Tropospheric Mixing Ratios Research Articles

ICLASS 1.1, a variational Inverse modelling framework for the Chemistry Land-surface Atmosphere Soil Slab model: description, validation, and application

Abstract. This paper provides a description of ICLASS 1.1, a variational Inverse modelling framework for the Chemistry Land-surface Atmosphere Soil Slab model. This framework can be used to study the atmospheric boundary layer, surface layer, or the exchange of gases, moisture, heat, and momentum between the land surface and the lower atmosphere. The general aim of the framework is to allow the assimilation of various streams of observations (fluxes, mixing ratios at multiple heights, etc.) to estimate model parameters, thereby obtaining a physical model that is consistent with a diverse set of observations. The framework allows the retrieval of parameters in an objective manner and enables the estimation of information that is difficult to obtain directly by observations, for example, free tropospheric mixing ratios or stomatal conductances. Furthermore, it allows the estimation of possible biases in observations. Modelling the carbon cycle at the ecosystem level is one of the main intended fields of application. The physical model around which the framework is constructed is relatively simple yet contains the core physics to simulate the essentials of a well-mixed boundary layer and of the land–atmosphere exchange. The model includes an explicit description of the atmospheric surface layer, a region where scalars show relatively large gradients with height. An important challenge is the strong non-linearity of the model, which complicates the estimation of the best parameter values. The constructed adjoint of the tangent linear model can be used to mitigate this challenge. The adjoint allows for an analytical gradient of the objective cost function, which is used for minimisation of this function. An implemented Monte Carlo way of running ICLASS can further help to handle non-linearity and provides posterior statistics on the estimated parameters. The paper provides a technical description of the framework, includes a validation of the adjoint code, in addition to tests for the full inverse modelling framework, and a successful example application for a grassland in the Netherlands.

Global tropospheric halogen (Cl, Br, I) chemistry and its impact on oxidants

Abstract. We present an updated mechanism for tropospheric halogen (Cl + Br + I) chemistry in the GEOS-Chem global atmospheric chemical transport model and apply it to investigate halogen radical cycling and implications for tropospheric oxidants. Improved representation of HOBr heterogeneous chemistry and its pH dependence in our simulation leads to less efficient recycling and mobilization of bromine radicals and enables the model to include mechanistic sea salt aerosol debromination without generating excessive BrO. The resulting global mean tropospheric BrO mixing ratio is 0.19 ppt (parts per trillion), lower than previous versions of GEOS-Chem. Model BrO shows variable consistency and biases in comparison to surface and aircraft observations in marine air, which are often near or below the detection limit. The model underestimates the daytime measurements of Cl2 and BrCl from the ATom aircraft campaign over the Pacific and Atlantic, which if correct would imply a very large missing primary source of chlorine radicals. Model IO is highest in the marine boundary layer and uniform in the free troposphere, with a global mean tropospheric mixing ratio of 0.08 ppt, and shows consistency with surface and aircraft observations. The modeled global mean tropospheric concentration of Cl atoms is 630 cm−3, contributing 0.8 % of the global oxidation of methane, 14 % of ethane, 8 % of propane, and 7 % of higher alkanes. Halogen chemistry decreases the global tropospheric burden of ozone by 11 %, NOx by 6 %, and OH by 4 %. Most of the ozone decrease is driven by iodine-catalyzed loss. The resulting GEOS-Chem ozone simulation is unbiased in the Southern Hemisphere but too low in the Northern Hemisphere.

Upward transport into and within the Asian monsoon anticyclone as inferred from StratoClim trace gas observations

