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Results obtained in the course of unique observations (as part of the TROICA project) of the composition and state of the atmosphere over Russia have been summarized. Scientists and engineers from different countries took part in these observations. The main task of these observations was to measure atmospheric contents of trace gases and aerosols and both meteorological and radiative characteristics of the atmosphere using a mobile laboratory designed and brought into operation specially for transcontinental observations along the network of Russian electrified railroads. A large database obtained in the TROICA experiments using the mobile laboratory, in field experiments, and at scientific stations is still under analysis. In this work, the most important results published earlier and obtained recently are discussed, which makes it possible to form a comprehensive picture of the spatial distribution and temporal variability of the atmospheric composition over northern Eurasia.

An application of radiocarbon (14C) in atmospheric chemistry is reviewed. 14C produced by cosmic neutrons immediately forms 14CO, which reacts with hydroxyl radicals (OH) to 14CO2. By this the distribution and seasonality (the lifetime of 14CO is ∼1 month) of the pivotal atmospheric oxidant OH can be established. 14CO measurement is a complex but unique application which benefitted enormously from the realization of AMS, bearing in mind that 14CO abundance is of the order of merely 10 molecules per cm3 not only provides 14CO an independent measure for the OH based self-cleansing capacity of the troposphere, but also enabled detection of 14C production due to high energy solar protons in 1989. Although its production takes place throughout the atmosphere and does not have the character of a point source, transport processes in the atmosphere affect the distribution of 14CO. Vertical mixing in the troposphere renders gradients in its production rate less critical, but considerable meridional gradients exist. One question has remained open, namely confirmation of calculated 14C production by direct measurement. A new sampling method is proposed. The conclusions are a guide to future work on 14CO in relation to OH and atmospheric transport.

A gas detection system has been developed, characterized, and deployed for pressurized gas-phase sample analyses and near-real-time online measurements. It consists of a cryogenic pre-concentrator (CryoTrap), a gas chromatograph (GC), and a new high-resolution atomic emission detector (AED III HR). Here the CryoTrap–GC–AED instrumental setup is presented, and the performance for iodine (1635 ± 135 counts I atom−1 pptv−1), sulfur (409 ± 57 counts S atom−1 pptv−1), carbon (636 ± 69 counts C atom−1 pptv−1), bromine (9.1 ± 1.8 counts Br atom−1 pptv−1), and nitrogen (28 ± 2 counts N atom−1 pptv−1) emission lines is reported and discussed. The limits of detection (LODs) are in the low parts per trillion by volume range (0.5–9.7 pptv), and the signal is linear to at least 4 orders of magnitude, which makes it a suitable method for diverse volatile organic compound (VOC) measurements in the atmosphere, even in remote unpolluted regions. The new system was utilized in a field study in a boreal forest at Hyytiälä, Finland, in late summer 2016, which made monoterpene measurements possible among other VOCs. Furthermore, pressurized global whole-air samples, collected on board the Lufthansa Airbus A340-600 IAGOS–CARIBIC aircraft in the upper troposphere and lower stratosphere region, were measured with the new setup, providing data for many VOCs, including the long-lived organosulfur compound carbonyl sulfide.

A gas detection system has been developed, characterized and deployed for pressurized gas phase sample analyses and near real-time online measurements. It consists of a cryogenic pre-concentrator (CryoTrap), a gas chromatograph (GC), and a new high-resolution atomic emission detector (AED III). Here the CryoTrap–GC–AED instrumental setup is presented and the performance for iodine (1635 ± 135 counts I-atom-1 pptv-1), sulfur (409 ± 57 counts S-atom-1 pptv-1), carbon (636 ± 69 counts C-atom-1 pptv-1), bromine (9.1 ± 1.8 counts Br-atom-1 pptv-1) and nitrogen (28 ± 2 counts N-atom-1 pptv-1) emission lines is reported and discussed. The limits of detection (LODs) are in the low pptv range (0.5–9.7 pptv) and the signal is linear to at least 4 orders of magnitude, which makes it a suitable method for diverse volatile organic compound (VOC) measurements in the atmosphere, even in remote, unpolluted regions. The new system was utilized in a field study in a boreal forest at Hyytiälä, Finland in late summer 2016 which made monoterpene measurements possible among the other VOCs. Furthermore, pressurized global whole-air sample measurement collected onboard the Lufthansa Airbus A340-600 IAGOS-CARIBIC aircraft in the upper troposphere and lower stratosphere region was carried out with the new setup, providing the observational data of many VOCs, including the long-lived organosulfur compound carbonyl sulfide.

We present new observations of trace gases in the stratosphere based on a cost-effective sampling technique that can access much higher altitudes than aircraft. The further development of this method now provides detection of species with abundances in the parts per trillion (ppt) range and below. We obtain mixing ratios for six gases (CFC-11, CFC-12, HCFC-22, H-1211, H-1301, and SF6), all of which are important for understanding stratospheric ozone depletion and circulation. After demonstrating the quality of the data through comparisons with ground-based records and aircraft-based observations we combine them with the latter to demonstrate its potential. We first compare it with results from a global model driven by three widely used meteorological reanalyses. Secondly, we focus on CFC-11 as recent evidence has indicated renewed atmospheric emissions of that species relevant on a global scale. Because the stratosphere represents the main sink region for CFC-11, potential changes in stratospheric circulation and troposphere-stratosphere exchange fluxes have been identified as the largest source of uncertainty for the accurate quantification of such emissions. Our observations span over a decade (up until 2018) and therefore cover the period of the slowdown of CFC-11 global mixing ratio decreases measured at the Earth's surface. The spatial and temporal coverage of the observations is insufficient for a global quantitative analysis, but we do find some trends that are in contrast with expectations; indicating that the stratosphere may have contributed to the slower concentration decline in recent years. Further investigating the reanalysis-driven model data we find that the required dynamical changes in the stratosphere required to explain the apparent change in tropospheric CFC-11 emissions after 2013 are possible, but with a very high uncertainty range. This is partly caused by the high variability of mass flux from the stratosphere to the troposphere, especially at time scales of a few years, and partly by large differences between runs driven by different reanalysis products, none of which agree with our observations well enough for such a quantitative analysis.

