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This paper presents an analysis of the recent tropospheric molecular hydrogen (H2) budget with a particular focus on soil uptake and surface emissions. A variational inversion scheme is combined with observations from the RAMCES and EUROHYDROS atmospheric networks, which include continuous measurements performed between mid-2006 and mid-2009. Net H2 surface flux, soil uptake distinct from surface emissions and finally, soil uptake, biomass burning, anthropogenic emissions and N2 fixation-related emissions separately were inverted in several scenarios. The various inversions generate an estimate for each term of the H2 budget. The net H2 flux per region (High Northern Hemisphere, Tropics and High Southern Hemisphere) varies between −8 and 8 Tg yr−1. The best inversion in terms of fit to the observations combines updated prior surface emissions and a soil deposition velocity map that is based on soil uptake measurements. Our estimate of global H2 soil uptake is −59 ± 4.0 Tg yr−1. Forty per cent of this uptake is located in the High Northern Hemisphere and 55% is located in the Tropics. In terms of surface emissions, seasonality is mainly driven by biomass burning emissions. The inferred European anthropogenic emissions are consistent with independent H2 emissions estimated using a H2/CO mass ratio of 0.034 and CO emissions considering their respective uncertainties. To constrain a more robust partition of H2 sources and sinks would need additional constraints, such as isotopic measurements.
Active chlorine species play a dominant role in the catalytic destruction of stratospheric ozone in the polar vortices during the late winter and early spring seasons. Recently, the correct understanding of the ClO dimer cycle was challenged by the release of new laboratory absorption cross sections (Pope et al., 2007) yielding significant model underestimates of observed ClO and ozone loss (von Hobe et al., 2007). Under this aspect, Arctic stratospheric limb emission measurements carried out by the balloon version of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS-B) from Kiruna (Sweden) on 11 January 2001 and 20/21 March 2003 have been reanalyzed with regard to the chlorine reservoir species ClONO2 and the active species, ClO and ClOOCl (Cl2O2). New laboratory measurements of IR absorption cross sections of ClOOCl for various temperatures and pressures allowed for the first time the retrieval of ClOOCl mixing ratios from remote sensing measurements. High values of active chlorine (ClOx) of roughly 2.3 ppbv at 20 km were observed by MIPAS-B in the cold mid-winter Arctic vortex on 11 January 2001. While nighttime ClOOCl shows enhanced values of nearly 1.1 ppbv at 20 km, ClONO2 mixing ratios are less than 0.1 ppbv at this altitude. In contrast, high ClONO2 mixing ratios of nearly 2.4 ppbv at 20 km have been observed in the late winter Arctic vortex on 20 March 2003. No significant ClOx amounts are detectable on this date since most of the active chlorine has already recovered to its main reservoir species ClONO2. The observed values of ClOx and ClONO2 are in line with the established chlorine chemistry. The thermal equilibrium constants between the dimer formation and its dissociation, as derived from the balloon measurements, are on the lower side of reported data and in good agreement with values recommended by von Hobe et al. (2007). Calculations with the ECHAM/MESSy Atmospheric Chemistry model (EMAC) using established kinetics show similar chlorine activation and deactivation, compared to the measurements in January 2001 and March 2003, respectively.
Active chlorine species play a dominant role in the catalytic destruction of stratospheric ozone in the polar vortices during the late winter and early spring seasons. Recently, the correct understanding of the ClO dimer cycle was challenged by the release of new laboratory absorption cross sections (Pope et al., 2007) yielding significant model underestimates of observed ClO and ozone loss (von Hobe et al., 2007). Under this aspect, nocturnal Arctic stratospheric limb emission measurements carried out by the balloon version of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS-B) from Kiruna (Sweden) on 11 January 2001 and 20/21 March 2003 have been reanalyzed with regard to the chlorine reservoir species ClONO2 and the active species, ClO and ClOOCl (Cl2O2). New laboratory measurements of IR absorption cross sections of ClOOCl for various temperatures and pressures allowed for the first time the retrieval of ClOOCl mixing ratios from remote sensing measurements. High values of active chlorine (ClOx) of roughly 2.3 ppbv at 20 km were observed by MIPAS-B in the cold mid-winter Arctic vortex on 11 January 2001. While nighttime ClOOCl shows enhanced values of nearly 1.1 ppbv at 20 km, ClONO2 mixing ratios are less than 0.1 ppbv at this altitude. In contrast, high ClONO2 mixing ratios of nearly 2.4 ppbv at 20 km have been observed in the late winter Arctic vortex on 20 March 2003. No significant ClOx amounts are detectable on this date since most of the active chlorine has already recovered to its main reservoir species ClONO2. The observed values of ClOx and ClONO2 are in line with the established polar chlorine chemistry. The thermal equilibrium constants between the dimer formation and its dissociation, as derived from the balloon measurements, are on the lower side of reported data and in good agreement with values recommended by von Hobe et al. (2007). Calculations with the ECHAM/MESSy Atmospheric Chemistry model (EMAC) using established kinetics show similar chlorine activation and deactivation, compared to the measurements in January 2001 and March 2003, respectively.
AirCore samplers have been increasingly used to capture vertical profiles of trace gases reaching from the ground up to about 30 km, in order to validate remote sens- ing instruments and to investigate transport processes in the stratosphere. When deployed to a weather balloon, accu- rately attributing the trace gas measurements to the sampling altitudes is nontrivial, especially in the stratosphere. In this paper we present the CO-spiking experiment, which can be deployed to any AirCore on any platform in order to evalu- ate different computational altitude attribution processes and to experimentally derive the vertical resolution of the profile by injecting small volumes of signal gas at predefined GPS altitudes during sampling. We performed two CO-spiking flights with an AirCore from the Goethe University Frankfurt (GUF) deployed to a weather balloon in Traînou, France, in June 2019. The altitude retrieval based on an instantaneous pressure equilibrium assumption slightly overestimates the sampling altitudes, especially at the top of the profiles. For these two flights our altitude attribution is accurate within 250 m below 20 km. Above 20 km the positive bias becomes larger and reaches up to 1.2 km at 27 km altitude. Differences in descent velocities are shown to have a major impact on the altitude attribution bias. We parameterize the time lag between the theoretically attributed altitude and the actual CO-spike release altitude for both flights together and use it to empirically correct our AirCore altitude retrieval. Regard- ing the corrected profiles, the altitude attribution is accurate within ±120 m throughout the profile. Further investigations are needed in order to test for the scope of validity of this correction parameter regarding different ambient conditions and maximum flight altitudes. We derive the vertical resolu- tion from the CO spikes of both flights and compare it to the modeled vertical resolution. The modeled vertical resolution is too optimistic compared to the experimentally derived res- olution throughout the profile, albeit agreeing within 220 m. All our findings derived from the two CO-spiking flights are strictly bound to the GUF AirCore dimensions. The newly introduced CO-spiking experiment can be used to test differ- ent combinations of AirCore configurations and platforms in future studies.
Chlorine monoxide (ClO) plays a key role in stratospheric ozone loss processes at midlatitudes. We present two balloon-borne in situ measurements of ClO conducted in northern hemisphere midlatitudes during the period of the maximum of total inorganic chlorine loading in the atmosphere. Both ClO measurements were conducted on board the TRIPLE balloon payload, launched in November 1996 in León, Spain, and in May 1999 in Aire sur l'Adour, France. For both flights a ClO daylight and night-time vertical profile was derived over an altitude range of approximately 15-35 km. ClO mixing ratios are compared to model simulations performed with the photochemical box model version of the Chemical Lagrangian Model of the Stratosphere (CLaMS). Simulations along 24-hour backward trajectories were performed to study the diurnal variation of ClO in the midlatitude lower stratosphere. Model simulations for the flight launched in Aire sur l'Adour 1999 show an excellent agreement with the ClO measurements. For the flight launched in León 1996, an overall good agreement is found, whereas the flight is characterized by a more complex dynamical situation due to a possible mixture of vortex and non-vortex air. We note that for both flights at solar zenith angles greater than 86°-87° simulated ClO mixing ratios are higher than observed ClO mixing ratios. However, the present findings indicate that no substantial uncertainties exist in midlatitude chlorine chemistry of the stratosphere.
This study presents a comprehensive and critical assessment of the meteorological conditions and atmospheric flow during the Lagrangian-type "Hill Cap Cloud Thuringia 2010" experiment (HCCT-2010). HCCT-2010 was performed in September and October 2010 at Mt. Schmücke in the Thuringian forest, Germany, applying three measurements sites (upwind, in-cloud, downwind) to study physical and chemical aerosol-cloud-interactions. A Lagrangian-type hill cap cloud experiment requires suitable cloud and particularly connected airflow conditions, i.e. representative air masses at the different measurement sites. Therefore, the present study aimed at the identification of time periods during the 6-weeks duration of the campaign, where such conditions were fulfilled and which can be used in further data examinations.