Abstract. Every year during the Asian summer monsoon season from about mid-June to early September, a stable anticyclonic circulation system forms over the Himalayas. This Asian summer monsoon (ASM) anticyclone has been shown to promote transport of air into the stratosphere from the Asian troposphere, which contains large amounts of anthropogenic pollutants. Essential details of Asian monsoon transport, such as the exact timescales of vertical transport, the role of convection in cross-tropopause exchange, and the main location and level of export from the confined anticyclone to the stratosphere are still not fully resolved. Recent airborne observations from campaigns near the ASM anticyclone edge and centre in 2016 and 2017, respectively, show a steady decrease in carbon monoxide (CO) and increase in ozone (O3) with height starting from tropospheric values of around 100 ppb CO and 30–50 ppb O3 at about 365 K potential temperature. CO mixing ratios reach stratospheric background values below ∼25 ppb at about 420 K and do not show a significant vertical gradient at higher levels, while ozone continues to increase throughout the altitude range of the aircraft measurements. Nitrous oxide (N2O) remains at or only marginally below its 2017 tropospheric mixing ratio of 333 ppb up to about 400 K, which is above the local tropopause. A decline in N2O mixing ratios that indicates a significant contribution of stratospheric air is only visible above this level. Based on our observations, we draw the following picture of vertical transport and confinement in the ASM anticyclone: rapid convective uplift transports air to near 16 km in altitude, corresponding to potential temperatures up to about 370 K. Although this main convective outflow layer extends above the level of zero radiative heating (LZRH), our observations of CO concentration show little to no evidence of convection actually penetrating the tropopause. Rather, further ascent occurs more slowly, consistent with isentropic vertical velocities of 0.7–1.5 K d−1. For the key tracers (CO, O3, and N2O) in our study, none of which are subject to microphysical processes, neither the lapse rate tropopause (LRT) around 380 K nor the cold point tropopause (CPT) around 390 K marks a strong discontinuity in their profiles. Up to about 20 to 35 K above the LRT, isolation of air inside the ASM anticyclone prevents significant in-mixing of stratospheric air (throughout this text, the term in-mixing refers specifically to mixing processes that introduce stratospheric air into the predominantly tropospheric inner anticyclone). The observed changes in CO and O3 likely result from in situ chemical processing. Above about 420 K, mixing processes become more significant and the air inside the anticyclone is exported vertically and horizontally into the surrounding stratosphere.

Profiling of formaldehyde, glyoxal, methylglyoxal, and CO over the Amazon: normalized excess mixing ratios and related emission factors in biomass burning plumes

Abstract. We report on airborne measurements of tropospheric mixing ratios and vertical profiles of formaldehyde (CH2O), glyoxal (C2H2O2), methylglyoxal and higher carbonyls (C3H4O2*) (see below), and carbon monoxide (CO) over the Amazon Basin during the ACRIDICON-CHUVA campaign from the German High Altitude and Long-range research aircraft (HALO) in autumn 2014. The joint observation of in situ CO and remotely measured CH2O, C2H2O2, and C3H4O2*, together with visible imagery and air mass back-trajectory modelling using NOAA HYSPLIT (National Oceanic Atmospheric Administration, HYbrid Single-Particle Lagrangian Integrated Trajectory), allows us to discriminate between the probing of background tropical air, in which the concentration of the measured species results from the oxidation of biogenically emitted volatile organic compounds (VOCs, mostly isoprene), and measurements of moderately to strongly polluted air masses affected by biomass burning emissions or the city plume of Manaus. For 12 near-surface measurements of fresh biomass burning plumes, normalized excess mixing ratios of C2H2O2 and C3H4O2* with respect to CH2O are inferred and compared to recent studies. The mean glyoxal-to-formaldehyde ratio RGF=0.07 (range 0.02–0.11) is in good agreement with recent reports which suggest RGF to be significantly lower than previously assumed in global chemical transport models (CTMs). The mean methylglyoxal-to-formaldehyde ratio RMF=0.98 (range 0.09–1.50) varies significantly during the different observational settings but overall appears to be much larger (up to a factor of 5) than previous reports suggest even when applying a correction factor of 2.0±0.5 to account for the additional dicarbonyls included in the C3H4O2* measurements. Using recently reported emission factors of CH2O for tropical forests, our observations suggest emission factors of EFG=0.25 (range 0.11 to 0.52) g kg−1 for C2H2O2 and EFM = 4.7 (range 0.5 to 8.64) g kg−1 for C3H4O2*. While EFG agrees well with recent reports, EFM is (like RMF) slightly larger than reported in other studies, presumably due to the different plume ages or fuels studied. Our observations of these critical carbonyls and intermediate oxidation products may support future photochemical modelling of air pollution over tropical vegetation, as well as validate past and present space-borne observations of the respective species.

