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The aerosol distribution in Europe was simulated with the Community Multiscale Air Quality (CMAQ) model system version 4.5 for the years 2000 and 2001. The results were compared with daily averages of PM<sub>10</sub> measurements taken in the framework of EMEP and with aerosol optical depth (AOD) values measured within AERONET. The modelled total aerosol mass is typically about 30–60% lower than the corresponding measurements. However a comparison of the chemical composition of the aerosol revealed a considerably better agreement between the modelled and the measured aerosol components for ammonium, nitrate and sulfate, which are on average only 15–20% underestimated. Sligthly worse agreement was determined for sea salt, that was only avaliable at two sites. The largest discrepancies result from the aerosol mass which was not chemically specified by the measurements. The agreement between measurements and model is better in winter than in summer. The modelled organic aerosol mass is higher in summer than in winter but it is significantly underestimated by the model. This could be one of the main reasons for the discrepancies between measurements and model results. The other is that primary coarse particles are underestimated in the emissions. The probability distribution function of the PM<sub>10</sub> measurements follows a log-normal distribution at most sites. The model is only able to reproduce this distribution function at non-coastal low altitude stations. The AOD derived from the model results is 20–70% lower than the values observed within AERONET. This is mainly attributed to the missing aerosol mass in the model. The day-to-day variability of the AOD and the log-normal distribution functions are quite well reproduced by the model. The seasonality on the other hand is underestimated by the model results because better agreement is achieved in winter.
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N<sub>2</sub>-broadened half widths and pressure shifts were obtained for transitions in the 2ν<sub>3</sub> methane band. Laboratory measurements recorded at 0.011 cm<sup>−1</sup> resolution with a Bruker 120 HR Fouriertransform spectrometer were analysed from 5860 to 6185 cm<sup>−1</sup>. A 140 cm gas cell was filled with methane at room temperature and N<sub>2</sub> as foreign gas at pressures ranging from 125 to 900 hPa. A multispectrum nonlinear constrained least squares approach based on Optimal Estimation was applied to derive the spectroscopic parameters by simultaneously fitting laboratory spectra at different ambient pressures assuming a Voigt line-shape. At room temperature, the half widths ranged between 0.030 and 0.071 cm<sup>−1</sup> atm<sup>−1</sup>, and the pressure shifts varied from –0.002 to –0.025 cm<sup>−1</sup> atm<sup>−1</sup> for transitions up to J"=10. Especially for higher rotational levels, we find systematically narrower lines than HITRAN predicts. The Q and R branch of the new set of spectroscopic parameters is further tested with ground based direct sun Fourier transform infrared (FTIR) measurements where systematic fit residuals reduce by about a factor of 3–4. We report the implication of those differences on atmospheric methane measurements using high-resolution ground based FTIR measurements as well as low-resolution spectra from the SCanning Imaging Absorption SpectroMeter for Atmospheric ChartographY (SCIAMACHY) instrument onboard ENVISAT. We find that for SCIAMACHY, a latitudinal and seasonally varying bias of about 1% can be introduced by erroneous broadening parameters.
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Despite the acknowledged relevance of aerosol-derived water-soluble organic carbon (WSOC) to climate and biogeochemical cycling, characterization of aerosol WSOC has been limited. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) was utilized in this study to provide detailed molecular level characterization of the high molecular weight (HMW; m/z>223) component of aerosol-derived WSOC collected from rural sites in Virginia and New York, USA. More than 3000 peaks were detected by ESI FT-ICR MS within a m/z range of 223–600 for each sample. Approximately 86% (Virginia) and 78% (New York) of these peaks were assigned molecular formulas using only carbon (C), hydrogen (H), oxygen (O), nitrogen (N), and sulfur (S) as elemental constituents. H/C and O/C molar ratios were plotted on van Krevelen diagrams and indicated a strong contribution of lignin-like and lipid-like compounds to the aerosol-derived WSOC samples. Approximately 1–4% of the peaks in the aerosol-derived WSOC mass spectra were classified as black carbon (BC) on the basis of double bond equivalents calculated from the assigned molecular formulas. In addition, several high-magnitude peaks in the mass spectra of samples from both sites corresponded to molecular formulas proposed in previous secondary organic aerosol (SOA) laboratory investigations indicating that SOAs are important constituents of the WSOC. Overall, ESI FT-ICR MS provides a level of resolution adequate for detailed compositional and source information of the HMW constituents of aerosol-derived WSOC.
