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We conducted measurements of up to the five important short-lived brominated species in the marine boundary layer (MBL) of the mid-latitudes (List/Sylt, North Sea) in June 2009 and of the tropical Western Pacific during the TransBrom ship campaign in October 2009. For the one-week time series in List mean mixing ratios of 2.0, 1.1, 0.2, 0.1 ppt were analysed for CHBr3, CH2Br2, CHBr2Cl and CH2BrCl, with maxima of 5.8 and 1.6 ppt for the two main components CHBr3 and CH2Br2. Along the cruise track in the Western Pacific (between 41° N and 13° S) mean mixing ratios of 1.0, 0.9, 0.2, 0.1 and 0.1 ppt for CHBr3, CH2Br2, CHBrCl2, CHBr2Cl and CH2BrCl were determined. Air samples with coastal influence showed considerably higher mixing ratios than the samples with open ocean origin. Correlation analyses of the two datasets yielded strong linear relationships between the mixing ratios of four of the five species (except for CH2BrCl). Using a combined dataset from the two campaigns, rough estimates of the molar emission ratios between the correlated substances were derived as follows: 9/1/0.3/0.3 for CHBr3/CH2Br2/CHBrCl2/CHBr2Cl. Additional measurements were made in the tropical tropopause layer (TTL) above Teresina (Brazil, 5.07° S, 42.87° W) in June 2008, using balloon-borne cryogenic whole air sampling technique. Near the level of zero clear-sky net radiative heating (LZRH) at 14.8 km about 2.25 ppt organic bromine was bound to the five short-lived species, making up 13 % of total organic bromine (17.82 ppt). CH2Br2 (1.45 ppt) and CHBr3 (0.56 ppt) accounted for 90 % of the budget of short-lived compounds in that region. Near the tropopause (at 17.5 km) organic bromine from short-lived substances was reduced to 1.35 ppt, with 1.07 ppt and 0.12 ppt attributed to CH2Br2 and CHBr3 respectively.
We conducted measurements of the five important short-lived organic bromine species in the marine boundary layer (MBL). Measurements were made in the Northern Hemisphere mid-latitudes (Sylt Island, North Sea) in June 2009 and in the tropical Western Pacific during the TransBrom ship campaign in October 2009. For the one-week time series on Sylt Island, mean mixing ratios of CHBr3, CH2Br2, CHBr2Cl and CH2BrCl were 2.0, 1.1, 0.2, 0.1 ppt, respectively. We found maxima of 5.8 and 1.6 ppt for the two main components CHBr3 and CH2Br2. Along the cruise track in the Western Pacific (between 41° N and 13° S) we measured mean mixing ratios of 0.9, 0.9, 0.2, 0.1 and 0.1 ppt for CHBr3, CH2Br2, CHBrCl2, CHBr2Cl and CH2BrCl. Air samples with coastal influence showed considerably higher mixing ratios than the samples with open ocean origin. Correlation analyses of the two data sets yielded strong linear relationships between the mixing ratios of four of the five species (except for CH2BrCl). Using a combined data set from the two campaigns and a comparison with the results from two former studies, rough estimates of the molar emission ratios between the correlated substances were: 9/1/0.35/0.35 for CHBr3/CH2Br2/CHBrCl2/CHBr2Cl. Additional measurements were made in the tropical tropopause layer (TTL) above Teresina (Brazil, 5° S) in June 2008, using balloon-borne cryogenic whole air sampling technique. Near the level of zero clear-sky net radiative heating (LZRH) at 14.8 km about 2.25 ppt organic bromine was bound to the five short-lived species, making up 13% of total organic bromine (17.82 ppt). CH2Br2 (1.45 ppt) and CHBr3 (0.56 ppt) accounted for 90% of the budget of short-lived compounds in that region. Near the tropopause (at 17.5 km) organic bromine from these substances was reduced to 1.35 ppt, with 1.07 and 0.12 ppt attributed to CH2Br2 and CHBr3, respectively.