The following topics were studied in detail: (i) the general synoptic weather situations including the mesoscale flow conditions by means of a classification of advected air masses and calculation of non-dimensional flow parameters (e.g. Froude number), (ii) local meteorological conditions, including synoptic front passages, the presence of orographic or frontal cloudiness, cloud base heights and vertical stratification, and (iii) local flow conditions by means of statistical analyses using the quasi-inert trace gas ozone and selected size bins of particle number size distributions as well as SF6 tracer experiments in the campaign area. A comprehensive analyses using statistical measures such as the COD (Coefficient Of Divergence) and cross-correlation have been carried out for the first time in the context of a Lagrangian-type hill cap cloud experiment. Suitable criteria for the aimed statistical analyses were thus developed and applied in the present study to characterise the local flow connectivity in detail.
The comprehensive examination resulted in a total of 14 so-called "Full Cloud Events" (FCE), which are shown to conform to the Lagrange-type experimental philosophy of HCCT-2010. In addition, 15 so-called "Non-Cloud Events" (NCEs) could be established, which can be used as reference cases as they provide similarly suitable flow conditions but no cloud at the summit site. Orographic cloudiness was identified for approx. one third of the FCE periods, while about two thirds were associated to synoptic fronts. The statistical flow analyses indicate the existence of a strong link between the sites during the events, particularly under constant south-westerly flow conditions, high wind speeds and slightly stable stratification. The COD analyses using continuously measured concentrations of ozone and the 49 nm diameter particle bin revealed particularly for COD values below 0.1 very consistent time series, i.e. closely linked air masses between the different sites. The cross-correlation analysis revealed under connected flow conditions typical overflow times of about 15 to 30 min between the two valley sites. Additionally, the performed SF6 tracer experiments during the campaign clearly demonstrate that under appropriate meteorological conditions a Lagrangian-type approach is valid and that the connected flow validation procedure developed in this work is suitable for identifying such conditions. Finally, an overall evaluation of the identified FCEs is presented, which provides the basis for subsequent investigations of the measured chemical and physical data during HCCT-2010.
We investigate the contribution of oceanic methyl iodide (CH3I) to the stratospheric iodine budget. Based on CH3I measurements from three tropical ship campaigns and the Lagrangian transport model FLEXPART, we provide a detailed analysis of CH3I transport from the ocean surface to the cold point in the upper tropical tropopause layer (TTL). While average oceanic emissions differ by less than 50% from campaign to campaign, the measurements show much stronger variations within each campaign. A positive correlation between the oceanic CH3I emissions and the efficiency of CH3I troposphere–stratosphere transport has been identified for some cruise sections. The mechanism of strong horizontal surface winds triggering large emissions on the one hand and being associated with tropical convective systems, such as developing typhoons, on the other hand, could explain the identified correlations. As a result of the simultaneous occurrence of large CH3I emissions and strong vertical uplift, localized maximum mixing ratios of 0.6 ppt CH3I at the cold point have been determined for observed peak emissions during the SHIVA (Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere)-Sonne research vessel campaign in the coastal western Pacific. The other two campaigns give considerably smaller maxima of 0.1 ppt CH3I in the open western Pacific and 0.03 ppt in the coastal eastern Atlantic. In order to assess the representativeness of the large local mixing ratios, we use climatological emission scenarios to derive global upper air estimates of CH3I abundances. The model results are compared with available upper air measurements, including data from the recent ATTREX and HIPPO2 aircraft campaigns. In the eastern Pacific region, the location of the available measurement campaigns in the upper TTL, the comparisons give a good agreement, indicating that around 0.01 to 0.02 ppt of CH3I enter the stratosphere. However, other tropical regions that are subject to stronger convective activity show larger CH3I entrainment, e.g., 0.08 ppt in the western Pacific. Overall our model results give a tropical contribution of 0.04 ppt CH3I to the stratospheric iodine budget. The strong variations in the geographical distribution of CH3I entrainment suggest that currently available upper air measurements are not representative of global estimates and further campaigns will be necessary in order to better understand the CH3I contribution to stratospheric iodine.
We investigate the contribution of oceanic methyl iodide (CH3I) to the stratospheric iodine budget. Based on CH3I measurements during three tropical ship campaigns and the Lagrangian transport model FLEXPART we provide a detailed analysis of CH3I transport from the ocean surface to the cold point in the upper tropical tropopause layer (TTL). While average oceanic emissions differ by less than 50% from campaign to campaign, the measurements show much stronger variations within each campaign. A positive correlation between the oceanic CH3I emissions and the efficiency of CH3I troposphere–stratosphere transport has been identified for some cruise sections. The mechanism of strong horizontal surface winds triggering large emissions on the one hand and being associated with tropical convective systems, such as developing typhoons, on the other hand, could explain the identified correlations. As a result of the simultaneous occurrence of large CH3I emissions and strong vertical uplift, localized maximum mixing ratios of 0.6 ppt CH3I at the cold point have been determined for observed peak emissions during the SHIVA-Sonne campaign in the coastal West Pacific. The other two campaigns give considerable smaller maxima of 0.1 ppt CH3I for the TransBrom campaign in the open West Pacific and 0.03 ppt for emissions from the coastal East Atlantic during the DRIVE campaign. In order to assess the representativeness of the large local mixing ratios we use climatological emission scenarios to derive global upper air estimates of CH3I abundances. The model results are compared to available upper air measurements including data from the recent ATTREX and HIPPO2 aircraft campaigns. In the East Pacific region, the location of the available measurement campaigns in the upper TTL, the comparisons give a good agreement indicating that around 0.01 to 0.02 ppt of CH3I enter the stratosphere. However, other tropical regions, which are subject to stronger convective activity show larger CH3I entrainment, e.g., 0.08 ppt in the West Pacific. The strong variations in the geographical distribution of CH3I entrainment suggest that currently available upper air measurements are not representative of global estimates and further campaigns will be necessary in order to better understand the CH3I contribution to stratospheric iodine.
In late 2013, a whole air flask collection programme was started at Taunus Observatory (TO) in central Germany. Being a rural site in close proximity to the Rhine–Main area, Taunus Observatory allows assessment of emissions from a densely populated region. Owing to its altitude of 825 m, the site also regularly experiences background conditions, especially when air masses approach from north-westerly directions. With a large footprint area mainly covering central Europe north of the Alps, halocarbon measurements at the site have the potential to improve the database for estimation of regional and total European halogenated greenhouse gas emissions. Flask samples are collected weekly for offline analysis using a GC/MS system simultaneously employing a quadrupole as well as a time-of-flight mass spectrometer. As background reference, additional samples are collected approximately once every 2 weeks at the Mace Head Atmospheric Research Station (MHD) when air masses approach from the site's clean air sector. Thus the time series at TO can be linked to the in situ AGAGE measurements and the NOAA flask sampling programme at MHD. An iterative baseline identification procedure separates polluted samples from baseline data. While there is good agreement of baseline mixing ratios between TO and MHD, with a larger variability of mixing ratios at the continental site, measurements at TO are regularly influenced by elevated halocarbon mixing ratios. Here, first time series are presented for CFC-11, CFC-12, HCFC-22, HFC-134a, HFC-227ea, HFC-245fa, and dichloromethane. While atmospheric mixing ratios of the chlorofluorocarbons (CFCs) decrease, they increase for the hydrochlorofluorocarbons (HCFCs) and the hydrofluorocarbons (HFCs). Small unexpected differences between CFC-11 and CFC-12 are found with regard to frequency and relative enhancement of high mixing ratio events and seasonality, although production and use of both compounds are strictly regulated by the Montreal Protocol, and therefore a similar decrease in atmospheric mixing ratios should occur. Dichloromethane, a solvent about which recently concerns have been raised regarding its growing influence on stratospheric ozone depletion, does not show a significant trend with regard to both baseline mixing ratios and the occurrence of pollution events at Taunus Observatory for the time period covered, indicating stable emissions in the regions that influence the site. An analysis of trajectories from the Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) model reveals differences in halocarbon mixing ranges depending on air mass origin.
In late 2013, a whole air flask collection program started at the Taunus Observatory (TO) in central Germany. Being a rural site in close vicinity to the densely populated Rhein-Main area, Taunus Observatory allows to assess local and regional emissions. Owed to its altitude of 825 m, the site also regularly experiences background conditions, especially when air masses approach from north-westerly directions. With a large footprint area mainly covering central Europe north of the Alps, halocarbon measurements at the site have the potential to improve the data base for estimation of regional and total European halogenated greenhouse gas emissions. Flask samples are collected weekly for offline analysis using a GC-MS system employing a quadrupole as well as a time-of-flight mass spectrometer. As background reference, additional samples are collected approximately bi-weekly at the Mace Head Atmospheric Research Station (MHD) when air masses approach from the site’s clean air sector. Thus the TO time series can be linked to the in-situ AGAGE measurements and the NOAA flask sampling program at MHD. An iterative baseline identification procedure separates polluted samples from baseline data. While there is good agreement of baseline mixing ratios between TO and MHD, with a larger variability of mixing ratios at the continental site, measurements at TO are regularly influenced by elevated halocarbon mixing ratios. Here, first time series are presented for CFC-11, CFC-12, HCFC-22, HFC-134a, HFC-227ea, HFC-245fa, and dichloromethane. While atmospheric mixing ratios of the CFCs decrease, they increase for the HCFC and the HFCs. Small unexpected differences between CFC-11 and CFC-12 are found with regard to the occurrence of high mixing ratio events and seasonality, although production and use of both compounds are strictly regulated by the Montreal Protocol, and therefore a similar decrease of atmospheric mixing ratios should occur. Dichloromethane, a solvent about which recently concerns have risen regarding its growing influence on stratospheric ozone depletion, does not show a significant trend with regard to both, baseline mixing ratios and the occurrence of pollution events at Taunus Observatory for the time period covered, indicating stable emissions in the regions that influence the site. An analysis of HYSPLIT trajectories reveals differences in halocarbon mixing ranges depending on air mass origin.