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During the INTEX-B (Intercontinental Chemical Transport Experiment)/ MILAGRO (Megacities Initiative: Local and Global Research Observations) experiments in March 2006 and the associated IONS-06 (INTEX Ozonesonde Network Study; <a href="http://croc.gsfc.nasa.gov/intexb/ions06.html" target="_blank">http://croc.gsfc.nasa.gov/intexb/ions06.html</a>), regular ozonesonde launches were made over 15 North American sites. The soundings were strategically positioned to study inter-regional flows and meteorological interactions with a mixture of tropospheric O<sub>3</sub> sources: local pollution; O<sub>3</sub> associated with convection and lightning; stratosphere-troposphere exchange. The variability of tropospheric O<sub>3</sub> over the Mexico City Basin (MCB; 19° N, 99° W) and Houston (30° N, 95° W) is reported here. MCB and Houston profiles displayed a double tropopause in most soundings and a subtropical tropopause layer with frequent wave disturbances, identified through O<sub>3</sub> laminae as gravity-wave induced. Ozonesondes launched over both cities in August and September 2006 (IONS-06, Phase 3) displayed a thicker tropospheric column O<sub>3</sub> (~7 DU or 15–20%) than in March 2006; nearly all of the increase was in the free troposphere. In spring and summer, O<sub>3</sub> laminar structure manifested mixed influences from the stratosphere, convective redistribution of O<sub>3</sub> and precursors, and O<sub>3</sub> from lightning NO. Stratospheric O<sub>3</sub> origins were present in 39% (MCB) and 60% (Houston) of the summer sondes. Comparison of summer 2006 O<sub>3</sub> structure with summer 2004 sondes (IONS-04) over Houston showed 7% less tropospheric O<sub>3</sub> in 2006. This may reflect a sampling contrast, August to mid-September 2006 instead of July-mid August 2004.
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Surface active organic compounds have been observed in marine boundary layer aerosol. Here, we investigate the effect such surfactants have on the uptake of nitric acid (HNO<sub>3</sub>), an important removal reaction of nitrogen oxides in the marine boundary layer. The uptake of gaseous HNO<sub>3</sub> on deliquesced NaCl aerosol was measured in a flow reactor using HNO<sub>3</sub> labelled with the short-lived radioactive isotope <sup>13</sup>N. The uptake coefficient γ on pure deliquesced NaCl aerosol was γ=0.5±0.2 at 60% relative humidity and 30 ppb HNO<sub>3</sub>(g). The uptake coefficient was reduced by a factor of 5–50 when the aerosol was coated with saturated linear fatty acids with carbon chain lengths of 18 and 15 atoms in monolayer quantities. In contrast, neither shorter saturated linear fatty acids with 12 and 9 carbon atoms, nor coatings with the unsaturated oleic acid (C18, cis-double bond) had a detectable effect on the rate of HNO<sub>3</sub> uptake. It is concluded that it is the structure of the monolayers formed, which determines their resistance towards HNO<sub>3</sub> uptake. Fatty acids (C18 and C15), which form a highly ordered film in the so-called liquid condensed state, represent a significant barrier towards HNO<sub>3</sub> uptake, while monolayers of shorter-chain fatty acids (C9, C12) and of the unsaturated oleic acid form a less ordered film in the liquid expanded state and do not hinder the uptake. Similarly, high contents of humic acids in the aerosol, a structurally inhomogeneous, quite water soluble mixture of oxidised high molecular weight organic compounds did not affect HNO<sub>3</sub> uptake. As surfactant films on naturally occurring aerosol are expected to be less structured due to their chemical inhomogeneity, it is likely that their inhibitory effect on HNO<sub>3</sub> uptake is smaller than that observed here for the C15 and C18 fatty acid monolayers.