Lalinet Network Status

LALINET (Latin American Lidar Network) follows its goal to consolidation as a federative lidar network to provide regional coverage over Latin America in providing aerosol and greenhouse gas profiles following QA/QC protocols and promoting the development of researchers and students in atmopheric science field. We show recent results on different approaches for studying the optical properties of the atmosphere regarding aerosols at tropospheric and stratospheric level and greenhouse gas mixing ratio profiles followed by our recent support and validation efforts towards present and future satellite missions.

Satellite-retrieved vertical profiles of methane over the Indian region: impact of synoptic­scale meteorology

ABSTRACT The altitude distribution of methane (CH4) is the least addressed topic in the greenhouse gas assessment over the Indian region. In the absence of the in-situ measurements, the satellite-based retrievals of the vertical distribution of CH4 using Atmospheric Infrared Sounder (AIRS) measurements during the period 2003–2015 were made use in this study for the first time to understand the 3D distribution (latitude-longitude-altitude) of CH4 over Indian region. Significant regional and seasonal variations are observed in the vertical distribution of CH4, even though it is a long-lived greenhouse gas and known to be well-mixed. Over most of the regions, the highest mixing ratio is observed during post-monsoon months and minimum in the pre-monsoon/monsoon season. The presence of a ‘high altitude peak’ in CH4 (around 1880 ppbv) around 300 hPa–250 hPa was noted in post-monsoon which is caused by the monsoon-associated convective updrafts and the anti-cyclonic system. The vertical profiles show seasonal variations which are region as well as altitude-dependent. Over the oceanic region, the highest seasonal amplitude of CH4 mixing ratio was observed over North–Arabian Sea due to the proximity of the source rich land regions. During the winter and pre-monsoon months, the latitudinal differences are absent throughout the troposphere. A consistent increasing trend in CH4, ranging from 1 ppbv year–1 to 6 ppbv year–1 is seen at all the tropospheric altitudes, with faster growth rates at higher altitudes, maximizing at 300 hPa–150 hPa. An approximate estimate of direct forcing due to CH4 lies in the range 0.80 W m–2–0.83 W m–2. The paper also presents a comparison of the in-situ measured upper tropospheric CH4 mixing ratio from CARIBIC (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container) flight data and AIRS retrievals.

Brominated VSLS and their influence on ozone under a changing climate

Abstract. Very short-lived substances (VSLS) contribute as source gases significantly to the tropospheric and stratospheric bromine loading. At present, an estimated 25 % of stratospheric bromine is of oceanic origin. In this study, we investigate how climate change may impact the ocean–atmosphere flux of brominated VSLS, their atmospheric transport, and chemical transformations and evaluate how these changes will affect stratospheric ozone over the 21st century. Under the assumption of fixed ocean water concentrations and RCP6.0 scenario, we find an increase of the ocean–atmosphere flux of brominated VSLS of about 8–10 % by the end of the 21st century compared to present day. A decrease in the tropospheric mixing ratios of VSLS and an increase in the lower stratosphere are attributed to changes in atmospheric chemistry and transport. Our model simulations reveal that this increase is counteracted by a corresponding reduction of inorganic bromine. Therefore the total amount of bromine from VSLS in the stratosphere will not be changed by an increase in upwelling. Part of the increase of VSLS in the tropical lower stratosphere results from an increase in the corresponding tropopause height. As the depletion of stratospheric ozone due to bromine depends also on the availability of chlorine, we find the impact of bromine on stratospheric ozone at the end of the 21st century reduced compared to present day. Thus, these studies highlight the different factors influencing the role of brominated VSLS in a future climate.

A new time-independent formulation of fractional release

Abstract. The fractional release factor (FRF) gives information on the amount of a halocarbon that is released at some point into the stratosphere from its source form to the inorganic form, which can harm the ozone layer through catalytic reactions. The quantity is of major importance because it directly affects the calculation of the ozone depletion potential (ODP). In this context time-independent values are needed which, in particular, should be independent of the trends in the tropospheric mixing ratios (tropospheric trends) of the respective halogenated trace gases. For a given atmospheric situation, such FRF values would represent a molecular property.We analysed the temporal evolution of FRF from ECHAM/MESSy Atmospheric Chemistry (EMAC) model simulations for several halocarbons and nitrous oxide between 1965 and 2011 on different mean age levels and found that the widely used formulation of FRF yields highly time-dependent values. We show that this is caused by the way that the tropospheric trend is handled in the widely used calculation method of FRF.Taking into account chemical loss in the calculation of stratospheric mixing ratios reduces the time dependence in FRFs. Therefore we implemented a loss term in the formulation of the FRF and applied the parameterization of a mean arrival time to our data set.We find that the time dependence in the FRF can almost be compensated for by applying a new trend correction in the calculation of the FRF. We suggest that this new method should be used to calculate time-independent FRFs, which can then be used e.g. for the calculation of ODP.