Methane (CH4) is an important greenhouse gas, and its atmospheric budget is determined by interacting sources and sinks in a dynamic global environment. Methane observations indicate that after almost a decade of stagnation, from 2006, a sudden and continuing global mixing ratio increase took place. We applied a general circulation model to simulate the global atmospheric budget, variability, and trends of methane for the period 1997–2016. Using interannually constant CH4 a priori emissions from 11 biogenic and fossil source categories, the model results are compared with observations from 17 Advanced Global Atmospheric Gases Experiment (AGAGE) and National Oceanic and Atmospheric Administration (NOAA) surface stations and intercontinental Civil Aircraft for the Regular observation of the atmosphere Based on an Instrumented Container (CARIBIC) flights, with > 4800 CH4 samples, gathered on > 320 flights in the upper troposphere and lowermost stratosphere. Based on a simple optimization procedure, methane emission categories have been scaled to reduce discrepancies with the observational data for the period 1997–2006. With this approach, the all-station mean dry air mole fraction of 1780 nmol mol−1 could be improved from an a priori root mean square deviation (RMSD) of 1.31 % to just 0.61 %, associated with a coefficient of determination (R2) of 0.79. The simulated a priori interhemispheric difference of 143.12 nmol mol−1 was improved to 131.28 nmol mol−1, which matched the observations quite well (130.82 nmol mol−1). Analogously, aircraft measurements were reproduced well, with a global RMSD of 1.1 % for the measurements before 2007, with even better results on a regional level (e.g., over India, with an RMSD of 0.98 % and R2=0.65). With regard to emission optimization, this implied a 30.2 Tg CH4 yr−1 reduction in predominantly fossil-fuel-related emissions and a 28.7 Tg CH4 yr−1 increase of biogenic sources. With the same methodology, the CH4 growth that started in 2007 and continued almost linearly through 2013 was investigated, exploring the contributions by four potential causes, namely biogenic emissions from tropical wetlands, from agriculture including ruminant animals, and from rice cultivation, and anthropogenic emissions (fossil fuel sources, e.g., shale gas fracking) in North America. The optimization procedure adopted in this work showed that an increase in emissions from shale gas (7.67 Tg yr−1), rice cultivation (7.15 Tg yr−1), and tropical wetlands (0.58 Tg yr−1) for the period 2006–2013 leads to an optimal agreement (i.e., lowest RMSD) between model results and observations.

The hydroxyl (OH) radical is the key oxidant in the global atmosphere as it controls the concentrations of toxic gases like carbon monoxide and climate relevant gases like methane. In some regions, oxidation by chlorine (Cl) radical is also important, and in the stratosphere both OH and Cl radicals impact ozone. An empirical method is presented to determine effective OH concentrations in the troposphere and lower stratosphere, based on CH4, CH3Cl, and SF6 data from aircraft measurements (IAGOS-CARIBIC) and a ground-based station (NOAA). Tropospheric OH average values of 10.9 × 105 (σ = 9.6 × 105) molecules cm−3 and stratospheric OH average values of 1.1 × 105 (σ = 0.8 × 105) molecules cm−3 were derived over mean ages derived from SF6. Using CH4 led to higher OH estimates due to the temperature dependence of the CH4 + OH reaction in the troposphere and due to the presence of Cl in the stratosphere. Exploiting the difference in effective OH calculated from CH3Cl and CH4 we determine the main altitude for tropospheric CH4 oxidation to be 4.5 ~ 10.5 km and the average Cl radical concentration in the lower stratosphere to be 1.1 × 104 (σ = 0.6 × 104) molecules cm−3 (with a 35% measurement uncertainty). Furthermore, the data are used to examine the temporal trend in annual average stratospheric OH and Cl radical concentrations between 2010 and 2015. The year 2013 showed highest stratospheric OH and lowest Cl but no clear temporal trend was observed in the data in this period. These data serve as a baseline for future studies of stratospheric circulation changes. A method to ascertain the effective concentration of OH in certain regions of the atmosphere by measuring ‘‘proxy’’ species has been developed. Knowing how much of the radical OH is present in the atmosphere is important because of its role in breaking down polluting gases such as CO, NOx and volatile organic compounds. Now, a team led by Jonathan Williams at the Max Planck Institute for Chemistry, in Mainz, Germany, has shown how long-term aircraft and ground-based measurements of CH4, CH3Cl and SF6 can be used to determine the effective concentration of OH in the troposphere and the stratosphere. The method is used to estimate the OH concentration over the time period 2008–2015 and—as long as the same ‘‘proxy’’ gases are measured—will allow the impact of future atmospheric events to be assessed.

In a changing climate, potential stratospheric circulation changes require long-term monitoring. Stratospheric trace gas measurements are often used as a proxy for stratospheric circulation changes via the mean age of air values derived from them. In this study, we investigated five potential age of air tracers – the perfluorocarbons CF4, C2F6 and C3F8 and the hydrofluorocarbons CHF3 (HFC-23) and HFC-125 – and compare them to the traditional tracer SF6 and a (relatively) shorter-lived species, HFC-227ea. A detailed uncertainty analysis was performed on mean ages derived from these new tracers to allow us to confidently compare their efficacy as age tracers to the existing tracer, SF6. Our results showed that uncertainties associated with the mean age derived from these new age tracers are similar to those derived from SF6, suggesting that these alternative compounds are suitable in this respect for use as age tracers. Independent verification of the suitability of these age tracers is provided by a comparison between samples analysed at the University of East Anglia and the Scripps Institution of Oceanography. All five tracers give younger mean ages than SF6, a discrepancy that increases with increasing mean age. Our findings qualitatively support recent work that suggests that the stratospheric lifetime of SF6 is significantly less than the previous estimate of 3200 years. The impact of these younger mean ages on three policy-relevant parameters – stratospheric lifetimes, fractional release factors (FRFs) and ozone depletion potentials – is investigated in combination with a recently improved methodology to calculate FRFs. Updates to previous estimations for these parameters are provided.

