ALBERT

Description: 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.

Description: During several balloon flights inside the Arctic polar vortex in early 2003, unusual trace gas distributions were observed, which indicate a strong influence of mesospheric air in the stratosphere. The tuneable diode laser (TDL) instrument SPIRALE (Spectroscopie Infra-Rouge par Absorption de Lasers Embarqués) measured unusually high CO values (up to 600 ppb) on 27 January at about 30 km altitude. The cryosampler BONBON sampled air masses with very high molecular Hydrogen, extremely low SF6 and enhanced CO values on 6 March at about 25 km altitude. Finally, the MIPAS (Michelson Interferometer for Passive Atmospheric Sounding) Fourier Transform Infra-Red (FTIR) spectrometer showed NOy values which are significantly higher than NOy* (the NOy derived from a correlation between N2O and NOy under undisturbed conditions), on 21 and 22 March in a layer centred at 22 km altitude. Thus, the mesospheric air seems to have been present in a layer descending from about 30 km in late January to 25 km altitude in early March and about 22 km altitude on 20 March. We present corroborating evidence from a model study using the KASIMA (KArlsruhe SImulation model of the Middle Atmosphere) model that also shows a layer of mesospheric air, which descended into the stratosphere in November and early December 2002, before the minor warming which occurred in late December 2002 lead to a descent of upper stratospheric air, cutting off a layer in which mesospheric air is present. This layer then descended inside the vortex over the course of the winter. The same feature is found in trajectory calculations, based on a large number of trajectories started in the vicinity of the observations on 6 March. Based on the difference between the mean age derived from SF6 (which has an irreversible mesospheric loss) and from CO2 (whose mesospheric loss is much smaller and reversible) we estimate that the fraction of mesospheric air in the layer observed on 6 March, must have been somewhere between 35% and 100%.

Description: Fourteen global atmospheric transport models were evaluated by comparing the simulation of 222Rn against measurements at three continental stations in Germany: Heidelberg, Freiburg and Schauinsland. Hourly concentrations simulated by the models using a common 222Rn-flux without temporal variations were investigated for 2002 and 2003. We found that the mean simulated concentrations in Heidelberg are related to the diurnal amplitude of boundary layer height in each model. Summer mean concentrations simulated by individual models were negatively correlated with the seasonal mean of diurnal amplitude of boundary layer height, while in winter the correlation was positive. We also found that the correlations between simulated and measured concentrations at Schauinsland were higher when the simulated concentrations were interpolated to the station altitude in most models. Temporal variations of the mismatch between simulated and measured concentrations suggest that there are significant interannual variations in the 222Rn exhalation rate in this region. We found that the local inversion layer during daytime in summer in Freiburg has a significant effect on 222Rn concentrations. We recommend Freiburg concentrations for validation of models that resolve local stable layers and those at Heidelberg for models without this capability.

Description: 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.

Description: The continuous in-situ measurement of δ18O in atmospheric CO2 opens a new door to differentiating between CO2 source and sink components with high temporal resolution. Continuous 13C-CO2 measurement systems have been commercially available already for some time, but until now, only few instruments have been able to provide a continuous measurement of the oxygen isotope ratio in CO2. Besides precise 13C/12C observations, the Fourier Transform InfraRed (FTIR) spectrometer also measures the 18O/16O ratio of CO2, but the precision and accuracy of the measurements has not been evaluated yet. Here we present a first analysis of δ18O-CO2 (and δ13C-CO2) measurements with the FTIR in Heidelberg. We find that our spectrometer measures 18O in CO2 with a reproducibility of better than 0.3‰ at a temporal resolution of less than 10 min, as determined from surveillance gas measurements over a period of ten months. An Allan deviation test shows that the δ18O repeatability reaches 0.15‰ for half-hourly means. The compatibility of our spectroscopic measurements was determined by comparing FTIR measurements of calibration gases and ambient air to mass-spectrometric measurements of flask samples, filled with the cylinder gases or episodically collected over a diurnal cycle (event). We found that direct cylinder gas measurements agree to 0.01 ± 0.04‰ (mean and standard deviation) for δ13C-CO2 and 0.01 ± 0.11‰ for δ18O. Two weekly episodes of recent ambient air measurements, one in winter and one in summer, are discussed in view of the question, which potential insights and new challenges combined highly resolved δ18O-CO2 and δ13C-CO2 records may provide in terms of better understanding regional scale continental carbon exchange processes.

Description: 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.

