Continuous isotopic composition measurements of tropospheric CO₂ at Jungfraujoch (3580 m a.s.l.), Switzerland: real-time observation of regional pollution events

A quantum cascade laser based absorption spectrometer (QCLAS) is applied for the first time to perform in situ, continuous and high precision isotope ratio measurements of CO₂ in the free troposphere. Time series of the three main CO₂ isotopologue mixing ratios (¹²C¹⁶CO₂, ¹³C¹⁶CO₂ and ¹²C¹⁸O¹⁶O) have simultaneously been measured at one second time resolution over two years (from August 2008 to present) at the High Altitude Research Station Jungfraujoch (3580 m a.s.l., Switzerland). This work focuses on periods in February 2009 only, when sudden and pronounced enhancements in the tropospheric CO₂ were observed. These short-term changes were closely correlated with variations in CO mixing ratios measured at the same site, indicating combustion related emissions as potential source. The analytical precision of 0.046‰ (at 50 s integration time) for both δ¹³C and δ¹⁸O and the high temporal resolution allowed the application of the Keeling plot method for source signature identification. The spatial origin of these CO₂ emission sources was then determined by backward Lagrangian particle dispersion simulations

Evaluation of in situ measurements of atmospheric carbon monoxide at Mount Waliguan, China

Quasicontinuous measurements of carbon monoxide (CO) recorded over three years at Mount Waliguan (WLG), a global baseline station in remote western China, were examined using back trajectory analysis. The data include a revision to correct the working reference scale to the WMO2000 scale and corrections for drift in the reference gases. Between July 2004 and June 2007, CO exhibited large fluctuations and the 5 %, 50 % and 95 %-percentiles of relevant CO mixing ratios were 102 ppb, 126 ppb and 194 ppb. Approximately 50 % of all observed data were selected as CO background data using a mathematical procedure of robust local regression, with the remainder affected by regional-scale pollution. The monthly mean background CO mixing ratios showed a minimum in summer and a maximum in late winter, although all seasons were affected by short-term enhancements that exceeded background levels. The CO data were compared to values observed at the high alpine research station at Jungfraujoch, Switzerland. Smaller seasonal amplitudes were observed at WLG compared to the Jungfraujoch due to lower winter and spring CO levels, however, episodic enhancements of polluted air were greater at WLG. The air parcels arriving at WLG came predominately from the west, except in summer when advection from the east and southeast prevailed. Transport from the east or southeast typically brought polluted air to the site, having passed over populated urban areas upwind. A large number of elevated CO mixing ratios could also be associated with advection from the northwest of WLG via the central Xinjiang Uygur Autonomous Region (XUAR) and the Ge'ermu urban area where growing industrial activities as well as crops residue burning provide sources of CO. Air masses passing over northwestern Gansu were associated with relatively high CO values suggesting an anthropogenic influence, which was likely due to anthropogenic emissions from northwestern China (based on back-trajectory and potential source contribution analysis and on the INTEX-B: intercontinental Chemical Transport Experiment-Phase B). Background conditions were observed most frequently in air parcels from remote Tibet west of WLG. The probability that air parcels pass over regions of clean or polluted regions was further identified using potential source contribution function (PSCF) analysis

Assessment of recent advances in measurement techniques for atmospheric carbon dioxide and methane observations

This is the final version. Available from European Geosciences Union via the DOI in this record. Until recently, atmospheric carbon dioxide (CO2) and methane (CH4) measurements were made almost exclusively using nondispersive infrared (NDIR) absorption and gas chromatography with flame ionisation detection (GC/FID) techniques, respectively. Recently, commercially available instruments based on spectroscopic techniques such as cavity ring-down spectroscopy (CRDS), off-axis integrated cavity output spectroscopy (OA-ICOS) and Fourier transform infrared (FTIR) spectroscopy have become more widely available and affordable. This resulted in a widespread use of these techniques at many measurement stations. This paper is focused on the comparison between a CRDS "travelling instrument" that has been used during performance audits within the Global Atmosphere Watch (GAW) programme of the World Meteorological Organization (WMO) with instruments incorporating other, more traditional techniques for measuring CO2 and CH4 (NDIR and GC/FID). We demonstrate that CRDS instruments and likely other spectroscopic techniques are suitable for WMO/GAW stations and allow a smooth continuation of historic CO2 and CH4 time series. Moreover, the analysis of the audit results indicates that the spectroscopic techniques have a number of advantages over the traditional methods which will lead to the improved accuracy of atmospheric CO2 and CH4 measurements

