ± 9 years. The observed monthly‐to‐biennial variations in lifetime and tropical abundance are well matched by four independent chemistry‐transport models driven by reanalysis meteorological fields for the period of observation (2005–2010), but all these models overestimate the lifetime due to lower abundances in the critical loss region near 32 km in the tropics. These models plus a chemistry‐climate model agree on the nitrous oxide feedback factor on its own lifetime of 0.94 ± 0.01, giving N2O perturbations an effective residence time of 109 years. Combining this new empirical lifetime with model estimates of residence time and preindustrial lifetime (123 years) adjusts our best estimates of the human‐natural balance of emissions today and improves the accuracy of projected nitrous oxide increases over this century.

[1] Events involving stratosphere-troposphere exchange (STE) of ozone, such as tropopause folds and westerly ducts, are readily identified in observations and models, but a quantitative flux specifying where and when stratospheric ozone is mixed into the troposphere is not readily discerned from either. This work presents a new diagnostic based on determining when stratospheric air is mixed and diluted down to tropospheric abundances (<100 ppb) and hence effectively participates in tropospheric chemistry. The method is applied to two years of high-resolution, global meteorological fields (1.9 degrees, 40 levels) from the ECMWF forecast model derived by U. Oslo for chemistry transport modeling and used in TRACE-P studies. The UCI CTM is run here with linearized stratospheric ozone chemistry (Linoz) and a parameterized tropospheric sink. In terms of events, the CTM accurately follows a March 2001 westerly duct stratospheric intrusion into the tropical eastern Pacific as observed by TOMS and calculates a 48-hour burst of STE O3 flux for that region. The influx associated with the event (0.3 Tg) is much less than the anomalous amount seen as an isolated island in column ozone (1.7 Tg). A climatology of monthly mean STE fluxes is similar for both years (January to December 1997 and May 2000 to April 2001), but the warm phase of ENSO December 1997 is distinctly different from the cold phase of ENSO month December 2000. Global ozone fluxes are about 515 Tg (year 1997) and 550 Tg (year 2000/2001) with an equal amount into each hemisphere, and larger springtime fluxes for both hemispheres. In terms of geographical distribution, Northern Hemisphere regions of high ozone flux follow the jet streams over the oceans in the winter and over the continents in the summer, in agreement with many previous studies. In contrast, we find the largest STE flux is located in the subtropics during late spring, particularly over the Tibetan Plateau in May. This hot spot of STE is not a numerical artifact, it occurs in both meteorological years, and it appears to be caused by the rapid erosion of the tropopause. Ozone fluxes in the Southern Hemisphere have less variability (either temporal or spatial), and they occur mainly in the subtropical region (25°S-35°S) regardless of season. The poles, throughout the year, show minimal STE O3 flux.Citation: Hsu, J., M. J. Prather, and O. Wild (2005), Diagnosing the stratosphere-to-troposphere flux of ozone in a chemistry transport model,

[1] 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.

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.

Lingering Atmospheric Perturbations Nitrous oxide and methane are chemically active greenhouse gases whose atmospheric abundances are greatly influenced by anthropogenic emissions. Prather and Hsu (p. 952 ) used an atmospheric chemistry model to show how nitrous oxide emissions lower the concentration of tropospheric methane through a chain of chemical reactions that include stratospheric ozone depletion, changes in solar ultraviolet radiation fluxes, altered fluxes of ozone transport from the stratosphere to the troposphere, and increases in the amount of tropospheric hydroxyl radicals. This mechanism acts on a 108-year-long time scale—10 times longer than the atmospheric residence time of methane.

We study the mechanisms driving stratosphere‐troposphere exchange of ozone fluxes within a chemistry‐transport model. For years 2004–2006, year‐round, most of the stratosphere‐to‐troposphere flux of O3 is associated with shear and folding around the subtropical jet, and this jet‐related flux peaks for the northern hemisphere in May. Over the northern mid‐latitude continents, however, surface convection penetrates to stratospheric levels of O3 (250 ppb), enhancing the O3 flux by 19% of the northern hemisphere total, and shifting the peak flux to June. This convection‐related O3 flux represents 49% of the total over northern mid‐latitudes in June.