Bayesian Optimization of the Community Land Model Simulated Biosphere–Atmosphere Exchange using CO2 Observations from a Dense Tower Network and Aircraft Campaigns over Oregon

Abstract The vast forests and natural areas of the Pacific Northwest compose one of the most productive ecosystems in the Northern Hemisphere. The heterogeneous landscape of Oregon poses a particular challenge to ecosystem models. This study presents a framework using a scaling factor Bayesian inversion to improve the modeled atmosphere–biosphere exchange of CO2. Observations from five CO/CO2 towers, eddy covariance towers, and airborne campaigns were used to constrain the Community Land Model, version 4.5 (CLM4.5), simulated terrestrial CO2 exchange at a high spatial and temporal resolution (1/24°; 3 hourly). To balance aggregation errors and the degrees of freedom in the inverse modeling system, the authors applied an unsupervised clustering approach for the spatial structuring of the model domain. Data from flight campaigns were used to quantify the uncertainty introduced by the Lagrangian particle dispersion model that was applied for the inversions. The average annual statewide net ecosystem productivity (NEP) was increased by 32% to 29.7 TgC yr−1 by assimilating the tropospheric mixing ratio data. The associated uncertainty was decreased by 28.4%–29% on average over the entire Oregon model domain with the lowest uncertainties of 11% in western Oregon. The largest differences between posterior and prior CO2 fluxes were found for the Coast Range ecoregion of Oregon that also exhibits the highest availability of atmospheric observations and associated footprints. In this area, covered by highly productive Douglas fir forest, the differences between the prior and posterior estimate of NEP averaged 3.84 TgC yr−1 during the study period from 2012 through 2014.

Retrieval of HCFC-142b (CH3CClF2) from ground-based high-resolution infrared solar spectra: Atmospheric increase since 1989 and comparison with surface and satellite measurements

We have developed an approach for retrieving HCFC-142b (CH3CClF2) from ground-based high-resolution infrared solar spectra, using its ν7 band Q branch in the 900–906cm−1 interval. Interferences by HNO3, CO2 and H2O have to be accounted for. Application of this approach to observations recorded within the framework of long-term monitoring activities carried out at the northern mid-latitude, high-altitude Jungfraujoch station in Switzerland (46.5°N, 8.0°E, 3580m above sea level) has provided a total column times series spanning the 1989 to mid-2015 time period. A fit to the HCFC-142b daily mean total column time series shows a statistically-significant long-term trend of (1.23±0.08×1013moleccm−2) per year from 2000 to 2010, at the 2-σ confidence level. This corresponds to a significant atmospheric accumulation of (0.94±0.06) ppt (1ppt=1/1012) per year for the mean tropospheric mixing ratio, at the 2−σ confidence level. Over the subsequent time period (2010–2014), we note a significant slowing down in the HCFC-142b buildup. Our ground-based FTIR (Fourier Transform Infrared) results are compared with relevant data sets derived from surface in situ measurements at the Mace Head and Jungfraujoch sites of the AGAGE (Advanced Global Atmospheric Gases Experiment) network and from occultation measurements by the ACE-FTS (Atmospheric Chemistry Experiment-Fourier Transform Spectrometer) instrument on-board the SCISAT satellite.