We report results from a worldwide interlaboratory comparison of samples among laboratories that measure (or measured) stable carbon and hydrogen isotope ratios of atmospheric CH4 (δ13C-CH4 and δD-CH4). The offsets among the laboratories are larger than the measurement reproducibility of individual laboratories. To disentangle plausible measurement offsets, we evaluated and critically assessed a large number of intercomparison results, some of which have been documented previously in the literature. The results indicate significant offsets of δ13C-CH4 and δD-CH4 measurements among data sets reported from different laboratories; the differences among laboratories at modern atmospheric CH4 level spread over ranges of 0.5 ‰ for δ13C-CH4 and 13 ‰ for δD-CH4. The intercomparison results summarized in this study may be of help in future attempts to harmonize δ13C-CH4 and δD-CH4 data sets from different laboratories in order to jointly incorporate them into modelling studies. However, establishing a merged data set, which includes δ13C-CH4 and δD-CH4 data from multiple laboratories with desirable compatibility, is still challenging due to differences among laboratories in instrument settings, correction methods, traceability to reference materials and long-term data management. Further efforts are needed to identify causes of the interlaboratory measurement offsets and to decrease those to move towards the best use of available δ13C-CH4 and δD-CH4 data sets.

Measurements of halogenated hydrocarbons in ambient air frequently rely on canister sampling followed by offline laboratory analysis. This allows for a large number of compounds to be analysed under stable conditions, maximising measurement precision. However, individual compounds might be affected during sampling and storage of canister samples. In order to assess halocarbon stability in whole air samples from the upper troposphere and lowermost stratosphere, we performed stability tests using the air sampling unit High REsolution Sampler (HIRES) which is part of the CARIBIC (Civil Aircraft for the Regular Investigation of the Atmosphere Based on an Instrument Container) instrument package. HIRES holds 88 light-weight stainless steel cylinders that are pressurized in flight to 4.5 bar using metal bellows pumps. The HIRES sampling unit was first deployed in 2010, but has up to now not been used for regular halocarbon analysis with exception of chloromethane. The sample collection unit was tested for sampling and storage effects of 28 halogenated compounds. The focus was on compound stability in the stainless steel canisters during storage of up to five weeks and on the influence of ozone, since flights take place in the upper troposphere and lowermost stratosphere with ozone mixing ratios of up to several hundred ppbV. Most of the investigated (hydro)chlorofluorocarbons and long-lived hydrofluorocarbons were found to be stable over a storage time of up to five weeks and were unaltered by ozone being present during pressurization. Some compounds such as for example dichloromethane, trichloromethane and tetrachloroethene started to decrease in the canisters after a storage time of more than two weeks or exhibited lowered mixing ratios in samples pressurized with ozone present. Few compounds such as for example tetrachloromethane and tribromomethane were found to be not stable in the HIRES stainless-steel canisters independent of ozone levels. Also growth was observed during storage for some species, namely for HFC-152a, HFC-23, and Halon-1301.

The particle number size distribution is an important parameter to characterize the atmospheric aerosol and its influence on the Earth's climate. Here we describe a new Optical Particle Size Spectrometer (OPSS) for measurements of the accumulation mode particle number size distribution in the tropopause region onboard a passenger aircraft (IAGOS-CARIBIC observatory (In-service Aircraft for a Global Observing System – Civil Aircraft for Regular Investigation of the Atmosphere Based on an Instrument Container)). A modified "KS93 particle sensor" from RION Co., Ltd. together with a new airflow system and a dedicated data acquisition system are the key components of the CARIBIC OPSS. The instrument records individual particle pulses in the particle size range 130–1110 nm diameter (for a particle refractive index of 1.47-i0.006 for an upper tropospheric (UT) aerosol particle) and thus allows the post-flight choice of the time resolution and the size distribution bin width. The CARIBIC OPSS has a 50 % particle detection diameter of 152 nm and a maximum asymptotic counting efficiency of 98 %. The instruments measurement performance shows no pressure dependency and no coincidence for free tropospheric conditions. The size response function of the CARIBIC OPSS was obtained by a polystyrene latex calibration in combination with model calculations. Particle number size distributions measured with the new OPSS in the lowermost stratosphere agreed within a factor of two in concentration with balloon-borne measurements over western North America. Since June 2010 the CARIBIC OPSS is deployed once per month in the IAGOS-CARIBIC observatory.

Nitrogen oxide (NO and NOy) measurements were performed onboard an in-service aircraft within the framework of CARIBIC (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container). A total of 330 flights were completed from May 2005 through April 2013 between Frankfurt/Germany and destination airports in Canada, the USA, Brazil, Venezuela, Chile, Argentina, Colombia, South Africa, China, South Korea, Japan, India, Thailand, and the Philippines. Different regions show differing NO and NOy mixing ratios. In the mid-latitudes, observed NOy and NO generally shows clear seasonal cycles in the upper troposphere with a maximum in summer and a minimum in winter. Mean NOy mixing ratios vary between 1.36 nmol/mol in summer and 0.27 nmol/mol in winter. Mean NO mixing ratios range between 0.05 nmol/mol and 0.22 nmol/mol. Regions south of 40°N show no consistent seasonal dependence. Based on CO observations, low, median and high CO air masses were defined. According to this classification, more data was obtained in high CO air masses in the regions south of 40°N compared to the midlatitudes. This indicates that boundary layer emissions are more important in these regions. In general, NOy mixing ratios are highest when measured in high CO air masses. This dataset is one of the most comprehensive NO and NOy dataset available today for the upper troposphere and is therefore highly suitable for the validation of atmosphere-chemistry-models.