Description: A 2-month measurement campaign with a Fourier transform infrared analyser as a travelling comparison instrument (TCI) was performed at the Advanced Global Atmospheric Gases Experiment (AGAGE) and World Meteorological Organization (WMO) Global Atmosphere Watch (GAW) station at Mace Head, Ireland. The aim was to evaluate the compatibility of atmospheric methane (CH4), carbon dioxide (CO2) and nitrous oxide (N2O) measurements of the routine station instrumentation, consisting of a gas chromatograph (GC) for CH4 and N2O as well as a cavity ring-down spectroscopy (CRDS) system for CH4 and CO2. The advantage of a TCI approach for quality control is that the comparison covers the entire ambient air measurement system, including the sample intake system and the data evaluation process. For initial quality and performance control, the TCI was run in parallel with the Heidelberg GC before and after the measurement campaign at Mace Head. Median differences between the Heidelberg GC and the TCI were well within the WMO inter-laboratory compatibility target for all three greenhouse gases. At Mace Head, the median difference between the station GC and the TCI were −0.04 nmol mol−1 for CH4 and −0.37 nmol mol−1 for N2O (GC-TCI). For N2O, a similar difference (−0.40 nmol mol−1) was found when measuring surveillance or working gas cylinders with both instruments. This suggests that the difference observed in ambient air originates from a calibration offset that could partly be due to a difference between the WMO N2O X2006a reference scale used for the TCI and the Scripps Institution of Oceanography (SIO-1998) scale used at Mace Head and in the whole AGAGE network. Median differences between the CRDS G1301 and the TCI at Mace Head were 0.12 nmol mol−1 for CH4 and 0.14 μmol mol−1 for CO2 (CRDS G1301 – TCI). The difference between both instruments for CO2 could not be explained, as direct measurements of calibration gases show no such difference. The CH4 differences between the TCI, the GC and the CRDS G1301 at Mace Head are much smaller than the WMO inter-laboratory compatibility target, while this is not the case for CO2 and N2O.

Description: Despite the potential of isotope measurements to improve our understanding of the global atmospheric molecular hydrogen (H2) cycle, few H2 isotope data have been published so far. Now, within the EUROpean network for atmospheric HYDRogen Observations and Studies project (EUROHYDROS), weekly to monthly air samples from six locations in a global sampling network have been analysed for H2 mixing ratio (m(H2)) and the stable isotopic composition of the H2 (δ(D,H2), hereafter referred to as δD). The time series thus obtained now cover one to five years for all stations. This is the largest set of ground station observations of δD so far. Annual average δD values are higher at the Southern Hemisphere (SH) than at the Northern Hemisphere (NH) stations; the maximum is observed at Neumayer (Antarctica), and the minimum at the non-arctic NH stations. The maximum seasonal differences in δD range from ≈18 ‰ at Neumayer to ≈45 ‰ at Schauinsland (Southern Germany); in general, seasonal variability is largest at the NH stations. The timing of minima and maxima differs per station as well. In Alert (Arctic Canada), the variations in δD and m(H2) can be approximated as simple harmonic functions with a ≈5-month relative phase shift. This out-of-phase seasonal behaviour of δD and m(H2) can also be detected, but delayed and with a ≈6-month relative phase shift, at Mace Head and Cape Verde. However, no seasonal δD cycle could be observed at Schauinsland, which likely reflects the larger influence of local sources and sinks at this continental station. At the two SH stations, no seasonal cycle could be detected in the δD data. If it is assumed that the sink processes are the main drivers of the observed seasonality in m(H2) and δD on the NH, the relative seasonal variations can be used to estimate the relative sink strength of the two major sinks, deposition to soils and atmospheric oxidation by the hydroxyl (OH) radical. For the NH coastal and marine stations this analysis suggests that the relative contribution of soil uptake to the total annual H2 removal increases with latitude.

Description: 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.

Description: We present the first reconstruction of the Northern Hemisphere (NH) high latitude atmospheric carbon monoxide (CO) mole fraction from Greenland firn air. Firn air samples were collected at three deep ice core sites in Greenland (NGRIP in 2001, Summit in 2006 and NEEM in 2008). CO records from the three sites agree well with each other as well as with recent atmospheric measurements, indicating that CO is well preserved in the firn at these sites. CO atmospheric history was reconstructed back to the year 1950 from the measurements using a combination of two forward models of gas transport in firn and an inverse model. The reconstructed history suggests that Arctic CO in 1950 was 140–150 nmol mol−1, which is higher than today's values. CO mole fractions rose by 10–15 nmol mol−1 from 1950 to the 1970s and peaked in the 1970s or early 1980s, followed by a ≈ 30 nmol mol−1 decline to today's levels. We compare the CO history with the atmospheric histories of methane, light hydrocarbons, molecular hydrogen, CO stable isotopes and hydroxyl radicals (OH), as well as with published CO emission inventories and results of a historical run from a chemistry-transport model. We find that the reconstructed Greenland CO history cannot be reconciled with available emission inventories unless unrealistically large changes in OH are assumed. We argue that the available CO emission inventories strongly underestimate historical NH emissions, and fail to capture the emission decline starting in the late 1970s, which was most likely due to reduced emissions from road transportation in North America and Europe.