Impacts of updated spectroscopy on thermal infrared retrievals of methane evaluated with HIPPO data

Abstract. Errors in the spectroscopic parameters used in the forward radiative transfer model can introduce spatially, temporally, and altitude-dependent biases in trace gas retrievals. For well-mixed trace gases such as methane, where the variability of tropospheric mixing ratios is relatively small, reducing such biases is particularly important. We use aircraft observations from all five missions of the HIAPER Pole-to-Pole Observations (HIPPO) of the Carbon Cycle and Greenhouse Gases Study to evaluate the impact of updates to spectroscopic parameters for methane (CH4), water vapor (H2O), and nitrous oxide (N2O) on thermal infrared retrievals of methane from the NASA Aura Tropospheric Emission Spectrometer (TES). We find that updates to the spectroscopic parameters for CH4 result in a substantially smaller mean bias in the retrieved CH4 when compared with HIPPO observations. After an N2O-based correction, the bias in TES methane upper tropospheric representative values for measurements between 50° S and 50° N decreases from 56.9 to 25.7 ppbv, while the bias in the lower tropospheric representative value increases only slightly (from 27.3 to 28.4 ppbv). For retrievals with less than 1.6 degrees of freedom for signal (DOFS), the bias is reduced from 26.8 to 4.8 ppbv. We also find that updates to the spectroscopic parameters for N2O reduce the errors in the retrieved N2O profile.

Impact of the Asian monsoon anticyclone on the variability of mid-to-upper tropospheric methane above the Mediterranean Basin

Abstract. The space and time variabilities of methane (CH4) total column and upper tropospheric mixing ratios are analysed above the Mediterranean Basin (MB) as part of the Chemical and Aerosol Mediterranean Experiment (ChArMEx) programme. Since the analysis of the mid-to-upper tropospheric CH4 distribution from spaceborne sensors and model outputs is challenging, we have adopted a climatological approach and have used a wide variety of data sets. We have combined spaceborne measurements from the Thermal And Near infrared Sensor for carbon Observations – Fourier Transform Spectrometer (TANSO-FTS) instrument on the Greenhouse gases Observing SATellite (GOSAT) satellite, the Atmospheric InfraRed Spectrometer (AIRS) on the AURA platform and the Infrared Atmospheric Sounder Interferometer (IASI) instrument aboard the MetOp-A platform with model results from the Chemical Transport Model (CTM) MOCAGE, and the Chemical Climate Models (CCMs) CNRM-AOCCM and LMDz-OR-INCA (according to different emission scenarios). In order to minimize systematic errors in the spaceborne measurements, we have only considered maritime pixels over the MB. The period of interest spans from 2008 to 2011 considering satellite and MOCAGE data and, regarding the CCMs, from 2001 to 2010. Although CH4 is a long-lived tracer with lifetime of ~12 years and is supposed to be well mixed in the troposphere, an east–west gradient in CH4 is observed and modelled in the mid-to-upper troposphere with a maximum in the Western MB in all seasons except in summer when CH4 accumulates above the Eastern MB. The peak-to-peak amplitude of the east–west seasonal variation in CH4 above the MB in the upper troposphere (300 hPa) is weak but almost twice as great in the satellite measurements (~25 ppbv) as in the model data (~15 ppbv). The maximum of CH4 in summer above the eastern MB can be explained by a series of dynamical processes only occurring in summer. The Asian monsoon traps and uplifts high amounts of CH4 to the upper troposphere where they build up. The Asian Monsoon Anticyclone redistributes these elevated CH4 amounts towards North Africa and the Middle East to finally reach and descend in the eastern MB. In the lower troposphere, the CH4 variability is mainly driven by the local sources of emission in the vicinity of the MB.

Very short-lived bromomethanes measured by the CARIBIC observatory over the North Atlantic, Africa and Southeast Asia during 2009–2013