Measurements of halogenated trace gases 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, maximizing measurement precision. However, individual compounds might be affected during the 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 high-resolution sampler (HIRES) air sampling unit, which is part of the Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container (CARIBIC) instrument package. The HIRES unit holds 88 lightweight stainless-steel cylinders that are pressurized in flight to 4.5 bar using metal bellows pumps. The HIRES unit was first deployed in 2010 but has up to now not been used for regular halocarbon analysis with the exception of chloromethane analysis. The sample collection unit was tested for the sampling and storage effects of 28 halogenated compounds. The focus was on compound stability in the stainless-steel canisters during storage of up to 5 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 parts per billion by volume (ppbv). Most of the investigated (hydro)chlorofluorocarbons and long-lived hydrofluorocarbons were found to be stable over a storage time of up to 5 weeks and were unaltered by ozone being present during pressurization. Some compounds such as dichloromethane, trichloromethane, and tetrachloroethene started to decrease in the canisters after a storage time of more than 2 weeks or exhibited lowered mixing ratios in samples pressurized with ozone present. A few compounds such as tetrachloromethane and tribromomethane were found to be unstable in the HIRES stainless-steel canisters independent of ozone levels. Furthermore, growth was observed during storage for some species, namely for HFC-152a, HFC-23, and Halon 1301.
Stability of halocarbons in whole air samples from the upper
troposphere and lowermost stratosphere
(2019)
Measurements of halogenated hydrocarbons of 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 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, namely for HFC-152a and HFC-23.
During the SHIVA (Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere) project an extensive dataset of all halogen species relevant for the atmospheric budget of total organic bromine has been collected in the West Pacific region using the FALCON aircraft operated by the German Aerospace agency DLR (Deutsches Zentrum für Luft- und Raumfahrt) covering a vertical range from the planetary boundary layer up to the ceiling altitude of the aircraft of 13 km. In total, more than 700 measurements were performed with the newly developed fully-automated in-situ instrument GHOST-MS (Gas cHromatograph for the Observation of Tracers – coupled with a Mass Spectrometer) by the Goethe University of Frankfurt (GUF) and with the onboard whole-air sampler WASP with subsequent ground based state-of-the-art GC/MS analysis by the University of East Anglia (UEA). Both instruments yield good agreement for all major (CHBr3 and CH2Br2) and minor (CHBrCl, CHBrCl2 and CHBr2Cl) VSLS (very short-lived substances), at least at the level of their 2 σ measurement uncertainties. In contrast to the suggestion that the Western Pacific could be a major source region for VSLS (Pyle et al., 2011), we found only slightly enhanced mixing ratios of brominated halogen source gases relative to the levels reported in Montzka et al. (2011) for other tropical regions. A budget for total organic bromine, including all four halons,CH3Br and the VSLS, is derived for the upper troposphere, the input region for the TTL and thus also for the stratosphere, compiled from the SHIVA dataset. With exception of the two minor VSLS CHBrCl2 and CHBr2Cl, excellent agreement with the values reported in Montzka et al. (2011) is found, while being slightly higher than previous studies from our group based on balloon-borne measurements.
The isotopic composition of methane in the stratosphere : high-altitude balloon sample measurements
(2011)
The isotopic composition of stratospheric methane has been determined on a large suite of air samples from stratospheric balloon flights covering subtropical to polar latitudes and a time period of 16 yr. 154 samples were analyzed for δC and 119 samples for δD, increasing the previously published dataset for balloon borne samples by an order of magnitude, and more than doubling the total available stratospheric data (including aircraft samples) published to date. The samples also cover a large range in mixing ratio from tropospheric values near 1800 ppb down to only 250 ppb, and the strong isotope fractionation processes accordingly increase the isotopic composition up to δ13C=−14‰ and δD= +190‰, the largest enrichments observed for atmospheric CH4 so far. When analyzing and comparing kinetic isotope effects (KIEs) derived from single balloon profiles, it is necessary to take into account the residence time in the stratosphere in combination with the observed mixing ratio and isotope trends in the troposphere, and the range of isotope values covered by the individual profile. Temporal isotope trends can also be determined in the stratosphere and compare reasonably well with the tropospheric trends. The effects of chemical and dynamical processes on the isotopic composition of CH4 in the stratosphere are discussed in detail. Different ways to interpret the data in terms of the relative fractions of the three important sink mechanisms (reaction with OH, O(1D)) and Cl, respectively), and their limitations, are investigated. The classical approach of using global mean KIE values can be strongly biased when profiles with different minimum mixing ratios are compared. Approaches for more local KIE investigations are suggested. It is shown that any approach for a formal sink partitioning from the measured data severely underestimates the fraction removed by OH, which is likely due to the insensitivity of the measurements to the kinetic fractionation in the lower stratosphere. Attempts can be made to correct for the lower stratospheric sink bias, but full quantitative interpretation of the CH4 isotope data in terms of the three sink reactions requires a global model.
The isotopic composition of methane in the stratosphere : high-altitude balloon sample measurements
(2011)
The isotopic composition of stratospheric methane has been determined on a large suite of air samples from stratospheric balloon flights covering subtropical to polar latitudes and a time period of 16 yr. 154 samples were analyzed for δ13C and 119 samples for δD, increasing the previously published dataset for balloon borne samples by an order of magnitude, and more than doubling the total available stratospheric data (including aircraft samples) published to date. The samples also cover a large range in mixing ratio from tropospheric values near 1800 ppb down to only 250 ppb, and the strong isotope fractionation processes accordingly increase the isotopic composition up to δ13C = −14‰ and δD = +190‰, the largest enrichments observed for atmospheric CH4 so far. When analyzing and comparing kinetic isotope effects (KIEs) derived from single balloon profiles, it is necessary to take into account the residence time in the stratosphere in combination with the observed mixing ratio and isotope trends in the troposphere, and the range of isotope values covered by the individual profile. The isotopic composition of CH4 in the stratosphere is affected by both chemical and dynamical processes. This severely hampers interpretation of the data in terms of the relative fractions of the three important sink mechanisms (reaction with OH, O(1D) and Cl). It is shown that a formal sink partitioning using the measured data severely underestimates the fraction removed by OH, which is likely due to the insensitivity of the measurements to the kinetic fractionation in the lower stratosphere. Full quantitative interpretation of the CH4 isotope data in terms of the three sink reactions requires a global model.
Balloon-borne measurements of CFC-11 (on flights of the DIRAC in situ gas chromatograph and the DESCARTES grab sampler), ClO and O3 were made during the 1999/2000 winter as part of the SOLVE-THESEO 2000 campaign. Here we present the CFC-11 data from nine flights and compare them first with data from other instruments which flew during the campaign and then with the vertical distributions calculated by the SLIMCAT 3-D CTM. We calculate ozone loss inside the Arctic vortex between late January and early March using the relation between CFC-11 and O3 measured on the flights, the peak ozone loss (1200 ppbv) occurs in the 440–470 K region in early March in reasonable agreement with other published empirical estimates. There is also a good agreement between ozone losses derived from three independent balloon tracer data sets used here. The magnitude and vertical distribution of the loss derived from the measurements is in good agreement with the loss calculated from SLIMCAT over Kiruna for the same days.
An accelerating Brewer-Dobson circulation (BDC) is a robust signal of climate change in model predictions but has been questioned by trace gas observations. We analyze stratospheric mean age of air and the full age spectrum as measures for the BDC and its trend. Age of air is calculated with the Chemical Lagrangian Model of the Stratosphere (CLaMS) driven by ERA-Interim, JRA-55 and MERRA-2 reanalysis data to assess the robustness of the representation of the BDC in current generation meteorological reanalyses. We find that climatological mean age significantly depends on the reanalysis, with JRA-55 showing the youngest and MERRA-2 the oldest mean age. Consideration of the age spectrum indicates that the older age for MERRA-2 is related to a stronger spectrum tail, likely related to weaker tropical upwelling and stronger recirculation. Seasonality of stratospheric transport is robustly represented in reanalyses, with similar mean age variations and age spectrum peaks. Long-term changes over 1989–2015 turn out to be similar for the reanalyses with mainly decreasing mean age accompanied by a shift of the age spectrum peak towards shorter transit times, resembling the forced response in climate model simulations to increasing greenhouse gas concentrations. For the shorter periods 1989–2001 and 2002–2015 age of air changes are less robust. Only ERA-Interim shows the hemispheric dipole pattern in age changes during 2002–2015 as viewed by recent satellite observations. Consequently, the representation of decadal variability of the BDC in current generation reanalyses appears less robust and a major uncertainty of modelling the BDC.
