Air was sampled from the porous firn layer at the NEEM site in Northern Greenland. We use an ensemble of ten reference tracers of known atmospheric history to characterise the transport properties of ...the site. By analysing uncertainties in both data and the reference gas atmospheric histories, we can objectively assign weights to each of the gases used for the depth-diffusivity reconstruction. We define an objective root mean square criterion that is minimised in the model tuning procedure. Each tracer constrains the firn profile differently through its unique atmospheric history and free air diffusivity, making our multiple-tracer characterisation method a clear improvement over the commonly used single-tracer tuning. Six firn air transport models are tuned to the NEEM site; all models successfully reproduce the data within a 1σ Gaussian distribution. A comparison between two replicate boreholes drilled 64 m apart shows differences in measured mixing ratio profiles that exceed the experimental error. We find evidence that diffusivity does not vanish completely in the lock-in zone, as is commonly assumed. The ice age- gas age difference (Δage) at the firn-ice transition is calculated to be 182+3−9 yr. We further present the first intercomparison study of firn air models, where we introduce diagnostic scenarios designed to probe specific aspects of the model physics. Our results show that there are major differences in the way the models handle advective transport. Furthermore, diffusive fractionation of isotopes in the firn is poorly constrained by the models, which has consequences for attempts to reconstruct the isotopic composition of trace gases back in time using firn air and ice core records.
Insoluble trace gases are trapped in polar ice at the firn-ice transition, at approximately 50 to 100 m below the surface, depending primarily on the site temperature and snow accumulation. Models of ...trace gas transport in polar firn are used to relate firn air and ice core records of trace gases to their atmospheric history. We propose a new model based on the following contributions. First, the firn air transport model is revised in a poromechanics framework with emphasis on the non-homogeneous properties and the treatment of gravitational settling. We then derive a nonlinear least square multi-gas optimisation scheme to calculate the effective firn diffusivity (automatic diffusivity tuning). The improvements gained by the multi-gas approach are investigated (up to ten gases for a single site are included in the optimisation process). We apply the model to four Arctic (Devon Island, NEEM, North GRIP, Summit) and seven Antarctic (DE08, Berkner Island, Siple Dome, Dronning Maud Land, South Pole, Dome C, Vostok) sites and calculate their respective depth-dependent diffusivity profiles. Among these different sites, a relationship is inferred between the snow accumulation rate and an increasing thickness of the lock-in zone defined from the isotopic composition of molecular nitrogen in firn air (denoted δ15N). It is associated with a reduced diffusivity value and an increased ratio of advective to diffusive flux in deep firn, which is particularly important at high accumulation rate sites. This has implications for the understanding of δ15N of N2 records in ice cores, in relation with past variations of the snow accumulation rate. As the snow accumulation rate is clearly a primary control on the thickness of the lock-in zone, our new approach that allows for the estimation of the lock-in zone width as a function of accumulation may lead to a better constraint on the age difference between the ice and entrapped gases.
Atmospheric concentrations of dichloromethane, CH2Cl2, a regulated toxic air pollutant and minor contributor to stratospheric ozone depletion, were reported to have peaked around 1990 and to be ...declining in the early part of the 21st century. Recent observations suggest this trend has reversed and that CH2Cl2 is once again increasing in the atmosphere. Despite the importance of ongoing monitoring and reporting of atmospheric CH2Cl2, no time series has been discussed in detail since 2006. The CARIBIC project (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container) has analysed the halocarbon content of whole-air samples collected at altitudes of between ~ 10-12 km via a custom-built container installed on commercial passenger aircraft since 1998, providing a long-term record of CH2Cl2 observations. In this paper we present this unique CH2Cl2 time series, discussing key flight routes which have been used at various times over the past 15 years. Between 1998 and 2012 increases were seen in all northern hemispheric regions and at different altitudes, ranging from ~ 7-10 ppt in background air to ~ 13-15 ppt in regions with stronger emissions (equating to a 38-69% increase). Of particular interest is the rising importance of India as a source of atmospheric CH2Cl2: based on CARIBIC data we provide regional emission estimates for the Indian subcontinent and show that regional emissions have increased from 3-14 Gg yr-1 (1998-2000) to 16-25 Gg yr-1 (2008). Potential causes of the increasing atmospheric burden of CH2Cl2 are discussed. One possible source is the increased use of CH2Cl2 as a feedstock for the production of HFC-32, a chemical used predominantly as a replacement for ozone-depleting substances in a variety of applications including air conditioners and refrigeration.