Abstract. Short-lived organic brominated compounds make up a significant part of the organic bromine budget in the atmosphere. Emissions of these compounds are highly variable and there are limited measurements, particularly in the extra-tropical upper troposphere/lower stratosphere and tropical troposphere. Measurements of five very short-lived bromomethanes (VSLB) were made in air samples collected on the CARIBIC project aircraft over three flight routes; Germany to Venezuela/Columbia during 2009–2011, Germany to South Africa during 2010 and 2011 and Germany to Thailand/Kuala Lumpur, Malaysia during 2012 and 2013. In the tropical troposphere, as the most important entrance region to the stratosphere, we observe a total mean organic bromine derived from these compounds across all flights at 10–12 km altitude of 3.4 ± 1.5 ppt. Individual mean tropical tropospheric mixing ratios across all flights were 0.43, 0.74, 0.14, 0.23 and 0.11 ppt for CHBr3, CH2Br2, CHBr2Cl, CHBrCl2 and CH2BrCl respectively. The highest levels of VSLB-derived bromine (4.20 ± 0.56 ppt) were observed in flights between Bangkok and Kuala Lumpur indicating that the South China Sea is an important source region for these compounds. Across all routes, CHBr3 and CH2Br2 accounted for 34% (4.7–71) and 48% (14–73) respectively of total bromine derived from the analysed VSLB in the tropical mid-upper troposphere totalling 82% (54–89). In samples collected between Germany and Venezuela/Columbia, we find decreasing mean mixing ratios with increasing potential temperature in the extra-tropics. Tropical mean mixing ratios are higher than extra-tropical values between 340–350 K indicating that rapid uplift is important in determining mixing ratios in the lower tropical tropopause layer in the West Atlantic tropics. O3 was used as a tracer for stratospherically influenced air and we detect rapidly decreasing mixing ratios for all VSLB above ∼100 ppb O3 corresponding to the extra-tropical tropopause layer.

Differences in the variability of measured and simulated tropospheric ozone mixing ratios over the Paso del Norte Region

The objective of this study is to present differences in the variability of observed and ozone-mixing ratios simulated by a three-dimensional atmospheric chemical model using two chemical mechanisms. In this study the Comprehensive Air Quality Model with Extensions is used to make ozone simulations with the Carbon Bond mechanism, versions 4 and 5. The Paso del Norte region is used as a test-bed for these simulations. The shared variance between the simulations and measurements is typical for air quality models ranging from 0.51 to 0.86 for both mechanisms. The smallest mean normalized gross error is about 31 % with CB4 but the normalized bias is over 30 % as well. Boundary conditions, emissions and other factors affect the levels of ozone of the simulated mixing ratios and therefore error and bias but these factors have a much less affect on the simulated ozone variability. The differences in the ozone variability of the measurements and the simulations are very large and different for the two chemical mechanisms. There are many more instances of low ozone mixing ratios in the measurements than in the simulated ozone. One possible explanation is that these differences are due to problems associated with comparing point measurements with grid averages. A more disturbing possibility is that the bias could be due to the procedures used in the development and testing of air quality modeling systems. Air quality mechanisms are evaluated against environmental chamber data where the chemistry occurs at high concentrations and this may lead to a systematic positive bias in ozone simulations.

Distribution of methane in the tropical upper troposphere measured by CARIBIC and CONTRAIL aircraft

We investigate the upper tropospheric distribution of methane (CH4) at low latitudes based on the analysis of air samples collected from aboard passenger aircraft. The distribution of CH4 exhibits spatial and seasonal differences, such as the pronounced seasonal cycles over tropical Asia and elevated mixing ratios over central Africa. Over Africa, the correlations of methane, ethane, and acetylene with carbon monoxide indicate that these high mixing ratios originate from biomass burning as well as from biogenic sources. Upper tropospheric mixing ratios of CH4were modeled using a chemistry transport model. The simulation captures the large‐scale features of the distributions along different flight routes, but discrepancies occur in some regions. Over Africa, where emissions are not well constrained, the model predicts a too steep interhemispheric gradient. During summer, efficient convective vertical transport and enhanced emissions give rise to a large‐scale CH4 maximum in the upper troposphere over subtropical Asia. This seasonal (monsoonal) cycle is analyzed with a tagged tracer simulation. The model confirms that in this region convection links upper tropospheric mixing ratios to regional sources on the Indian subcontinent, subtropical East Asia, and Southeast Asia. This type of aircraft data can therefore provide information about surface fluxes.