Significance Unique information about the abundance and evolution of wildfire-emitted black carbon (BC) in the lowermost part of the stratosphere (LMS) was obtained from long-term airborne measurements made in cooperation with Lufthansa through the Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container (CARIBIC) project, part of the In-service Aircraft for a Global Observing System (IAGOS) framework. Our results demonstrate that wildfires can dramatically increase BC mass concentration in the LMS, substantially enhance regional climate forcing, and are a challenge for model simulations. Climate change is expected to increase the frequency and spread of wildfires. Thus, recording a present-day baseline with extensive and long-term measurements should help to constrain model estimations of the climate impact of BC and foster our fundamental understanding of future climate change., Wildfires inject large amounts of black carbon (BC) particles into the atmosphere, which can reach the lowermost stratosphere (LMS) and cause strong radiative forcing. During a 14-month period of observations on board a passenger aircraft flying between Europe and North America, we found frequent and widespread biomass burning (BB) plumes, influencing 16 of 160 flight hours in the LMS. The average BC mass concentrations in these plumes (∼140 ng·m−3, standard temperature and pressure) were over 20 times higher than the background concentration (∼6 ng·m−3) with more than 100-fold enhanced peak values (up to ∼720 ng·m−3). In the LMS, nearly all BC particles were covered with a thick coating. The average mass equivalent diameter of the BC particle cores was ∼120 nm with a mean coating thickness of ∼150 nm in the BB plume and ∼90 nm with a coating of ∼125 nm in the background. In a BB plume that was encountered twice, we also found a high diameter growth rate of ∼1 nm·h−1 due to the BC particle coatings. The observed high concentrations and thick coatings of BC particles demonstrate that wildfires can induce strong local heating in the LMS and may have a significant influence on the regional radiative forcing of climate.

Three types of reference simulations, as recommended by the Chemistry–Climate Model Initiative (CCMI), have been performed with version 2.51 of the European Centre for Medium-Range Weather Forecasts – Hamburg (ECHAM)/Modular Earth Submodel System (MESSy) Atmospheric Chemistry (EMAC) model: hindcast simulations (1950–2011), hindcast simulations with specified dynamics (1979–2013), i.e. nudged towards ERA-Interim reanalysis data, and combined hindcast and projection simulations (1950–2100). The manuscript summarizes the updates of the model system and details the different model set-ups used, including the on-line calculated diagnostics. Simulations have been performed with two different nudging set-ups, with and without interactive tropospheric aerosol, and with and without a coupled ocean model. Two different vertical resolutions have been applied. The on-line calculated sources and sinks of reactive species are quantified and a first evaluation of the simulation results from a global perspective is provided as a quality check of the data. The focus is on the intercomparison of the different model set-ups. The simulation data will become publicly available via CCMI and the Climate and Environmental Retrieval and Archive (CERA) database of the German Climate Computing Centre (DKRZ). This manuscript is intended to serve as an extensive reference for further analyses of the Earth System Chemistry integrated Modelling (ESCiMo) simulations.

The global budget and trends of atmospheric methane (CH4) have been simulated with the EMAC atmospheric chemistry – general circulation model for the period 1997 through 2014. Observations from AGAGE and NOAA surface stations and intercontinental CARIBIC flights indicate a transient period of declining methane increase during 1997 through 1999, followed by seven years of stagnation and a sudden resumed increase after 2006. Starting the simulation with a global methane distribution, scaled to match the station measurements in January 1997 and using inter-annually constant CH4 sources from eleven categories together with photochemical and soil sinks, the model reproduces the observations during the transient and constant period from 1997 through 2006 in magnitude as well as seasonal and synoptic variability. The atmospheric CH4 calculations in our model setup are linearly dependent on the source strengths, allowing source segregated simulation of eleven biogenic and fossil emission categories (tagging), with the aim to analyze global observations and derive the source specific CH4 steady state lifetimes. Moreover, tagging enables a-posteriori rescaling of individual emissions with proportional effects on the corresponding inventories and offers a method to approximate the station measurements in terms of lowest RMS. Enhancing the a priori biogenic tropical wetland emissions by ~ 29 Tg/y, compensated by a reduction of anthropogenic fossil CH4 emissions, the all-station mean dry air mole fraction of 1792 nmol/mol could be simulated within a RMS of 0.37 %. The coefficient of determination R2 = 0.87 indicates good agreement with observed variability and the calculated 2000–2005 average interhemispheric methane difference between selected NH and SH stations of 119 nmol/mol matches the observations. The CH4 samples from 95 intercontinental CARIBIC flights for the period 1997–2006 are also accurately simulated by the model, with a 2000–2006 average CH4 mixing ratio of 1786 nmol/mol, and 65 % of the measured variability being captured. This includes tropospheric and stratospheric data. To explain the growth of CH4 from 2007 through 2013 in term of sources, an emission increase of 28.3 Tg/y CH4 is needed. We explore the contributions of two potential causes, one representing natural emissions from wetlands in the tropics and the other anthropogenic shale gas production emissions in North America. A 62.6 % tropical wetland contribution and of 37.4 % by shale gas emissions optimally fit the trend, and simulates CH4 from 2007–2013 with an RMS of 7.1 nmol/mol (0.39 %). The coefficient of determination of R2 = 0.91 indicates even higher significance than before 2006. The 4287 samples collected during 232 CARIBIC flights after 2007 are simulated with an RMS of 1.3 % and R2 = 0.8, indicating that the model reproduces the seasonal and synoptic variability of CH4 in the upper troposphere and lower stratosphere.