This paper investigates the global stratospheric Brewer–Dobson circulation (BDC) in the ERA5 meteorological reanalysis from the European Centre for Medium-Range Weather Forecasts (ECMWF). The analysis is based on simulations of stratospheric mean age of air, including the full age spectrum, with the Lagrangian transport model CLaMS (Chemical Lagrangian Model of the Stratosphere), driven by reanalysis winds and total diabatic heating rates. ERA5-based results are compared to results based on the preceding ERA-Interim reanalysis. Our results show a significantly slower BDC for ERA5 than for ERA-Interim, manifesting in weaker diabatic heating rates and higher age of air. In the tropical lower stratosphere, heating rates are 30 %–40 % weaker in ERA5, likely correcting a bias in ERA-Interim. At 20 km and in the Northern Hemisphere (NH) stratosphere, ERA5 age values are around the upper margin of the uncertainty range from historical tracer observations, indicating a somewhat slow–biased BDC. The age trend in ERA5 over the 1989–2018 period is negative throughout the stratosphere, as climate models predict in response to global warming. However, the age decrease is not linear but steplike, potentially caused by multi-annual variability or changes in the observations included in the assimilation. During the 2002–2012 period, the ERA5 age shows a similar hemispheric dipole trend pattern as ERA-Interim, with age increasing in the NH and decreasing in the Southern Hemisphere (SH). Shifts in the age spectrum peak and residual circulation transit times indicate that reanalysis differences in age are likely caused by differences in the residual circulation. In particular, the shallow BDC branch accelerates in both reanalyses, whereas the deep branch accelerates in ERA5 and decelerates in ERA-Interim.
This paper presents an analysis of the recent tropospheric molecular hydrogen (H2) budget with a particular focus on soil uptake and European surface emissions. A variational inversion scheme is combined with observations from the RAMCES and EUROHYDROS atmospheric networks, which include continuous measurements performed between mid-2006 and mid-2009. Net H2 surface flux, then deposition velocity and surface emissions and finally, deposition velocity, biomass burning, anthropogenic and N2 fixation-related emissions were simultaneously inverted in several scenarios. These scenarios have focused on the sensibility of the soil uptake value to different spatio-temporal distributions. The range of variations of these diverse inversion sets generate an estimate of the uncertainty for each term of the H2 budget. The net H2 flux per region (High Northern Hemisphere, Tropics and High Southern Hemisphere) varies between −8 and +8 Tg yr−1. The best inversion in terms of fit to the observations combines updated prior surface emissions and a soil deposition velocity map that is based on bottom-up and top-down estimations. Our estimate of global H2 soil uptake is −59±9 Tg yr−1. Forty per cent of this uptake is located in the High Northern Hemisphere and 55% is located in the Tropics. In terms of surface emissions, seasonality is mainly driven by biomass burning emissions. The inferred European anthropogenic emissions are consistent with independent H2 emissions estimated using a H2/CO mass ratio of 0.034 and CO emissions within the range of their respective uncertainties. Additional constraints, such as isotopic measurements would be needed to infer a more robust partition of H2 sources and sinks.
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.
The fractional release factor (FRF) gives information on the amount of a halocarbon that is released at some point in 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). To apply FRF in this context, steady-state values are needed, thus representing a molecular property for a given atmospheric situation. In particular, these values should be independent of the tropospheric trends of the respective halogenated trace gases.
We analyzed the temporal evolution of FRF from ECHAM/MESSy Atmospheric Chemistry (EMAC) model simulations for several halocarbons and nitrous oxide between 1965–2011 on different mean age levels and found that the current 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 current calculation method of FRF.
Taking into account chemical loss in the calculation of stratospheric mixing ratios reduces the time-dependence in correlations of different tracers. Therefore we implemented a loss term in the formulation of FRF and applied the parameterization of a "mean arrival time" to our data set.
We find that the time-dependence in FRF can almost be compensated by applying a new trend correction in the calculation of FRF. We suggest that this new method should be used to calculate time-independent FRF, which can then be used e.g. for the calculation of ODP
We present a compact and versatile cryofocusing– thermodesorption unit, which we developed for quantitative analysis of halogenated trace gases in ambient air. Possible applications include aircraft-based in situ measurements, in situ monitoring and laboratory operation for the analysis of flask samples. Analytes are trapped on adsorptive material cooled by a Stirling cooler to low temperatures (e.g. -80°C) and subsequently desorbed by rapid heating of the adsorptive material (e.g. 200°C). The set-up involves neither the exchange of adsorption tubes nor any further condensation or refocusing steps. No moving parts are used that would require vacuum insulation. This allows for a simple and robust design. Reliable operation is ensured by the Stirling cooler, which neither contains a liquid refrigerant nor requires refilling a cryogen. At the same time, it allows for significantly lower adsorption temperatures compared to commonly used Peltier elements. We use gas chromatography – mass spectrometry (GC–MS) for separation and detection of the preconcentrated analytes after splitless injection. A substance boiling point range of approximately -80 to +150°C and a substance mixing ratio range of less than 1 ppt (pmol mol−1)to more than 500 ppt in preconcentrated sample volumes of 0.1 to 10 L of ambient air is covered, depending on the application and its analytical demands. We present the instrumental design of the preconcentration unit and demonstrate capabilities and performance through the examination of analyte breakthrough during adsorption, repeatability of desorption and analyte residues in blank tests. Examples of application are taken from the analysis of flask samples collected at Mace Head Atmospheric Research Station in Ireland using our laboratory GC–MS instruments and by data obtained during a research flight with our in situ aircraft instrument GhOSTMS (Gas chromatograph for the Observation of Tracers – coupled with a Mass Spectrometer).
We present a compact and versatile cryofocusing–thermodesorption unit, which we developed for quantitative analysis of halogenated trace gases in ambient air. Possible applications include aircraft-based in situ measurements, in situ monitoring and laboratory operation for the analysis of flask samples. Analytes are trapped on adsorptive material cooled by a Stirling cooler to low temperatures (e.g. −80 °C) and subsequently desorbed by rapid heating of the adsorptive material (e.g. +200 °C). The set-up involves neither the exchange of adsorption tubes nor any further condensation or refocusing steps. No moving parts are used that would require vacuum insulation. This allows for a simple and robust design. Reliable operation is ensured by the Stirling cooler, which neither contains a liquid refrigerant nor requires refilling a cryogen. At the same time, it allows for significantly lower adsorption temperatures compared to commonly used Peltier elements. We use gas chromatography – mass spectrometry (GC–MS) for separation and detection of the preconcentrated analytes after splitless injection. A substance boiling point range of approximately −80 to +150 °C and a substance mixing ratio range of less than 1 ppt (pmol mol−1) to more than 500 ppt in preconcentrated sample volumes of 0.1 to 10 L of ambient air is covered, depending on the application and its analytical demands. We present the instrumental design of the preconcentration unit and demonstrate capabilities and performance through the examination of analyte breakthrough during adsorption, repeatability of desorption and analyte residues in blank tests. Examples of application are taken from the analysis of flask samples collected at Mace Head Atmospheric Research Station in Ireland using our laboratory GC–MS instruments and by data obtained during a research flight with our in situ aircraft instrument GhOST-MS (Gas chromatograph for the Observation of Tracers – coupled with a Mass Spectrometer).
We present the characterization and application of a new gas chromatography time-of-flight mass spectrometry instrument (GC-TOFMS) for the quantitative analysis of halocarbons in air samples. The setup comprises three fundamental enhancements compared to our earlier work (Hoker et al., 2015): (1) full automation, (2) a mass resolving power R = m/Δm of the TOFMS (Tofwerk AG, Switzerland) increased up to 4000 and (3) a fully accessible data format of the mass spectrometric data. Automation in combination with the accessible data allowed an in-depth characterization of the instrument. Mass accuracy was found to be approximately 5 ppm in mean after automatic recalibration of the mass axis in each measurement. A TOFMS configuration giving R = 3500 was chosen to provide an R-to-sensitivity ratio suitable for our purpose. Calculated detection limits are as low as a few femtograms by means of the accurate mass information. The precision for substance quantification was 0.15 % at the best for an individual measurement and in general mainly determined by the signal-to-noise ratio of the chromatographic peak. Detector non-linearity was found to be insignificant up to a mixing ratio of roughly 150 ppt at 0.5 L sampled volume. At higher concentrations, non-linearities of a few percent were observed (precision level: 0.2 %) but could be attributed to a potential source within the detection system. A straightforward correction for those non-linearities was applied in data processing, again by exploiting the accurate mass information. Based on the overall characterization results, the GC-TOFMS instrument was found to be very well suited for the task of quantitative halocarbon trace gas observation and a big step forward compared to scanning, quadrupole MS with low mass resolving power and a TOFMS technique reported to be non-linear and restricted by a small dynamical range.