Impact of the atmospheric sink and vertical mixing on nitrous oxide fluxes estimated using inversion methods

[1] This study investigates some of the principal errors arising in atmospheric inversion estimates of N2O surface fluxes. Using a synthetic data set of model-generated atmospheric N2O mixing ratio data, representative of the current observation network, we investigate the influence of errors in the stratospheric N2O sink and in vertical transport. Our inversion framework uses a variational formulation of the Bayesian problem, and atmospheric transport is modeled using the global circulation model LMDz. When only optimizing the surface fluxes (with a prescribed sink), bias errors in the sink magnitude translate into substantial bias errors in the retrieved global total surface fluxes. Conversely, we find that errors only in the temporal and horizontal distribution of the N2O sink (nonbiased magnitude) have a very small impact on tropospheric mixing ratios and thus on the retrieved surface fluxes. Bias errors in the modeled vertical transport, however, lead to notable changes in tropospheric N2O and, in particular, in the phase of the seasonal cycle. This also leads to bias errors in the spatial distribution of the derived surface fluxes, although not in the global total. Last, the simultaneous optimization of the surface fluxes and the sink magnitude was tested as a means to avoid biasing the fluxes by incorrect prior assumptions about the N2O lifetime. With this approach, a significant reduction in the error of the sink magnitude was achieved and biases in the surface fluxes were largely avoided, and this result was further enhanced when aircraft data were included in the inversion.

Representation of tropical deep convection in atmospheric models – Part 2: Tracer transport

Abstract. The tropical transport processes of 14 different models or model versions were compared, within the framework of the SCOUT-O3 (Stratospheric-Climate Links with Emphasis on the Upper Troposphere and Lower Stratosphere) project. The tested models range from the regional to the global scale, and include numerical weather prediction (NWP), chemical transport, and chemistry-climate models. Idealised tracers were used in order to prevent the model's chemistry schemes from influencing the results substantially, so that the effects of modelled transport could be isolated. We find large differences in the vertical transport of very short-lived tracers (with a lifetime of 6 h) within the tropical troposphere. Peak convective outflow altitudes range from around 300 hPa to almost 100 hPa among the different models, and the upper tropospheric tracer mixing ratios differ by up to an order of magnitude. The timing of convective events is found to be different between the models, even among those which source their forcing data from the same NWP model (ECMWF). The differences are less pronounced for longer lived tracers, however they could have implications for modelling the halogen burden of the lowermost stratosphere through transport of species such as bromoform, or short-lived hydrocarbons into the lowermost stratosphere. The modelled tracer profiles are strongly influenced by the convective transport parameterisations, and different boundary layer mixing parameterisations also have a large impact on the modelled tracer profiles. Preferential locations for rapid transport from the surface into the upper troposphere are similar in all models, and are mostly concentrated over the western Pacific, the Maritime Continent and the Indian Ocean. In contrast, models do not indicate that upward transport is highest over western Africa.

Depletion of the Ozone Layer in the 21st Century

Today the topics “ozone layer” and “ozone hole” have been placed on the back burner in public discussions of climate change. Since the mid-1980s it has been known that primarily chlorofluorocarbons (CFCs) and also halocarbons (compounds where carbon atoms are linked to fluorine, chlorine, bromine, or iodine, but also to hydrogen) are mainly responsible for the destruction of the ozone layer in the stratosphere (atmospheric layer at an altitude of 12 to 50 km). Hence the production and usage of these substances were nearly fully prohibited in the Montreal Protocol (1987) and in subsequent agreements. As a consequence of these international treaties the strong increase of CFC concentrations in the troposphere (atmospheric layer up to an altitude of about 12 km) has halted (Figure 1). Since the mid-1990s the amount of CFCs in the troposphere has been decreasing. As a result, a reduction in the stratospheric chlorine concentration has been observed in recent years. Therefore it is expected that the ozone layer will increase in thickness and that the ozone hole over the Antarctic will disappear. Owing to the long lifetimes of CFCs in the atmosphere, it will take until about the middle of this century before the stratospheric chlorine level returns to the values measured in the 1960s. One could conclude that the ozone layer will fully recover by the middle of this century. However, the reconstruction of the ozone layer also depends on other atmospheric processes which complicate a reliable assessment of the future evolution. As a result of increased concentrations of well-mixed greenhouse gases in the atmosphere (e.g. CO2, CH4, and N2O), the troposphere warms (greenhouse effect) and the stratosphere cools (enhanced emission of long-wavelength thermal radiation). A multitude of chemical reactions in the atmosphere depend on the predominating temperature. For example, the ozone content in the middle and upper stratosphere increases with decreasing temperature since the most important ozone-destroying reactions (homogeneous gasphase reactions) slow down. In contrast, lower temperatures in the lower stratosphere over the polar regions cause stronger ozone depletion as a result of heterogeneous chemical reactions on very cold cloud particles. As a consequence of changes in the thermal structure of the atmosphere, dynamic processes in the atmosphere are changing and impacting the distribution of the trace gases that have longer lifetimes. So far, studies with numerical atmospheric models, so-called climate–chemistry models (CCMs), have not provided a consistent picture with regard to the speed of ozone recovery. Results derived from model simulations agree on the point that the regeneration of the ozone layer will develop with regional differences. Model calculations indicate that, overall, processes related to climate change will cause an accelerated recovery of the ozone layer. Most CCMs predict a return to the ozone levels observed in the 1960s clearly before the middle of this century (Figure 2). Figure 1. Hemispheric monthly mean values of tropospheric mixing ratios (in ppt=parts per trillion=10 ) of the most important CFCs (CFC-12=CF2Cl2, CFC-11=CFCl3, and CFC-113=Cl2FC-CClF2). Crosses indicate measured values for the northern hemisphere, triangles for the southern hemisphere. Recent results are shown in the insets. (Taken from Figure 1-1 in Ref. [1].) AGAGE=Advanced Global Atmospheric Gases Experiment, ESRL=Earth System Research Laboratory, UCI=University of California, Irvine.