A DOAS (Differential Optical Absorption Spectroscopy) instrument was implemented and operated onboard a long-distance passenger aircraft within the framework of the CARIBIC project (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container). The instrument was designed to keep weight, size and power consumption low and to comply with civil aviation regulations. It records spectra of scattered light from three viewing directions (nadir, 10° above and below horizon) using a miniaturized telescope system. The telescopes are integrated in the main pylon of the inlet system which is mounted at the belly of the aircraft. Fibre bundles transmit light from the telescopes to spectrograph-detector units inside the DOAS container instrument. The latter is part of the removable CARIBIC instrument container, which is installed monthly on the aircraft for a series of measurement flights. During 30 flight operations within three years, measurements of HCHO, HONO, NO2, BrO, O3 and the oxygen dimer O4 were conducted. All of these trace gases except BrO could be analysed with a 30 s time resolution. HONO was detected for the first time in a deep convective cloud over central Asia, while BrO, NO2 and O3 could be observed in tropopause fold regions. Biomass burning signatures over South America could be seen and measurements during ascent and descent provided information on boundary layer trace gas profiles (e.g. NO2 or HCHO).

Inter-comparison of results from two kinds of aerosol systems in the CARIBIC (Civil Aircraft for the Regular Investigation of the atmosphere Based on a Instrument Container) passenger aircraft based observatory, operating during intercontinental flights at 9–12 km altitude, is presented. Aerosol from the lowermost stratosphere (LMS), the extra-tropical upper troposphere (UT) and the tropical mid troposphere (MT) were investigated. Aerosol particle volume concentration measured with an optical particle counter (OPC) is compared with analytical results of the sum of masses of all major and several minor constituents from aerosol samples collected with an impactor. Analyses were undertaken with the following accelerator-based methods: particle-induced X-ray emission (PIXE) and particle elastic scattering analysis (PESA). Data from 48 flights during 1 year are used, leading to a total of 106 individual comparisons. The ratios of the particle volume from the OPC and the total mass from the analyses were in 84% within a relatively narrow interval. Data points outside this interval are connected with inlet-related effects in clouds, large variability in aerosol composition, particle size distribution effects and some cases of non-ideal sampling. Overall, the comparison of these two CARIBIC measurements based on vastly different methods show good agreement, implying that the chemical and size information can be combined in studies of the MT/UT/LMS aerosol.

Hydrochlorofluorocarbon HCFC-133a (CF3CH2Cl) is an anthropogenic compound whose consumption for emissive use is restricted under the Montreal Protocol. A recent study showed rapidly increasing atmospheric abundances and emissions. We report that, following this rise, the at- mospheric abundance and emissions have declined sharply in the past three years. We find a Northern Hemisphere HCFC-133a increase from 0.13 ppt (dry air mole fraction in parts-per-trillion) in 2000 to 0.50 ppt in 2012–mid-2013 followed by an abrupt reversal to 0.44 ppt by early 2015. Global emissions derived from these observations peaked at 3.1 kt in 2011, followed by a rapid decline of 0.5 kt yr−2 to 1.5 kt yr−1 in 2014. Sporadic HCFC-133a pollution events are detected in Europe from our high-resolution HCFC-133a records at three European stations, and in Asia from sam- ples collected in Taiwan. European emissions are estimated to be

With the rapid growth in population and economic development, emissions of greenhouse gases (GHGs) from the Indian subcontinent have sharply increased during recent decades. However, evaluation of regional fluxes of GHGs and characterization of their spatial and temporal variations by atmospheric inversions remain uncertain due to a sparse regional atmospheric observation network. As a result of an Indo-French collaboration, three new atmospheric stations were established in India at Hanle (HLE), Pondicherry (PON) and Port Blair (PBL), with the objective of monitoring the atmospheric concentrations of GHGs and other trace gases. Here we present the results of the measurements of CO2, CH4, N2O, SF6, CO, and H2 from regular flask sampling at these three stations over the period 2007–2011. For each species, annual means, seasonal cycles and gradients between stations were calculated and related to variations in natural GHG fluxes, anthropogenic emissions, and monsoon circulations. Covariances between species at the synoptic scale were analyzed to investigate the likely source(s) of emissions. The flask measurements of various trace gases at the three stations have the potential to constrain the inversions of fluxes over southern and northeastern India. However, this network of ground stations needs further extension to other parts of India to better constrain the GHG budgets at regional and continental scales.

The influence of downwelling stratospheric sulfurous aerosol on the UT (upper troposphere) aerosol concentrations and on cirrus clouds is investigated using CARIBIC (Civil Aircraft for Regular Investigation of the Atmosphere Based on an Instrument Container observations) (between 1999–2002 and 2005–2013) and the cirrus reflectance product from Moderate Resolution Imaging Spectroradiometer (MODIS). The initial period, 1999–2002, was volcanically quiescent after which the sulfurous aerosol in the LMS (lowermost stratosphere) (SLMS) became enhanced by several volcanic eruptions starting 2005. From 2005 to 2008 and in 2013, volcanic aerosol from several tropical eruptions increased SLMS. Due to consequent subsidence, the sulfur loading of the upper troposphere (SUT) was increased by a factor of 2.5 compared to background levels. Comparison of SLMS and SUT during the seasons March–July and August–November shows a close coupling of the UT and LMS. Finally, the relationship between SLMS and the cirrus cloud reflectance (CR) retrieved from MODIS spectrometer (on board the satellites Terra and Aqua) is studied. SLMS and CR show a strong anticorrelation, with a factor of 3.5 increase in SLMS and decrease of CR by 8 ± 2% over the period 2001–2011. We propose that the increase of SLMS due to volcanism has caused the coinciding cirrus CR decrease, which would be associated with a negative radiative forcing in the Northern Hemisphere midlatitudes.