We present the characterization and application of a new gas chromatography time-of-flight mass spectrometry instrument (GC-TOFMS) for the quantitative analysis of halocarbons in air samples. The setup comprises three fundamental enhancements compared to our earlier work (Hoker et al., 2015): (1) full automation, (2) a mass resolving power R = m/Δm of the TOFMS (Tofwerk AG, Switzerland) increased up to 4000 and (3) a fully accessible data format of the mass spectrometric data. Automation in combination with the accessible data allowed an in-depth characterization of the instrument. Mass accuracy was found to be approximately 5 ppm in mean after automatic recalibration of the mass axis in each measurement. A TOFMS configuration giving R = 3500 was chosen to provide an R-to-sensitivity ratio suitable for our purpose. Calculated detection limits are as low as a few femtograms by means of the accurate mass information. The precision for substance quantification was 0.15 % at the best for an individual measurement and in general mainly determined by the signal-to-noise ratio of the chromatographic peak. Detector non-linearity was found to be insignificant up to a mixing ratio of roughly 150 ppt at 0.5 L sampled volume. At higher concentrations, non-linearities of a few percent were observed (precision level: 0.2 %) but could be attributed to a potential source within the detection system. A straightforward correction for those non-linearities was applied in data processing, again by exploiting the accurate mass information. Based on the overall characterization results, the GC-TOFMS instrument was found to be very well suited for the task of quantitative halocarbon trace gas observation and a big step forward compared to scanning, quadrupole MS with low mass resolving power and a TOFMS technique reported to be non-linear and restricted by a small dynamical range.
The transport of air masses originating from the Asian monsoon anticyclone into the extratropical upper troposphere and lower stratosphere (Ex-UTLS) above potential temperatures Θ = 380K was identified during the HALO aircraft mission TACTS in August and September 2012. In-situ measurements of CO, O3 and N2O during TACTS Flight 2 on the 30 August 2012 show the irreversible mixing of aged with younger (originating from the troposphere) stratospheric air masses within the Ex-UTLS. Backward trajectories calculated with the trajetory module of the CLaMS model indicate that these tropospherically affected air masses originate from the Asian monsoon anticyclone. From the monsoon circulation region these air masses are quasi-isentropically transported above Θ = 380 K into the Ex-UTLS where they subsequently mix with stratospheric air masses. The overall trace gas distribution measured during TACTS shows that this transport pathway has a significant impact on the Ex-UTLS during boreal summer and autumn. This leads to an intensification of the tropospheric influence on the Ex-UTLS with ∆Θ > 30 K (relative to the tropopause) within three weeks during the TACTS mission. In the same time period a weakening of the tropospheric influence on the lowermost stratosphere (LMS) is determined. Therefore, the study shows that the transport of air masses originating from the Asian summer monsoon region within the lower stratosphere above Θ = 380K is of major importance for the change of the chemical composition of the Ex-UTLS from summer to autumn.
The transport of air masses originating from the Asian monsoon anticyclone into the extratropical upper troposphere and lower stratosphere (Ex-UTLS) above potential temperatures Θ = 380 K was identified during the HALO aircraft mission TACTS in August and September 2012. In situ measurements of CO, O3 and N2O during TACTS flight 2 on 30 August 2012 show the irreversible mixing of aged stratospheric air masses with younger (recently transported from the troposphere) ones within the Ex-UTLS. Backward trajectories calculated with the trajectory module of CLaMS indicate that these tropospherically affected air masses originate from the Asian monsoon anticyclone. These air masses are subsequently transported above potential temperatures Θ = 380 K from the monsoon circulation region into the Ex-UTLS, where they subsequently mix with stratospheric air masses. The overall trace gas distribution measured during TACTS shows that this transport pathway had affected the chemical composition of the Ex-UTLS during boreal summer and autumn 2012. This leads to an intensification of the tropospheric influence on the extratropical lower stratosphere with PV > 8 pvu within 3 weeks during the TACTS mission. During the same time period a weakening of the tropospheric influence on the lowermost stratosphere (LMS) is determined. The study shows that the transport of air masses originating from the Asian summer monsoon region within the lower stratosphere affects the change in the chemical composition of the Ex-UTLS over Europe and thus contributes to the flushing of the LMS during summer 2012.
Calibration of TCCON column-averaged CO2: the first aircraft campaign over European TCCON sites
(2011)
The Total Carbon Column Observing Network (TCCON) is a ground-based network of Fourier Transform Spectrometer (FTS) sites around the globe, where the column abundances of CO2, CH4, N2O, CO and O2 are measured. CO2 is constrained with a precision better than 0.25 %. To achieve a similarly high accuracy, calibration to World Meteorological Organization (WMO) standards is required. This paper introduces the first aircraft calibration campaign of five European TCCON sites and a mobile FTS instrument. A series of WMO standards in-situ profiles were obtained over European TCCON sites via aircraft and compared with retrievals of CO2 column amounts from the TCCON instruments. The results of the campaign show that the FTS measurements are consistently biased 1.0 % ± 0.2 % low with respect to WMO standards, in agreement with previous TCCON calibration campaigns. The standard a priori profile for the TCCON FTS retrievals is shown to not add a bias. The same calibration factor is generated using aircraft profiles as a priori and with the TCCON standard a priori. With a calibration to WMO standards, the highly precise TCCON CO2 measurements of total column concentrations provide a suitable database for the calibration and validation of nadir-viewing satellites.
Calibration of TCCON column-averaged CO2: the first aircraft campaign over European TCCON sites
(2011)
The Total Carbon Column Observing Network (TCCON) is a ground-based network of Fourier Transform Spectrometer (FTS) sites around the globe, where the column abundances of CO2, CH4, N2O, CO and O2 are measured. CO2 is constrained with a precision better than 0.25% (1-σ). To achieve a similarly high accuracy, calibration to World Meteorological Organization (WMO) standards is required. This paper introduces the first aircraft calibration campaign of five European TCCON sites and a mobile FTS instrument. A series of WMO standards in-situ profiles were obtained over European TCCON sites via aircraft and compared with retrievals of CO2 column amounts from the TCCON instruments. The results of the campaign show that the FTS measurements are consistently biased 1.1% ± 0.2% low with respect to WMO standards, in agreement with previous TCCON calibration campaigns. The standard a priori profile for the TCCON FTS retrievals is shown to not add a bias. The same calibration factor is generated using aircraft profiles as a priori and with the TCCON standard a priori. With a calibration to WMO standards, the highly precise TCCON CO2 measurements of total column concentrations provide a suitable database for the calibration and validation of nadir-viewing satellites
AirCore-HR : a high-resolution column sampling to enhance the
vertical description of CH4 and CO2
(2017)
An original and innovative sampling system called AirCore was presented by NOAA in 2010 (Karion et al., 2010). It consists of a long ( > 100 m) and narrow (< 1 cm) stainless steel tube that can retain a profile of atmospheric air. The captured air sample has then to be analyzed with a gas analyzer for trace mole fraction. In this study, we introduce a new AirCore aiming to improve resolution along the vertical with the objectives to (i) better capture the vertical distribution of CO2 and CH4, (ii) provide a tool to compare AirCores and validate the estimated vertical resolution achieved by AirCores. This (high-resolution) AirCore-HR consists of a 300 m tube, combining 200 m of 0.125 in. (3.175 mm) tube and a 100 m of 0.25 in. (6.35 mm) tube. This new configuration allows us to achieve a vertical resolution of 300 m up to 15 km and better than 500 m up to 22 km (if analysis of the retained sample is performed within 3 h). The AirCore-HR was flown for the first time during the annual StratoScience campaign from CNES in August 2014 from Timmins (Ontario, Canada). High-resolution vertical profiles of CO2 and CH4 up to 25 km were successfully retrieved. These profiles revealed well-defined transport structures in the troposphere (also seen in CAMS-ECMWF high-resolution forecasts of CO2 and CH4 profiles) and captured the decrease of CO2 and CH4 in the stratosphere. The multi-instrument gondola also carried two other low-resolution AirCore-GUF that allowed us to perform direct comparisons and study the underlying processing method used to convert the sample of air to greenhouse gases vertical profiles. In particular, degrading the AirCore-HR derived profiles to the low resolution of AirCore-GUF yields an excellent match between both sets of CH4 profiles and shows a good consistency in terms of vertical structures. This fully validates the theoretical vertical resolution achievable by AirCores. Concerning CO2 although a good agreement is found in terms of vertical structure, the comparison between the various AirCores yields a large and variable bias (up to almost 3 ppm in some parts of the pro- files). The reasons of this bias, possibly related to the drying agent used to dry the air, are still being investigated. Finally, the uncertainties associated with the measurements are assessed, yielding an average uncertainty below 3 ppb for CH4 and 0.25 ppm for CO2 with the major source of uncertainty coming from the potential loss of air sample on the ground and the choice of the starting and ending point of the collected air sample inside the tube. In an ideal case where the sample would be fully retained, it would be possible to know precisely the pressure at which air was sampled last and thus to improve the overall uncertainty to about 0.1 ppm for CO2 and 2 ppb for CH4
AirCore-HR: a high resolution column sampling to enhance the vertical description of CH4 and CO2
(2016)
An original and innovative sampling system called AirCore was presented by NOAA in 2010 (Karion et al., 2010). It consists of a long (> 100 m) and narrow (< 1 cm) stainless steel tube that can retain a profile of atmospheric air. The captured air sample has then to be analyzed with a gas analyzer for trace mole fraction. In this study, we introduce a new AirCore aiming at improved resolution along the vertical with the objectives to: (i) better capture the vertical distribution of CO2 and CH4, (ii) provide a tool to compare AirCores and validate the estimated vertical resolution achieved by AirCores. This AirCore-HR (high resolution) consists of a 300 m tube, combining 200 m of 1/8 in. (3.175 mm) tube and a 100 m of 1/4 in. (6.35 mm) tube. This new configuration allows to achieve a vertical resolution of 300 m up to 15 km and better than 500 m up to 22 km (if analysis of the retained sample is performed within 3 hours). The AirCore-HR was flown for the first time during the annual StratoScience campaign from CNES in August 2014 from Timmins (Ontario, Canada). High-resolution vertical profiles of CO2 and CH4 up to 25 km were successfully retrieved. These profiles revealed well defined transport structures in the troposphere (also seen in CAMS-ECMWF high resolution forecasts of CO2 and CH4 profiles) and captured the decrease of CO2 and CH4 in the stratosphere. The multi-instruments gondola from the flight carried two other low-resolution AirCore-GUF that allowed to perform direct comparisons and study the underlying processing method used to convert the sample of air to greenhouse gases vertical profiles. In particular, degrading the AirCore-HR derived profiles to the low resolution of AirCore-GUF yields an excellent match between both sets of CH4 profiles, and shows a good consistency between vertical structures of CO2 and CH4. These results fully validate the theoretical vertical resolution achievable by AirCores. Finally, the uncertainties associated with the measurements are assessed, yielding an average uncertainty below 3 ppb for CH4 and 0.25 ppm for CO2 with the major source of uncertainty coming from the potential loss of air sample on the ground and the choice of the starting and ending point of the collected air sample inside the tube. In an ideal case where the sample would be fully retained, it would be possible to know precisely the pressure at which air was sampled last and thus to improve the overall uncertainty to about 0.1 ppm for CO2 and 2 ppb for CH4.