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.
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.
We report the first data set of atmospheric abundances for the following four perfluoroalkanes: n-decafluorobutane (n-C4F10), n-dodecafluoropentane (n-C5F12), n-tetradecafluorohexane (n-C6F14) and ...n-hexadecafluoroheptane (n-C7F16). All four compounds could be detected and quantified in air samples from remote locations in the Southern Hemisphere (at Cape Grim, Tasmania, archived samples dating back to 1978) and the upper troposphere (a passenger aircraft flying from Germany to South Africa). Further observations originate from air samples extracted from deep firn in Greenland and allow trends of atmospheric abundances in the earlier 20th century to be inferred. All four compounds were not present in the atmosphere prior to the 1960s. n-C4F10 and n-C5F12 were also measured in samples collected in the stratosphere with the data indicating that they have no significant sinks in this region. Emissions were inferred from these observations and found to be comparable with emissions from the EDGAR database for n-C6F14. However, emissions of n-C4F10, n-C5F12 and n-C7F16 were found to differ by up to five orders of magnitude between our approach and the database. Although the abundances of the four perfluorocarbons reported here are currently small (less than 0.3 parts per trillion) they have strong Global Warming Potentials several thousand times higher than carbon dioxide (on a 100-yr time horizon) and continue to increase in the atmosphere. We estimate that the sum of their cumulative emissions reached 325 million metric tonnes CO2 equivalent at the end of 2009.
The atmospheric records of four halons, H-1211 (CBrClF2), H-1301 (CBrF3), H-2402 (CBrF2CBrF2) and H-1202 (CBr2F2), measured from air collected at Cape Grim, Tasmania, between 1978 and 2011, are ...reported. Mixing ratios of H-1211, H-2402 and H-1202 began to decline in the early to mid-2000s, but those of H-1301 continue to increase up to mid-2011. These trends are compared to those reported by NOAA (National Oceanic and Atmospheric Administration) and AGAGE (Advanced Global Atmospheric Experiment). The observations suggest that the contribution of the halons to total tropospheric bromine at Cape Grim has begun to decline from a peak in 2008 of about 8.1 ppt. An extrapolation of halon mixing ratios to 2060, based on reported banks and predicted release factors, shows this decline becoming more rapid in the coming decades, with a contribution to total tropospheric bromine of about 3 ppt in 2060. Top-down global annual emissions of the halons were derived using a two-dimensional atmospheric model. The emissions of all four have decreased since peaking in the late 1980s–mid-1990s, but this decline has slowed recently, particularly for H-1301 and H-2402 which have shown no decrease in emissions over the past five years. The UEA (University of East Anglia) top-down model-derived emissions are compared to those reported using a top-down approach by NOAA and AGAGE and the bottom-up estimates of HTOC (Halons Technical Options Committee). The implications of an alternative set of steady-state atmospheric lifetimes are discussed. Using a lifetime of 14 yr or less for H-1211 to calculate top-down emissions estimates would lead to small, or even negative, estimated banks given reported production data. Finally emissions of H-1202, a product of over-bromination during the production process of H-1211, have continued despite reported production of H-1211 ceasing in 2010. This raises questions as to the source of these H-1202 emissions.