TransCom N2O model inter-comparison - Part 2:Atmospheric inversion estimates of N2O emissions

This study examines N2O emission estimates from five different atmospheric inversion frameworks based on chemistry transport models (CTMs). The five frameworks differ in the choice of CTM, meteorological data, prior uncertainties and inversion method but use the same prior emissions and observation data set. The posterior modelled atmospheric N2O mole fractions are compared to observations to assess the performance of the inversions and to help diagnose problems in the modelled transport. Additionally, the mean emissions for 2006 to 2008 are compared in terms of the spatial distribution and seasonality. Overall, there is a good agreement among the inversions for the mean global total emission, which ranges from 16.1 to 18.7 TgN yr(-1) and is consistent with previous estimates. Ocean emissions represent between 31 and 38% of the global total compared to widely varying previous estimates of 24 to 38%. Emissions from the northern mid- to high latitudes are likely to be more important, with a consistent shift in emissions from the tropics and subtropics to the mid- to high latitudes in the Northern Hemisphere; the emission ratio for 0-30A degrees N to 30-90A degrees N ranges from 1.5 to 1.9 compared with 2.9 to 3.0 in previous estimates. The largest discrepancies across inversions are seen for the regions of South and East Asia and for tropical and South America owing to the poor observational constraint for these areas and to considerable differences in the modelled transport, especially inter-hemispheric exchange rates and tropical convective mixing. Estimates of the seasonal cycle in N2O emissions are also sensitive to errors in modelled stratosphere-to-troposphere transport in the tropics and southern extratropics. Overall, the results show a convergence in the global and regional emissions compared to previous independent studies

Sources and nature of ice-nucleating particles in the free troposphere at Jungfraujoch in winter 2017

Primary ice formation in mixed-phase clouds is initiated by a minute subset of the ambient aerosol population, called ice-nucleating particles (INPs). The knowledge about their atmospheric concentration, composition, and source in cloud-relevant environments is still limited. During the 2017 joint INUIT/CLACE (Ice Nuclei research UnIT/CLoud–Aerosol Characterization Experiment) field campaign, observations of INPs as well as of aerosol physical and chemical properties were performed, complemented by source region modeling. This aimed at investigating the nature and sources of INPs. The campaign took place at the High-Altitude Research Station Jungfraujoch (JFJ), a location where mixed-phase clouds frequently occur. Due to its altitude of 3580 m a.s.l., the station is usually located in the lower free troposphere, but it can also receive air masses from terrestrial and marine sources via long-range transport. INP concentrations were quasi-continuously detected with the Horizontal Ice Nucleation Chamber (HINC) under conditions representing the formation of mixed-phase clouds at −31 ∘C. The INP measurements were performed in parallel to aerosol measurements from two single-particle mass spectrometers, the Aircraft-based Laser ABlation Aerosol MAss Spectrometer (ALABAMA) and the laser ablation aerosol particle time-of-flight mass spectrometer (LAAPTOF). The chemical identity of INPs is inferred by correlating the time series of ion signals measured by the mass spectrometers with the time series of INP measurements. Moreover, our results are complemented by the direct analysis of ice particle residuals (IPRs) by using an ice-selective inlet (Ice-CVI) coupled with the ALABAMA. Mineral dust particles and aged sea spray particles showed the highest correlations with the INP time series. Their role as INPs is further supported by source emission sensitivity analysis using atmospheric transport modeling, which confirmed that air masses were advected from the Sahara and marine environments during times of elevated INP concentrations and ice-active surface site densities. Indeed, the IPR analysis showed that, by number, mineral dust particles dominated the IPR composition (∼58 %), and biological and metallic particles are also found to a smaller extent (∼10 % each). Sea spray particles are also found as IPRs (17 %), and their fraction in the IPRs strongly varied according to the increased presence of small IPRs, which is likely due to an impact from secondary ice crystal formation. This study shows the capability of combining INP concentration measurements with chemical characterization of aerosol particles using single-particle mass spectrometry, source region modeling, and analysis of ice residuals in an environment directly relevant for mixed-phase cloud formation.</p