National Greenhouse Gas Inventories (GHGI) are submitted annually to the United Nations Framework Convention on Climate Change (UNFCCC). They are estimated in compliance with Intergovernmental Panel on Climate Change (IPCC) methodological guidance using activity data, emission factors and facility-level measurements. For some sources, the outputs from these calculations are very uncertain. Inverse modelling techniques that use high-quality, long-term measurements of atmospheric gases have been developed to provide independent verification of national GHGI. This is considered good practice by the IPCC as it helps national inventory compilers to verify reported emissions and to reduce emission uncertainty. Emission estimates from the InTEM (Inversion Technique for Emissions Modelling) model are presented for the UK for the hydrofluorocarbons (HFCs) reported to the UNFCCC (HFC-125, HFC-134a, HFC-143a, HFC-152a, HFC-23, HFC-32, HFC-227ea, HFC-245fa, HFC-43-10mee and HFC-365mfc). These HFCs have high Global Warming Potentials (GWPs) and the global background mole fractions of all but two are increasing, thus highlighting their relevance to the climate and a need for increasing the accuracy of emission estimation for regulatory purposes. This study presents evidence that the long-term annual increase in growth of HFC-134a has stopped and is now decreasing. For HFC-32 there is an early indication its rapid global growth period has ended, and there is evidence that the annual increase in global growth for HFC-125 has slowed from 2018. The inverse modelling results indicate that the UK implementation of European Union regulation of HFC emissions has been successful in initiating a decline in UK emissions in the since 2018. Comparison of the total InTEM UK HFC emissions in 2020 with the average from 2009–2012 shows a drop of 35%, indicating progress toward the target of a 79% decrease in sales by 2030. The total InTEM HFC emission estimates (2008–2018) are on average 73 (62–83)% of, or 4.3 (2.7–5.9) Tg CO2-eq yr−1 lower than, the total HFC emission estimates from the UK GHGI inventory. There are also significant discrepancies between the two estimates for the individual HFCs.
National greenhouse gas inventories (GHGIs) are submitted annually to the United Nations Framework Convention on Climate Change (UNFCCC). They are estimated in compliance with Intergovernmental Panel on Climate Change (IPCC) methodological guidance using activity data, emission factors and facility-level measurements. For some sources, the outputs from these calculations are very uncertain. Inverse modelling techniques that use high-quality, long-term measurements of atmospheric gases have been developed to provide independent verification of national GHGIs. This is considered good practice by the IPCC as it helps national inventory compilers to verify reported emissions and to reduce emission uncertainty. Emission estimates from the InTEM (Inversion Technique for Emission Modelling) model are presented for the UK for the hydrofluorocarbons (HFCs) reported to the UNFCCC (HFC-125, HFC-134a, HFC-143a, HFC-152a, HFC-23, HFC-32, HFC-227ea, HFC-245fa, HFC-43-10mee and HFC-365mfc). These HFCs have high global warming potentials (GWPs), and the global background mole fractions of all but two are increasing, thus highlighting their relevance to the climate and a need for increasing the accuracy of emission estimation for regulatory purposes. This study presents evidence that the long-term annual increase in growth of HFC-134a has stopped and is now decreasing. For HFC-32 there is an early indication, its rapid global growth period has ended, and there is evidence that the annual increase in global growth for HFC-125 has slowed from 2018. The inverse modelling results indicate that the UK implementation of European Union regulation of HFC emissions has been successful in initiating a decline in UK emissions from 2018. Comparison of the total InTEM UK HFC emissions in 2020 with the average from 2009–2012 shows a drop of 35 %, indicating progress toward the target of a 79 % decrease in sales by 2030. The total InTEM HFC emission estimates (2008–2018) are on average 73 (62–83) % of, or 4.3 (2.7–5.9) Tg CO2-eq yr−1 lower than, the total HFC emission estimates from the UK GHGI. There are also significant discrepancies between the two estimates for the individual HFCs.
Atmospheric observation-based global SF6 emissions - comparison of top-down and bottom-up estimates
(2009)
Emissions of sulphur hexafluoride (SF6), one of the strongest greenhouse gases on a per molecule basis, are targeted to be collectively reduced under the Kyoto Protocol. Because of its long atmospheric lifetime (≈3000 years), the accumulation of SF6 in the atmosphere is a direct measure of its global emissions. Examination of our extended data set of globally distributed high-precision SF6 observations shows an increase in SF6 abundance from near zero in the 1970s to a global mean of 6.7 ppt by the end of 2008. In-depth evaluation of our long-term data records shows that the global source of SF6 decreased after 1995, most likely due to SF6 emission reductions in industrialised countries, but increased again after 1998. By subtracting those emissions reported by Annex I countries to the United Nations Framework Convention of Climatic Change (UNFCCC) from our observation-inferred SF6 source leaves a surprisingly large gap of more than 70–80% of non-reported SF6 emissions in the last decade.
Emissions of sulphur hexafluoride (SF6), one of the strongest greenhouse gases on a per molecule basis, are targeted to be collectively reduced under the Kyoto Protocol. Because of its long atmospheric lifetime (estimated as 800 to 3200 years), the accumulation of SF6 in the atmosphere is a direct measure of its global emissions. Examination of our extended data set of globally distributed high-precision SF6 observations shows an increase in SF6 abundance from near zero in the 1970s to a global mean of 6.7 ppt by the end of 2008. In-depth evaluation of our long-term data records shows that the global source of SF6 decreased after 1995, most likely due to SF6 emission reductions in industrialised countries, but increased again after 1998. By subtracting those emissions reported by Annex I countries to the United Nations Framework Convention of Climatic Change (UNFCCC) from our observation-inferred SF6 source leaves a surprisingly large gap of more than 70–80% of non-reported SF6 emissions in the last decade. This suggests a strong under-estimation of emissions in Annex I countries and underlines the urgent need for independent atmospheric verification of greenhouse gases emissions accounting.