Air samples collected at Cape Grim, Tasmania between 1978 and 2008 and during a series of more recent aircraft sampling programmes have been analysed to determine the atmospheric abundance and trend ...of octafluorocyclobutane (c-C4F8 or PFC-318). c-C4F8 has an atmospheric lifetime in excess of 3000 yr and a global warming potential (GWP) of 10 300 (100 yr time horizon), making it one of the most potent greenhouse gases detected in the atmosphere to date. The abundance of c-C4F8 in the Southern Hemisphere has risen from 0.35 ppt in 1978 to 1.2 ppt in 2010, and is currently increasing at a rate of around 0.03 ppt yr−1. It is the third most abundant perfluorocarbon (PFC) in the present day atmosphere, behind CF4 (~75 ppt) and C2F6 (~4 ppt). Although a number of potential sources of c-C4F8 have been reported, including the electronics and semi-conductor industries, there remains a large discrepancy in the atmospheric budget. Using a 2-D global model to derive top-down global emissions based on the Cape Grim measurements yields a recent (2007) emission rate of around 1.1 Gg yr−1 and a cumulative emission up to and including 2007 of 38.1 Gg. Emissions reported on the EDGAR emissions database for the period 1986–2005 represent less than 1% of the top-down emissions for the same period, which suggests there is a large unaccounted for source of this compound. It is also apparent that the magnitude of this source has varied considerably over the past 30 yr, declining sharply in the late 1980s before increasing again in the mid-1990s.
The stratospheric degradation of chlorofluorocarbons (CFCs) releases chlorine, which is a major contributor to the destruction of stratospheric ozone (O3). A recent study reported strong chlorine ...isotope fractionation during the breakdown of the most abundant CFC (CFC-12, CCl2F2, Laube et al., 2010a), similar to effects seen in nitrous oxide (N2O). Using air archives to obtain a long-term record of chlorine isotope ratios in CFCs could help to identify and quantify their sources and sinks. We analyse the three most abundant CFCs and show that CFC-11 (CCl3F) and CFC-113 (CClF2CCl2F) exhibit significant stratospheric chlorine isotope fractionation, in common with CFC-12. The apparent isotope fractionation ( epsilon app) for mid- and high-latitude stratospheric samples are respectively -2.4 (0.5) and -2.3 (0.4) ppt for CFC-11, -12.2 (1.6) and -6.8 (0.8) ppt for CFC-12 and -3.5 (1.5) and -3.3 (1.2) ppt for CFC-113, where the number in parentheses is the numerical value of the standard uncertainty expressed in per mil. Assuming a constant isotope composition of emissions, we calculate the expected trends in the tropospheric isotope signature of these gases based on their stratospheric 37Cl enrichment and stratosphere-troposphere exchange. We compare these projections to the long-term delta (37Cl) trends of all three CFCs, measured on background tropospheric samples from the Cape Grim air archive (Tasmania, 1978-2010) and tropospheric firn air samples from Greenland (North Greenland Eemian Ice Drilling (NEEM) site) and Antarctica (Fletcher Promontory site). From 1970 to the present day, projected trends agree with tropospheric measurements, suggesting that within analytical uncertainties, a constant average emission isotope delta ( delta ) is a compatible scenario. The measurement uncertainty is too high to determine whether the average emission isotope delta has been affected by changes in CFC manufacturing processes or not. Our study increases the suite of trace gases amenable to direct isotope ratio measurements in small air volumes (approximately 200 mL), using a single-detector gas chromatography-mass spectrometry (GC-MS) system.
During the Asian monsoon season, greenhouse gases and pollution emitted near the ground are rapidly uplifted by convection up to an altitude of â¼ 13 km, with slower ascent and mixing with the ...stratospheric background above. Here, we address the robustness of the representation of these transport processes in different reanalysis data sets using ERA5, ERA-Interim and ERA5 1"x1". This transport assessment includes the mean age of air from global three-dimensional simulations by the Lagrangian transport model CLaMS (Chemical Lagrangian Model of the Stratosphere), as well as different trajectory-based transport times and associated ascent rates compared with observation-based age of air and ascent rates of long-lived trace gases from airborne measurements during the Asian summer monsoon 2017 in Nepal.
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