Long-Term Changes in Lower Tropospheric Baseline Ozone Concentrations:

Two recent papers have quantified long-term ozone (O3) changes observed at northernmidlatitude sites that are believed to represent baseline (here understood as representative of continental to hemispheric scales) conditions. Three chemistry-climate models (NCAR CAM-chem, GFDL-CM3, and GISS-E2-R) have calculated retrospective tropospheric O3 concentrations as part of the Atmospheric Chemistry and Climate Model Intercomparison Project and Coupled Model Intercomparison Project Phase 5 model intercomparisons. We present an approach for quantitative comparisons of model results with measurements for seasonally averaged O3 concentrations. There is considerable qualitative agreement between the measurements and the models, but there are also substantial and consistent quantitative disagreements. Most notably, models (1) overestimate absolute O3 mixing ratios, on average by approximately 5 to 17 ppbv in the year 2000, (2) capture only approximately 50% of O3 changes observed over the past five to six decades, and little of observed seasonal differences, and (3) capture approximately 25 to 45% of the rate of change of the long-term changes. These disagreements are significant enough to indicate that only limited confidence can be placed on estimates of present-day radiative forcing of tropospheric O3 derived from modeled historic concentration changes and on predicted future O3 concentrations. Evidently our understanding of tropospheric O3, or the incorporation of chemistry and transport processes into current chemical climate models, is incomplete. Modeled O3 trends approximately parallel estimated trends in anthropogenic emissions of NO(sub x), an important O3 precursor, while measured O3 changes increase more rapidly than these emission estimates

Inverse modelling of European CH4 emissions during 2006-2012 using different inverse models and reassessed atmospheric observations

We present inverse modelling (top down) estimates of European methane (CH4) emissions for 2006-2012 based on a new quality-controlled and harmonised in situ data set from 18 European atmospheric monitoring stations. We applied an ensemble of seven inverse models and performed four inversion experiments, investigating the impact of different sets of stations and the use of a priori information on emissions.The inverse models infer total CH4 emissions of 26.8 (20.2-29.7) TgCH(4) yr(-1) (mean, 10th and 90th percentiles from all inversions) for the EU-28 for 2006-2012 from the four inversion experiments. For comparison, total anthropogenic CH4 emissions reported to UNFCCC (bottom up, based on statistical data and emissions factors) amount to only 21.3 TgCH(4) yr(-1) (2006) to 18.8 TgCH(4) yr(-1) (2012). A potential explanation for the higher range of top-down estimates compared to bottom-up inventories could be the contribution from natural sources, such as peatlands, wetlands, and wet soils. Based on seven different wetland inventories from the Wetland and Wetland CH4 Inter-comparison of Models Project (WETCHIMP), total wetland emissions of 4.3 (2.3-8.2) TgCH(4) yr(-1) from the EU-28 are estimated. The hypothesis of significant natural emissions is supported by the finding that several inverse models yield significant seasonal cycles of derived CH4 emissions with maxima in summer, while anthropogenic CH4 emissions are assumed to have much lower seasonal variability. Taking into account the wetland emissions from the WETCHIMP ensemble, the top-down estimates are broadly consistent with the sum of anthropogenic and natural bottom-up inventories. However, the contribution of natural sources and their regional distribution remain rather uncertain.Furthermore, we investigate potential biases in the inverse models by comparison with regular aircraft profiles at four European sites and with vertical profiles obtained during the Infrastructure for Measurement of the European Carbon Cycle (IMECC) aircraft campaign. We present a novel approach to estimate the biases in the derived emissions, based on the comparison of simulated and measured enhancements of CH4 compared to the background, integrated over the entire boundary layer and over the lower troposphere. The estimated average regional biases range between -40 and 20% at the aircraft profile sites in France, Hungary and Poland.</p

S. aureus MscL Is a Pentamer In Vivo but of Variable Stoichiometries In Vitro: Implications for Detergent-Solubilized Membrane Proteins

Detergent-induced rearrangements of membrane-protein subunits explain why two MscL channel stoichiometries have been resolved by X-ray crystallography - but S. aureus MscL is truly a pentamer in vivo