Production and use of many synthetic halogenated trace gases are regulated internationally due to their contribution to stratospheric ozone depletion or climate change. In many applications they have been replaced by shorter-lived compounds, which have become measurable in the atmosphere as emissions increased. Non-target monitoring of trace gases rather than targeted measurements of well-known substances is needed to keep up with such changes in the atmospheric composition. We regularly deploy gas chromatography (GC) coupled to time-of-flight mass spectrometry (TOF-MS) for analysis of flask air samples and in situ measurements at the Taunus Observatory, a site in central Germany. TOF-MS acquires data over a continuous mass range that enables a retrospective analysis of the dataset, which can be considered a type of digital air archive. This archive can be used if new substances come into use and their mass spectrometric fingerprint is identified. However, quantifying new replacement halocarbons can be challenging, as mole fractions are generally low, requiring high measurement precision and low detection limits. In addition, calibration can be demanding, as calibration gases may not contain sufficiently high amounts of newly measured substances or the amounts in the calibration gas may have not been quantified. This paper presents an indirect data evaluation approach for TOF-MS data, where the calibration is linked to another compound which could be quantified in the calibration gas. We also present an approach to evaluate the quality of the indirect calibration method, select periods of stable instrument performance and determine well suited reference compounds. The method is applied to three short-lived synthetic halocarbons: HFO-1234yf, HFO-1234ze(E), and HCFO-1233zd(E). They represent replacements for longer-lived hydrofluorocarbons (HFCs) and exhibit increasing mole fractions in the atmosphere.
The indirectly calibrated results are compared to directly calibrated measurements using data from TOF-MS canister sample analysis and TOF-MS in situ measurements, which are available for some periods of our dataset. The application of the indirect calibration method on several test cases can result in uncertainties of around 6 % to 11 %. For hydro(chloro-)fluoroolefines (denoted H(C)FOs), uncertainties up to 23 % are achieved. The indirectly calculated mole fractions of the investigated H(C)FOs at Taunus Observatory range between measured mole fractions at urban Dübendorf and Jungfraujoch stations in Switzerland.
We report the first measurements of 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), a substitute for ozone depleting compounds, in remote regions of the atmosphere and present evidence for its rapid growth. Observed mixing ratios ranged from below 0.01 ppt in deep firn air to 0.59 ppt in the northern mid-latitudinal upper troposphere. Firn air samples collected in Greenland were used to reconstruct a history of atmospheric abundance. Year-on-year increases were deduced, with acceleration in the growth rate from 0.026 ppt per year in 2000 to 0.057 ppt per year in 2007. Upper tropospheric air samples provide evidence for a continuing growth until late 2009. Fur- thermore we calculated a stratospheric lifetime of 370 years from measurements of air samples collected on board high altitude aircraft and balloons. Emission estimates were determined from the reconstructed atmospheric trend and suggest that current "bottom-up" estimates of global emissions for 2005 are too high by more than a factor of three.
We report the first measurements of 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), a substitute for ozone depleting compounds, in air samples originating from remote regions of the atmosphere and present evidence for its accelerating growth. Observed mixing ratios ranged from below 0.01 ppt in deep firn air to 0.59 ppt in the current northern mid-latitudinal upper troposphere. Firn air samples collected in Greenland were used to reconstruct a history of atmospheric abundance. Year-on-year increases were deduced, with acceleration in the growth rate from 0.029 ppt per year in 2000 to 0.056 ppt per year in 2007. Upper tropospheric air samples provide evidence for a continuing growth until late 2009. Furthermore we calculated a stratospheric lifetime of 370 years from measurements of air samples collected on board high altitude aircraft and balloons. Emission estimates were determined from the reconstructed atmospheric trend and suggest that current "bottom-up" estimates of global emissions for 2005 are too high by a factor of three.
Estimates of the recovery time of stratospheric ozone heavily rely on the exact knowledge of the processes that lead to the decomposition of the relevant halogenated source gases. Crucial parameters in this context are Fractional Release Factors (FRFs) as well as stratospheric lifetimes and Ozone Depletion Potentials (ODPs). We here present data from the analysis of air samples collected between 2009 and 2011 on board research aircraft flying in the mid- and high latitudinal stratosphere and infer the above-mentioned parameters for ten major source gases:CFCl3 (CFC-11), CF2Cl2 (CFC-12), CF2ClCFCl2(CFC-113), CCl4 (carbon tetrachloride),CH3CCl3 (methyl chloroform), CHF2Cl (HCFC-22), CH3CFCl2 (HCFC-141b), CH3CF2Cl (HCFC-142b), CF2ClBr (H-1211), and CF3Br (H-1301). The inferred correlations of their FRFs with mean ages of air reveal less decomposition as compared to previous studies for most compounds. When using the calculated set of FRFs to infer equivalent stratospheric chlorine we find a reduction of more than 20% as compared to the values inferred in the most recent Scientific Assessment of Ozone Depletion by the World Meteorological Organisation (WMO, 2011). We also note that FRFs and their correlations with mean age are not generally time-independent as often assumed. The stratospheric lifetimes were calculated relative to that of CFC-11. Within our uncertainties the inferred ratios between lifetimes agree with those between stratospheric lifetimes from recent WMO reports except for CFC-11, CFC-12 and CH3CCl3. Finally we calculate lower ODPs than WMO for six out of ten compounds with changes most pronounced for the three HCFCs. Collectively these newly calculated values may have important implications for the severity and recovery time of stratospheric ozone loss.
Estimates of the recovery time of stratospheric ozone heavily rely on the exact knowledge of the processes that lead to the decomposition of the relevant halogenated source gases. Crucial parameters in this context are fractional release factors (FRFs) as well as stratospheric lifetimes and ozone depletion potentials (ODPs). We here present data from the analysis of air samples collected between 2009 and 2011 on board research aircraft flying in the mid- and high-latitude stratosphere and infer the above-mentioned parameters for ten major source gases: CFCl3 (CFC-11), CF2Cl2 (CFC-12), CF2ClCFCl2 (CFC-113), CCl4 (carbon tetrachloride), CH3CCl3 (methyl chloroform), CHF2Cl (HCFC-22), CH3CFCl2 (HCFC-141b), CH3CF2Cl (HCFC-142b), CF2ClBr (H-1211), and CF3Br (H-1301). The inferred correlations of their FRFs with mean ages of air reveal less decomposition as compared to previous studies for most compounds. When using the calculated set of FRFs to infer equivalent stratospheric chlorine, we find a reduction of more than 20% as compared to the values inferred in the most recent Scientific Assessment of Ozone Depletion by the World Meteorological Organisation (WMO, 2011). We also note that FRFs and their correlations with mean age are not generally time-independent as often assumed. The stratospheric lifetimes were calculated relative to that of CFC-11. Within our uncertainties the ratios between stratospheric lifetimes inferred here agree with the values in recent WMO reports except for CFC-11, CFC-12 and CH3CCl3. Finally, we calculate lower ODPs than recommended by WMO for six out of ten compounds, with changes most pronounced for the three HCFCs. Collectively these newly calculated values may have important implications for the severity and recovery time of stratospheric ozone loss.
The total stratospheric organic chlorine and bromine burden was derived from balloon-borne measurements in the tropics (Teresina, Brazil, 5°04´ S, 42°52´ W) in 2005. Whole air samples were collected cryogenically at altitudes between 15 and 34 km. For the first time, we report measurements of a set of 28 chlorinated and brominated substances in the tropical upper troposphere and stratosphere including ten substances with an atmospheric lifetime of less than half a year. The substances were quantified using pre-concentration techniques followed by Gas Chromatography with Mass Spectrometric detection. In the tropical tropopause layer at altitudes between 15 and 17 km we found 1.1–1.4% of the chlorine and 6–8% of the bromine to be present in the form of very short-lived organic compounds. By combining the data with tropospheric reference data and age of air observations the abundances of inorganic chlorine and bromine (Cly and Bry) were derived. At an altitude of 34 km we calculated 3062 ppt of Cly and 17.5 ppt of Bry from the decomposition of both long- and short-lived organic source gases. Furthermore we present indications for the presence of additional organic brominated substances in the tropical upper troposphere and stratosphere.
Fractional release factors of long-lived halogenated organic compounds in the tropical stratosphere
(2010)
Fractional release factors (FRFs) of organic trace gases are time-independent quantities that influence the calculation of Global Warming Potentials and Ozone Depletion Potentials. We present the first set of vertically resolved FRFs for 15 long-lived halocarbons in the tropical stratosphere up to 34 km altitude. They were calculated from measurements on air samples collected on board balloons and a high altitude aircraft. We compare the derived dependencies of FRFs on the mean stratospheric transit times (the so-called mean ages of air) with similarly derived FRFs originating from measurements at higher latitudes and find significant differences. Moreover a comparison with averaged FRFs currently used by the World Meteorological Organisation revealed the limitations of these measures due to their observed vertical and latitudinal variability. The presented data set could be used to improve future ozone level and climate projections.
Fractional release factors of long-lived halogenated organic compounds in the tropical stratosphere
(2009)
Fractional release factors (FRFs) of organic trace gases are time-independent quantities that influence the calculation of Global Warming Potentials and Ozone Depletion Potentials. We present the first set of vertically resolved FRFs for 15 long-lived halo carbons in the tropical stratosphere up to 34 km altitude. They were calculated from measurements on air samples collected on board balloons and a high altitude aircraft. We compare the derived dependencies of FRFs on the mean stratospheric transit times (the so-called mean ages of air) with similarly derived FRFs originating from measurements at higher latitudes and find significant differences. Moreover a comparison with averaged FRFs currently used by the World Meteorological Organisation revealed the latter to be imprecise measures due to their observed vertical and latitudinal variability. The presented data set could thus be used to improve future ozone level and climate projections.
