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We present a comprehensive estimate of nitrous oxide (N2O) emissions using observations and models from 1995 to 2008. High-frequency records of tropospheric N2O are available from measurements at Cape Grim, Tasmania; Cape Matatula, American Samoa; Ragged Point, Barbados; Mace Head, Ireland; and at Trinidad Head, California using the Advanced Global Atmospheric Gases Experiment (AGAGE) instrumentation and calibrations. The Global Monitoring Division of the National Oceanic and Atmospheric Administration/Earth System Research Laboratory (NOAA/ESRL) has also collected discrete air samples in flasks and in situ measurements from remote sites across the globe and analyzed them for a suite of species including N2O. In addition to these major networks, we include in situ and aircraft measurements from the National Institute of Environmental Studies (NIES) and flask measurements from the Tohoku University and Commonwealth Scientific and Industrial Research Organization (CSIRO) networks. All measurements show increasing atmospheric mole fractions of N2O, with a varying growth rate of 0.1–0.7% per year, resulting in a 7.4% increase in the background atmospheric mole fraction between 1979 and 2011. Using existing emission inventories as well as bottom-up process modeling results, we first create globally gridded a priori N2O emissions over the 37 years since 1975. We then use the three-dimensional chemical transport model, Model for Ozone and Related Chemical Tracers version 4 (MOZART v4), and a Bayesian inverse method to estimate global as well as regional annual emissions for five source sectors from 13 regions in the world. This is the first time that all of these measurements from multiple networks have been combined to determine emissions. Our inversion indicates that global and regional N2O emissions have an increasing trend between 1995 and 2008. Despite large uncertainties, a significant increase is seen from the Asian agricultural sector in recent years, most likely due to an increase in the use of nitrogenous fertilizers, as has been suggested by previous studies.

We use an atmospheric general circulation model (AGCM) driven chemistry-transport model (ACTM) to simulate the evolution of sulfur hexafluoride (SF6) in the troposphere. The model results are compared with continuous measurements at 6 sites over 71° N–90° S. These comparisons demonstrate that the ACTM simulations lie within the measurement uncertainty over the analysis period (1999–2006) and capture salient features of synoptic, seasonal and interannual SF6 variability. To understand transport timescales of SF6 within the troposphere, transport times of air parcels from the surface to different regions of the troposphere ("age") are estimated from a simulation of an idealized tracer. The age estimation error and its sensitivity to the selection of reanalysis meteorology for ACTM nudging or the tracer transport by deep cumulus convection as represented in the model are discussed. Monthly-mean, 2-box model exchange times (τex) are calculated from both the observed and simulated SF6 time series at the 6 observing sites and show favorable agreement, suggesting that the ACTM adequately represents large-scale interhemispheric transport. The simulated SF6 variability is further investigated through decomposition of the mixing ratio time-tendency into advective, convective, and vertical diffusive components. The transport component analysis illustrates the role of each process in SF6 synoptic variability at the site level and provides insight into the seasonality of τex.

Profiles of CFC-11 (CCl$_{3}$F) and CFC-12 (CCl$_{2}$F$_{2}$) of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) aboard the European satellite Envisat have been retrieved from versions MIPAS/4.61 to MIPAS/ 4.62 and MIPAS/5.02 to MIPAS/5.06 level-1b data using the scientific level-2 processor run by Karlsruhe Institute of Technology (KIT), Institute of Meteorology and Climate Research (IMK) and Consejo Superior de Investigaciones Científicas (CSIC), Instituto de Astrofísica de Andalucía (IAA). These profiles have been compared to measurements taken by the balloon-borne cryosampler, Mark IV (MkIV) and MIPAS-Balloon (MIPAS-B), the airborne MIPAS-STRatospheric aircraft (MIPAS-STR), the satellite-borne Atmospheric Chemistry Experiment Fourier transform spectrometer (ACE-FTS) and the High Resolution Dynamic Limb Sounder (HIRDLS), as well as the groundbased Halocarbon and other Atmospheric Trace Species (HATS) network for the reduced spectral resolution period (RR: January 2005–April 2012) of MIPAS. ACE-FTS, MkIV and HATS also provide measurements during the high spectral resolution period (full resolution, FR: July 2002–March 2004) and were used to validate MIPAS CFC-11 and CFC- 12 products during that time, as well as profiles from the Improved Limb Atmospheric Spectrometer, ILAS-II. In general, we find that MIPAS shows slightly higher values for CFC-11 at the lower end of the profiles (below 15 km) and in a comparison of HATS ground-based data and MIPAS measurements at 3 km below the tropopause. Differences range from approximately 10 to 50 pptv ( ~5–20 %) during the RR period. In general, differences are slightly smaller for the FR period. An indication of a slight high bias at the lower end of the profile exists for CFC-12 as well, but this bias is far less pronounced than for CFC-11 and is not as obvious in the relative differences between MIPAS and any of the comparison instruments. Differences at the lower end of the profile (below ~15 km) and in the comparison of HATS and MIPAS measurements taken at 3 km below the tropopause mainly stay within 10–50 pptv (corresponding to ~ 2–10% for CFC-12) for the RR and the FR period. Between ~15 and 30 km, most comparisons agree within 10–20 pptv (10–20 %), apart from ILAS-II, which shows large differences above ~17 km. Overall, relative differences are usually smaller for CFC-12 than for CFC-11. For both species – CFC-11 and CFC-12 – we find that differences at the lower end of the profile tend to be larger at higher latitudes than in tropical and subtropical regions. In addition, MIPAS profiles have a maximum in their mixing ratio around the tropopause, which is most obvious in tropical mean profiles. Comparisons of the standard deviation in a quiescent atmosphere (polar summer) show that only the CFC-12 FR error budget can fully explain the observed variability, while for the other products (CFC-11 FR and RR and CFC-12 RR) only two-thirds to three-quarters can be explained. Investigations regarding the temporal stability show very small negative drifts in MIPAS CFC-11 measurements. These instrument drifts vary between ~1 and 3% decade$^{-1}$. For CFC-12, the drifts are also negative and close to zero up to ~30 km. Above that altitude, larger drifts of up to 50% decade$^{-1}$ appear which are negative up to ~35 km and positive, but of a similar magnitude, above.