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.
Chlorine and bromine atoms lead to catalytic depletion of ozone in the stratosphere. Therefore the use and production of ozone-depleting substances (ODSs) containing chlorine and bromine is regulated by the Montreal Protocol to protect the ozone layer. Equivalent effective stratospheric chlorine (EESC) has been adopted as an appropriate metric to describe the combined effects of chlorine and bromine released from halocarbons on stratospheric ozone. Here we revisit the concept of calculating EESC. We derive a refined formulation of EESC based on an advanced concept of ODS propagation into the stratosphere and reactive halogen release. A new transit time distribution is introduced in which the age spectrum for an inert tracer is weighted with the release function for inorganic halogen from the source gases. This distribution is termed the release time distribution. We show that a much better agreement with inorganic halogen loading from the chemistry transport model TOMCAT is achieved compared with using the current formulation. The refined formulation shows EESC levels in the year 1980 for the mid-latitude lower stratosphere, which are significantly lower than previously calculated. The year 1980 is commonly used as a benchmark to which EESC must return in order to reach significant progress towards halogen and ozone recovery. Assuming that – under otherwise unchanged conditions – the EESC value must return to the same level in order for ozone to fully recover, we show that it will take more than 10 years longer than estimated in this region of the stratosphere with the current method for calculation of EESC. We also present a range of sensitivity studies to investigate the effect of changes and uncertainties in the fractional release factors and in the assumptions on the shape of the release time distributions. We further discuss the value of EESC as a proxy for future evolution of inorganic halogen loading under changing atmospheric dynamics using simulations from the EMAC model. We show that while the expected changes in stratospheric transport lead to significant differences between EESC and modelled inorganic halogen loading at constant mean age, EESC is a reasonable proxy for modelled inorganic halogen on a constant pressure level.
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.
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.
In this paper we present evidence that the observed increase in tropical upwelling after the year 2000 may be attributed to a change in the Brewer-Dobson circulation pattern. For this purpose, we use the concept of transit times derived from residual circulation trajectories and different in-situ measurements of ozone and nitrous dioxide. Observations from the Canadian midlatitude ozone profile record, probability density functions of in-situ N2O observations and a shift of the N2O-O3 correlation slopes, taken together, indicate that the increased upwelling in the tropics after the year 2000 appears to have triggered an intensification of tracer transport from the tropics into the extratropics in the lower stratosphere below about 500 K. This finding is corroborated by the fact that transit times along the shallow branch of the residual circulation into the LMS have decreased for the same time period (1993–2003). On a longer time scale (1979–2009), the transit time of the shallow residual circulation branch show a steady decrease of about −1 month/decade over the last 30 years, while the transit times of the deep branch remain unchanged. This highlights the fact that a change in the upwelling across the tropical tropopause is not a direct indicator for changes of the whole Brewer-Dobson circulation.
In this paper we present evidence that the observed increase in tropical upwelling after the year 2000 may be attributed to a change in the Brewer-Dobson circulation pattern. For this purpose, we use the concept of transit times derived from residual circulation trajectories and different in-situ measurements of ozone and nitrous dioxide. Observations from the Canadian midlatitude ozone profile record, probability density functions of in-situ N2O observations and a shift of the N2O-O3 correlation slopes, taken together, indicate that the increased upwelling in the tropics after the year 2000 appears to have triggered an intensification of tracer transport from the tropics into the extratropics in the lower stratosphere below about 500 K. This finding is corroborated by the fact that transit times along the shallow branch of the residual circulation into the LMS have decreased for the same time period (1993–2003). On a longer time scale (1979–2009), the transit time of the shallow residual circulation branch show a steady decrease of about −1 month/decade over the last 30 yr, while the transit times of the deep branch remain unchanged. This highlights that changes in the upwelling across the tropical tropopause are not sufficient as an indicator for changes in the entire Brewer-Dobson circulation.
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.