Accurate satellite-derived estimates of the tropospheric ozone impact on the global radiation budget

Abstract. Estimates of the radiative forcing due to anthropogenically-produced tropospheric O3 are derived primarily from models. Here, we use tropospheric ozone and cloud data from several instruments in the A-train constellation of satellites as well as information from the GEOS-5 Data Assimilation System to accurately estimate the radiative effect of tropospheric O3 for January and July 2005. Since we cannot distinguish between natural and anthropogenic sources with the satellite data, our derived radiative effect reflects the unadjusted (instantaneous) effect of the total tropospheric O3 rather than the anthropogenic component. We improve upon previous estimates of tropospheric ozone mixing ratios from a residual approach using the NASA Earth Observing System (EOS) Aura Ozone Monitoring Instrument (OMI) and Microwave Limb Sounder (MLS) by incorporating cloud pressure information from OMI. We focus specifically on the magnitude and spatial structure of the cloud effect on both the short- and long-wave radiative budget. The estimates presented here can be used to evaluate the various aspects of model-generated radiative forcing. For example, our derived cloud impact is to reduce the radiative effect of tropospheric ozone by ~16%. This is centered within the published range of model-produced cloud effect on unadjusted ozone radiative forcing.

Sulfuryl fluoride in the global atmosphere

The first calibrated high‐frequency, high‐precision, in situ atmospheric and archived air measurements of the fumigant sulfuryl fluoride (SO2F2) have been made as part of the Advanced Global Atmospheric Gas Experiment (AGAGE) program. The global tropospheric background concentration of SO2F2 has increased by 5 ± 1% per year from ∼0.3 ppt (parts per trillion, dry air mol fraction) in 1978 to ∼1.35 ppt in May 2007 in the Southern Hemisphere, and from ∼1.08 ppt in 1999 to ∼1.53 ppt in May 2007 in the Northern Hemisphere. The SO2F2 interhemispheric concentration ratio was 1.13 ± 0.02 from 1999 to 2007. Two‐dimensional 12‐box model inversions yield global total and global oceanic uptake atmospheric lifetimes of 36 ± 11 and 40 ± 13 years, respectively, with hydrolysis in the ocean being the dominant sink, in good agreement with 35 ± 14 years from a simple oceanic uptake calculation using transfer velocity and solubility. Modeled SO2F2 emissions rose from ∼0.6 Gg/a in 1978 to ∼1.9 Gg/a in 2007, but estimated industrial production exceeds these modeled emissions by an average of ∼50%. This discrepancy cannot be explained with a hypothetical land sink in the model, suggesting that only ∼2/3 of the manufactured SO2F2 is actually emitted into the atmosphere and that ∼1/3 may be destroyed during fumigation. With mean SO2F2 tropospheric mixing ratios of ∼1.4 ppt, its radiative forcing is small and it is probably an insignificant sulfur source to the stratosphere. However, with a high global warming potential similar to CFC‐11, and likely increases in its future use, continued atmospheric monitoring of SO2F2 is warranted.