In a changing climate, potential stratospheric circulation changes require long-term monitoring. Stratospheric trace gas measurements are often used as a proxy for stratospheric circulation changes via the mean age of air values derived from them. In this study, we investigated five potential age of air tracers – the perfluorocarbons CF4, C2F6 and C3F8 and the hydrofluorocarbons CHF3 (HFC-23) and HFC-125 – and compare them to the traditional tracer SF6 and a (relatively) shorter-lived species, HFC-227ea. A detailed uncertainty analysis was performed on mean ages derived from these new tracers to allow us to confidently compare their efficacy as age tracers to the existing tracer, SF6. Our results showed that uncertainties associated with the mean age derived from these new age tracers are similar to those derived from SF6, suggesting these alternative compounds are suitable, in this respect, for use as age tracers. Independent verification of the suitability of these age tracers is provided by a comparison between samples analysed at the University of East Anglia and the Scripps Institution of Oceanography. All five tracers give younger mean ages than SF6, a discrepancy that increases with increasing mean age. Our findings qualitatively support recent work that suggests the stratospheric lifetime of SF6 is significantly less than the previous estimate of 3200 years. The impact of these younger mean ages on three policy-relevant parameters – stratospheric lifetimes, Fractional Release Factors (FRFs), and Ozone Depletion Potentials – is investigated in combination with a recently improved methodology to calculate FRFs. Updates to previous estimations for these parameters are provided.

We report results from intercomparison exercises between laboratories that conduct measurements of stable carbon and hydrogen isotope ratios of atmospheric CH4 (δ13C-CH4 and δD-CH4). The offsets between the laboratories are larger than the measurement reproducibility of individual laboratories. To disentangle plausible offsets between worldwide laboratories, we evaluated and critically assessed a large number of intercomparison results documented previously in the literature. The results indicate significant offsets of δ13C-CH4 and δD-CH4 measurements among datasets reported from different laboratories; the data spread over ranges of 0.5 ‰ for δ13C-CH4 and 13 ‰ for δD-CH4. The intercomparison results summarized in this study may be of help when combining isotope datasets from different laboratories in future studies.

An extensive set of in situ water vapor (H2O) data obtained by the IAGOS-CARIBIC passenger aircraft at 10–12 km altitude over 8 years (2005–2013) is analyzed. A multifaceted description of the vertical distribution of H2O from the upper troposphere (UT) via the extratropical tropopause mixing layer (exTL) into the lowermost stratosphere (LMS) is given. Compared to longer-lived trace gases, H2O is highly variable in the UT and exTL. It undergoes considerable seasonal variation, with maxima in summer and in phase from the UT up to ~4 km above the tropopause. The transport and dehydration pathways of air starting at the Earth's surface and ending at 10–12 km altitude are reconstructed based upon (i) potential temperature (θ), (ii) relative humidity with respect to ice (RHi), and (iii) back trajectories as a function of altitude relative to the tropopause. RHi of an air mass was found to be primarily determined by its temperature change during recent vertical movement, i.e., cooling during ascent/expansion and warming during descent/compression. The data show, with great clarity, that H2O and RHi at 10–12 km altitude are controlled by three dominant transport/dehydration pathways: (i) the Hadley circulation, i.e., convective uplift in the tropics and poleward directed subsidence drying from the tropical tropopause layer with observed RHi down to 2%; (ii) warm conveyor belts and midlatitude convection transporting moist air into the UT with observed RHi usually above 60%; and (iii) the Brewer–Dobson shallow and deep branches with observed RHi down to 1%.

Until a decade ago, acetone was assumed to be a dominant HOx source in the dry extra-tropical upper troposphere (ex-UT). New photodissociation quantum yields of acetone and the lack of representative data from the ex-UT challenged that assumption. Regular mass spectrometric observations onboard the Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container (CARIBIC) passenger aircraft deliver the first representative distribution of acetone in the UT/LMS (UT/lowermost stratosphere). Based on diverse CARIBIC trace gas data and non-observed parameters taken from the model ECHAM5/MESSy for Atmospheric Chemistry, we quantify the HOx source in the UT/LMS from (photo)oxidation of acetone. The findings are contrasted to HOx production from ozone photolysis, overall the dominant tropospheric HOx source. It is shown that HOx production from acetone (photo)oxidation reaches up to 95% of the HOx source from ozone photolysis in autumn in the UT and on average ~61% in summer. That is, acetone is a significant source of HOx in the UT/LMS.

We present spatial and temporal variations of methyl chloride (CH3Cl) in the upper troposphere (UT) observed mainly by the Civil Aircraft for Regular Investigation of the atmosphere Based on an Instrument Container (CARIBIC) passenger aircraft for the years 2005–2011. The CH3Cl mixing ratio in the UT over Europe was higher than that observed at a European surface baseline station throughout the year, indicative of a persistent positive vertical gradient at Northern Hemisphere midlatitudes. A series of flights over Africa and South Asia show that CH3Cl mixing ratios increase toward tropical latitudes, and the observed UT CH3Cl level over these two regions and the Atlantic was higher than that measured at remote surface sites. Strong emissions of CH3Cl in the tropics combined with meridional air transport through the UT may explain such vertical and latitudinal gradients. Comparisons with carbon monoxide (CO) data indicate that noncombustion sources in the tropics dominantly contribute to forming the latitudinal gradient of CH3Cl in the UT. We also observed elevated mixing ratios of CH3Cl and CO in air influenced by biomass burning in South America and Africa, and the enhancement ratios derived for CH3Cl to CO in those regions agree with previous observations. In contrast, correlations indicate a high CH3Cl to CO ratio of 2.9 ± 0.5 ppt ppb−1 in the Asian summer monsoon anticyclone and domestic biofuel emissions in South Asia are inferred to be responsible. We estimated the CH3Cl emission in South Asia to be 134 ± 23 Gg Cl yr−1, which is higher than a previous estimate due to the higher CH3Cl to CO ratio observed in this study.