Background: Point of care devices for performing targeted coagulation substitution in bleeding patients have become increasingly important in recent years. New on the market is the Quantra® from HemoSonics (LC, Charlottesville, VA, US). It uses sonorheometry, a sonic estimation of elasticity via resonance (SEER), a novel ultrasound-based technology that measures viscoelastic properties of whole blood. Several studies have already shown the comparability with devices already established on the market such as the ROTEM® (TEM International GmbH, Munich, Germany).
Objective: In contrast to existing studies, the planned study will be the first prospective interventional study using the new Quantra® system in a cardiac surgical patient cohort. The aim is to investigate the non-inferiority between an already existing coagulation algorithm, based on ROTEM®/Multiplate®, and a new algorithm based on the Quantra®, for the treatment of coagulopathic cardiac surgical patients.
Methods: The study is divided into two phases. In an initial observation phase, whole blood samples of 20 patients will be analyzed using both ROTEM®/Multiplate® and Quantra® obtained at three defined points of time (prior to surgery, after completion of cardiopulmonary bypass, on arrival in the intensive care unit). The obtained threshold values will be used to create an algorithm for hemotherapy. In a second intervention phase, the new algorithm will be tested against an algorithm used routineously for years at our department for non-inferiority.
Results: The main objective of the examination is the cumulative loss of blood within 24 hours after surgery. Statistical calculations based on literature and in-house data suggest that the new algorithm is not inferior if the difference in cumulative blood loss is < 150ml/24 h.
Conclusions: Because of the comparability of the Quantra® sonorheometry system with ROTEM® rotational thromboelastometric measurement methods, the existing hemotherapy treatment algorithm can be adapted to the Quantra device with a proof of non-inferiority. Clinical Trial: International Registered Report Identifier (IRRID): clinicaltrials.gov: NCT03902275
We present novel measurements of five short-lived brominated source gases (CH2Br2, CHBr3, CH2ClBr, CHCl2Br and CHClBr2) obtained using a gas chromatograph-mass spectrometer system on board the High Altitude and Long Range Research Aircraft (HALO). The instrument is extremely sensitive due to the use of chemical ionisation, allowing detection limits in the lower parts per quadrillion (10-15) range. Data from three campaigns using the HALO aircraft are presented, where the Upper Troposphere/Lower Stratosphere (UTLS) of the Northern Hemisphere mid to high latitudes were sampled during winter and during late summer to early fall. We show that an observed decrease with altitude in the stratosphere is consistent with the relative lifetimes of the different compounds. Distributions of the five source gases and total organic bromine just below the tropopause shows an increase in mixing ratio with latitude, in particular during polar winter. This increase in mixing ratio is explained by increasing lifetimes at higher latitudes during winter. As the mixing ratio at the extratropical tropopause are generally higher than those derived for the tropical tropopause, extratropical troposphere-to-stratosphere transport will result in elevated levels of organic bromine in comparison to air transported over the tropical tropopause. The observations are compared to model estimates using different emission scenarios. A scenario which has emissions most strongly concentrated to low latitudes cannot reproduce the observed latitudinal distributions and will tend to overestimate bromine input through the tropical tropopause from CH2Br2 and CHBr3. Consequently, the scenario also overestimates the amount of brominated organic gases in the stratosphere. The two scenarios with the highest overall emissions of CH2Br2 tend to overestimate mixing ratios at the tropical tropopause but are in much better agreement with extratropical tropopause values, showing that not only total emissions but also latitudinal distributions in the emissions are of importance. While an increase in tropopause values with latitude is reproduced with all emission scenarios during winter, the simulated extratropical tropopause values are on average lower than the observations during late summer to fall. We show that a good knowledge of the latitudinal distribution of tropopause mixing ratios and of the fractional contributions of tropical and extratropical air is needed to derive stratospheric inorganic bromine in the lowermost stratosphere from observations. Depending on the underlying emission scenario, differences of a factor 2 in reactive bromine derived from observations and model outputs are found for the lowermost stratosphere, based on source gas injection. We conclude that a good representation of the contributions of different source regions is required in models for a robust assessment of the role of short-lived halogen source gases on ozone depletion in the UTLS.
The three-dimensional quantification of small scale processes in the upper troposphere and lower stratosphere is one of the challenges of current atmospheric research and requires the development of new measurement strategies. This work presents first results from the newly developed Gimballed Limb Observer for Radiance Imaging of the Atmosphere (GLORIA) obtained during the ESSenCe and TACTS/ESMVal aircraft campaigns. The focus of this work is on the so-called dynamics mode data characterized by a medium spectral and a very high spatial resolution. The retrieval strategy for the derivation of two- and three-dimensional constituent fields in the upper troposphere and lower stratosphere is presented. Uncertainties of the main retrieval targets (temperature, O3, HNO3 and CFC-12) and their spatial resolution are discussed. During ESSenCe, high resolution two-dimensional cross-sections have been obtained. Comparisons to collocated remote-sensing and in-situ data indicate a good agreement between the data sets. During TACTS/ESMVal a tomographic flight pattern to sense an intrusion of stratospheric air deep into the troposphere has been performed. This filament could be reconstructed with an unprecedented spatial resolution of better than 500 m vertically and 20 km × 20 km horizontally.
The three-dimensional quantification of small-scale processes in the upper troposphere and lower stratosphere is one of the challenges of current atmospheric research and requires the development of new measurement strategies. This work presents the first results from the newly developed Gimballed Limb Observer for Radiance Imaging of the Atmosphere (GLORIA) obtained during the ESSenCe (ESa Sounder Campaign) and TACTS/ESMVal (TACTS: Transport and composition in the upper troposphere/lowermost stratosphere, ESMVal: Earth System Model Validation) aircraft campaigns. The focus of this work is on the so-called dynamics-mode data characterized by a medium-spectral and a very-high-spatial resolution. The retrieval strategy for the derivation of two- and three-dimensional constituent fields in the upper troposphere and lower stratosphere is presented. Uncertainties of the main retrieval targets (temperature, O3, HNO3, and CFC-12) and their spatial resolution are discussed. During ESSenCe, high-resolution two-dimensional cross-sections have been obtained. Comparisons to collocated remote-sensing and in situ data indicate a good agreement between the data sets. During TACTS/ESMVal, a tomographic flight pattern to sense an intrusion of stratospheric air deep into the troposphere was performed. It was possible to reconstruct this filament at an unprecedented spatial resolution of better than 500 m vertically and 20 × 20 km horizontally.
A comprehensive set of stratospheric balloon and aircraft samples was analyzed for the position-dependent isotopic composition of nitrous oxide (N2O). Results for a total of 220 samples from between 1987 and 2003 are presented, nearly tripling the number of mass-spectrometric N2O isotope measurements in the stratosphere published to date. Cryogenic balloon samples were obtained at polar (Kiruna/Sweden, 68° N), mid-latitude (southern France, 44° N) and tropical sites (Hyderabad/India, 18° N). Aircraft samples were collected with a newly-developed whole air sampler on board of the high-altitude aircraft M55 Geophysica during the EUPLEX 2003 campaign. All samples were analyzed by laboratory mass spectrometry for their 18O/16O and position-dependent 15N/14N isotope ratios with very high precision (standard deviation about 0.15 per mil for 18O/16O and average 15N/14N ratios, about 0.5 per mil for 15NNO/14NNO and N15NO/N14NO ratios). For mixing ratios above 200 nmol mol−1, relative isotope enrichments (δ values) and mixing ratios display a compact relationship, which is nearly independent of latitude and season and which can be explained equally well by Rayleigh fractionation or mixing. However, for mixing ratios below 200 nmol mol−1 this compact relationship gives way to meridional, seasonal and interannual variations. A comparison to a previously published mid-latitude balloon profile even shows large zonal variations, justifying the use of three-dimensional models for further data interpretation.
In general, the magnitude of the apparent fractionation constants (apparent isotope effects) increases continuously with altitude and decreases from the equator to the North pole, which can be qualitatively understood by the interplay between the time-scales of N2O photochemistry and transport. Deviations from this behavior occur where polar vortex air mixes with nearly N2O-free upper stratospheric/mesospheric air (e.g., during the boreal winter of 2003 and possibly 1992). Aircraft observations in the polar vortex at mixing ratios below 200 nmol mol−1 deviate from isotope variations expected for both Rayleigh fractionation and end-member mixing, but could be explained by continuous weak mixing between intravortex and extravortex air (Plumb et al., 2000). Finally, correlations between 18O/16O and average 15N/14N isotope ratios or between the position-dependent 15N/14N isotope ratios show that photo-oxidation makes a large contribution to the total N2O sink in the lower stratosphere (up to 100%). Towards higher altitudes, the temperature dependence of these isotope correlations becomes visible in the stratospheric observations.