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.

Ozone-depleting substances emitted through human activities cause large-scale damage to the stratospheric ozone layer, and influence global climate. Consequently, the production of many of these substances has been phased out; prominent examples are the chlorofluorocarbons (CFCs), and their intermediate replacements, the hydrochlorofluorocarbons (HCFCs). So far, seven types of CFC and six types of HCFC have been shown to contribute to stratospheric ozone destruction. Here, we report the detection and quantification of a further three CFCs and one HCFC. We analysed the composition of unpolluted air samples collected in Tasmania between 1978 and 2012, and extracted from deep firn snow in Greenland in 2008, using gas chromatography with mass spectrometric detection. Using the firn data, we show that all four compounds started to emerge in the atmosphere in the 1960s. Two of the compounds continue to accumulate in the atmosphere. We estimate that, before 2012, emissions of all four compounds combined amounted to more than 74,000 tonnes. This is small compared with peak emissions of other CFCs in the 1980s of more than one million tonnes each year. However, the reported emissions are clearly contrary to the intentions behind the Montreal Protocol, and raise questions about the sources of these gases.

In TROICA (TRanscontinental Observations Into the Chemistry of the Atmosphere) campaigns (1999–2008), the simultaneous observations of near surface 222Rn concentrations and atmospheric boundary layer thermal structure were performed along the Trans-Siberian Railway across northern Eurasia from Moscow to Vladivostok, including central, southern and far eastern parts of Russia. The data on 222Rn and temperature vertical distribution are used to estimate 222Rn regional scale soil fluxes based on calculations of nocturnal 222Rn accumulation rates in the surface layer under inversion conditions. An effect of seasonal soil thawing on 2–4 times surface 222Rn concentration increase from summer 1999 to autumn 2005 is observed. The estimated 222Rn regional averaged fluxes vary over Russia from 29 ± 8 mBq m−2 s−1 in its so-called European territory to 95 ± 51 mBq m−2 s−1 in the southern area of Siberia. The highest 222Rn fluxes are derived in the regions of high tectonic activity and orogenic belts of central and eastern Siberia and in far eastern Russia. The observed high 222Rn flux variations in specific events show a strong effect of both soil and atmospheric conditions on 222Rn near-surface abundance and the derived seasonal patterns over the continent.

This work reassesses the global atmospheric budget of H2 with the TM5 model. The recent adjustment of the calibration scale for H2 translates into a change in the tropospheric burden. Furthermore, the ECMWF Reanalysis-Interim (ERA-Interim) data from the European Centre for Medium-Range Weather Forecasts (ECMWF) used in this study show slower vertical transport than the operational data used before. Consequently, more H2 is removed by deposition. The deposition parametrization is updated because significant deposition fluxes for snow, water, and vegetation surfaces were calculated in our previous study. Timescales of 1-2h are asserted for the transport of H2 through the canopies of densely vegetated regions. The global scale variability of H2 and [DH2] is well represented by the updated model. H2 is slightly overestimated in the Southern Hemisphere because too little H2 is removed by dry deposition to rainforests and savannahs. The variability in H2 over Europe is further investigated using a high-resolution model subdomain. It is shown that discrepancies between the model and the observations are mainly caused by the finite model resolution. The tropospheric burden is estimated at 165 +/- 8TgH2. The removal rates of H2 by deposition and photochemical oxidation are estimated at 53 +/- 4 and 23 +/- 2TgH2/yr, resulting in a tropospheric lifetime of 2.2 +/- 0.2year.

[1] Estimates of surface fluxes of carbon monoxide (CO) inferred from remote sensing observations or free tropospheric trace gas measurements using global chemical transport models can have significant uncertainties because of discrepancies in the vertical transport in the models, which make it challenging to unequivocally relate the observations back to the surface fluxes in the models. The new Measurement of Pollution in the Troposphere (MOPITT) version 5 retrievals provide greater sensitivity to lower tropospheric CO over land relative to the previous versions and are, therefore, useful for evaluating vertical transport in models. We have assimilated the new MOPITT CO retrievals, using the Goddard Earth Observing System (GEOS)-Chem model, to study the influence of vertical transport errors on inferred CO sources. We compared the source estimates obtained by assimilating the CO profiles, the column amounts, and the surface level retrievals for June–August 2006. The three different inversions produced large differences in the source estimates in regions of convection and strong CO emissions. The inversion using the CO profiles suggested an 85% increase in emissions in India/Southeast Asia, which exacerbated the model bias in the lower and middle troposphere, whereas using the surface level retrievals produced a 37% decrease in Indian/Southeast Asian emissions, which exacerbated the underestimate of CO in the upper troposphere. Globally, the inversion with the surface retrievals suggested a 22% reduction in emissions from the a priori estimate of 161 Tg CO/month (from combustion and the oxidation of biogenic volatile organic compounds), averaged in June–August 2006. The analysis results were validated with independent surface CO measurements from NOAA Global Monitoring Division (GMD) network and upper troposphere CO measurements from the Civil Aircraft for the Regular Investigation of the Atmosphere Based on an Instrumented Container (CARIBIC). We found that the inversion with the surface retrievals agreed best with surface CO data but produced the largest discrepancy with the CARIBIC aircraft data in the upper troposphere, suggesting the influence of vertical transport errors in the model. Our results show that the comparison of the a posteriori CO distributions obtained from the inversions using the surface and profile retrievals provides a means of characterizing the potential impact of the vertical transport biases on the source estimates and the CO distribution.

The El Nino-Southern Oscillation (ENSO) affects the tropospheric concentrations of many trace gases. Here we investigate the ENSO influence on mercury concentrations measured in the upper troposphere during Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrumented Container flights and at ground at Cape Point, South Africa, and Mace Head, Ireland. Mercury concentrations cross-correlate with Southern Oscillation Index (SOI) with a lag of 8 +/- 2 months. Highest mercury concentrations are always found at the most negative SOI values, i.e., 8 months after El Nino, and the amplitude of the interannual variations fluctuates between similar to 5 and 18%. The time lag is similar to that of CO whose interannual variations are driven largely by emissions from biomass burning (BB). The amplitude of the interannual variability of tropospheric mercury concentrations is consistent with the estimated variations in mercury emissions from BB. We thus conclude that BB is a major factor driving the interannual variation of tropospheric mercury concentrations.

The chlorine radical is a potent atmospheric oxidant, capable of perturbing tropospheric oxidative cycles normally controlled by the hydroxyl radical. Significantly faster reaction rates allow chlorine radicals to expedite oxidation of hydrocarbons, including methane, and in polluted environments, to enhance ozone production. Here we present evidence, from the CARIBIC airborne dataset, for extensive chlorine radical chemistry associated with Asian pollution outflow, from airborne observations made over the Malaysian Peninsula in winter. This region is known for persistent convection that regularly delivers surface air to higher altitudes and serves as a major transport pathway into the stratosphere. Oxidant ratios inferred from hydrocarbon relationships show that chlorine radicals were regionally more important than hydroxyl radicals for alkane oxidation and were also important for methane and alkene oxidation (>10%). Our observations reveal pollution-related chlorine chemistry that is both widespread and recurrent, and has implications for tropospheric oxidizing capacity, stratospheric composition and ozone chemistry.

Long term measurements in background air (Cape Grim, Tasmania) and firn air (NEEM, Greenland) of the potent long-lived greenhouse gas SF5CF3 show that emissions declined after the late 1990s, having grown since the 1950s, and became indistinguishable from zero after 2003. The timing of this decline suggests that emissions of this gas may have been related to the production of certain fluorochemicals; production of which have been recently phased out. An earlier observation of closely correlated atmospheric abundances of SF5CF3 and SF6 are shown here to have likely been purely coincidental, as their respective trends diverged after 2002. Due to its long lifetime (ca. 900 yr), atmospheric concentrations of SF5CF3 have not declined, and it is now well mixed between hemispheres, as is also shown here from interhemispheric aircraft measurements. Total cumulative emissions of SF5CF3 amount to around 5 kT.

Air samples collected at Cape Grim, Tasmania between 1978 and 2008 and during a series of more recent aircraft sampling programmes have been analysed to determine the atmospheric abundance and trend of octafluorocyclobutane (c-C4F8 or PFC-318). c-C4F8 has an atmospheric lifetime in excess of 3000 yr and a global warming potential (GWP) of 10 300 (100 yr time horizon), making it one of the most potent greenhouse gases detected in the atmosphere to date. The abundance of c-C4F8 in the Southern Hemisphere has risen from 0.35 ppt in 1978 to 1.2 ppt in 2010, and is currently increasing at a rate of around 0.03 ppt yr−1. It is the third most abundant perfluorocarbon (PFC) in the present day atmosphere, behind CF4 (~75 ppt) and C2F6 (~4 ppt). Although a number of potential sources of c-C4F8 have been reported, including the electronics and semi-conductor industries, there remains a large discrepancy in the atmospheric budget. Using a 2-D global model to derive top-down global emissions based on the Cape Grim measurements yields a recent (2007) emission rate of around 1.1 Gg yr−1 and a cumulative emission up to and including 2007 of 38.1 Gg. Emissions reported on the EDGAR emissions database for the period 1986–2005 represent less than 1% of the top-down emissions for the same period, which suggests there is a large unaccounted for source of this compound. It is also apparent that the magnitude of this source has varied considerably over the past 30 yr, declining sharply in the late 1980s before increasing again in the mid-1990s.

We present variations of methyl chloride (CH3Cl) and nitrous oxide (N2O) in the lowermost stratosphere (LMS) obtained from air samples collected by the In-service Aircraft for a Global Observing System-Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container (IAGOS-CARIBIC) passenger aircraft observatory for the period 2008-2012. To correct for the temporal increase of atmospheric N2O, the CARIBIC N2O data are expressed as deviations from the long-term trend at the northern hemispheric baseline station Mauna Loa, Hawaii (Delta N2O).Delta N2O undergoes a pronounced seasonal variation in the LMS with a minimum in spring. The amplitude increases going deeper in the LMS (up to potential temperature of 40 K above the thermal tropopause), as a result of the seasonally varying subsidence of air from the stratospheric overworld. Seasonal variation of CH3Cl above the tropopause is similar in phase to that of Delta N2O. Significant correlations are found between CH3Cl and Delta N2O in the LMS from winter to early summer, both being affected by mixing between stratospheric air and upper tropospheric air. This correlation, however, disappears in late summer to autumn. The slope of the CH3Cl-Delta N2O correlation observed in the LMS allows us to determine the stratospheric lifetime of CH3Cl to be 35 +/- 7 years. Finally, we examine the partitioning of stratospheric air and tropical/extratropical tropospheric air in the LMS based on a mass balance approach using Delta N2O and CH3Cl. This analysis clearly indicates efficient inflow of tropical tropospheric air into the LMS in summer and demonstrates the usefulness of CH3Cl as a tracer of tropical tropospheric air.