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We report the first atmospheric observations of the Chlorofluorocarbons (CFCs) trifluorochloroethene, 3-chloropentafluoropropene and 4,4-dichlorohexafluoro-1-butene by means of Gas Chromatography with Electron Capture and Mass Spectrometric detection (GC-ECD-MS) in air samples taken at the Taunus Observatory operated by the University of Frankfurt (Main) and the Jungfraujoch High Altitude Research Station in Switzerland. These substances belong to a class of CFCs containing a double bond and are suspected to originate from the production and thermal degradation of widely used fluoropolymers like polychlorotrifluoroethene (PCTFE). Their atmospheric lifetimes are expected to be rather short. A quantitative calibration could only be derived for trifluorochloroethene but not for the other species by now. Thus, we use a relative sensitivity method to get a first indication of the observed atmospheric abundances. Identification was possible because of an air plume containing high concentrations of these substances. We suggest that the abundances found on this occasion originated from a local source. However, we have also observed the novel CFCs in air masses representative of background conditions, though with much lower concentrations. These species and some of their degradation products are toxic and could also be relevant for stratospheric and tropospheric ozone depletion.
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Lightning NO<sub>x</sub> emissions calculated using the US National Lightning Detection Network data were found to account for 30% of the total NO<sub>x</sub> emissions for July–August 2004, a period chosen both for having higher lightning NO<sub>x</sub> production and high ozone levels, thus maximizing the likelihood that such emissions could impact peak ozone levels. Including such emissions led to modest, but sometimes significant increases in simulated surface ozone when using the Community Multi-scale Air Quality Model (CMAQ). Three model simulations were performed, two with the addition of lightning NO<sub>x</sub> emissions, and one without. Domain-wide daily maximum 8-h ozone changes due to lightning NO<sub>x</sub> were less than 2 ppbv in 71% of the cases with a maximum of 10 ppbv; whereas the difference in 1-h ozone was less than 2 ppbv in 77% of the cases with a maximum of 6 ppbv. Daily maximum 1-h and 8-h ozone for grids containing O<sub>3</sub> monitoring stations changed slightly, with more than 43% of the cases differing less than 2 ppbv. The greatest differences were 42 ppbv for both 1-h and 8-h O<sub>3</sub>, though these tended to be on days of lower ozone. Lightning impacts on the season-wide maximum 1-h and 8-h averaged ozone decreased starting from the 1st to 4th highest values (an average of 4th highest, 8-h values is used for attainment demonstration in the US). Background ozone values from the y-intercept of O<sub>3</sub> versus NO<sub>z</sub> curve were 42.2 and 43.9 ppbv for simulations without and with lightning emissions, respectively. Results from both simulations with lightning NO<sub>x</sub> suggest that while North American lightning production of NO<sub>x</sub> can lead to significant local impacts on a few occasions, they will have a relatively small impact on typical maximum levels and determination of Policy Relevant Background levels.
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This study presents the complementary picture of the pollution outflow provided by several satellite observations of carbon monoxide (CO), based on different observation techniques. This is illustrated by an analysis of the Asian outflow during the spring of 2005, through comparisons with simulations by the LMDz-INCA global chemistry transport model. The CO observations from the MOPITT and SCIAMACHY nadir sounders, which provide vertically integrated information with excellent horizontal sampling, and from the ACE-FTS solar occultation instrument, which has limited spatial coverage but allows the retrieval of vertical profiles, are used. Combining observations from MOPITT (mainly sensitive to the free troposphere) and SCIAMACHY (sensitive to the full column) allows a qualitative evaluation of the boundary layer CO. The model tends to underestimate this residual compared to the observations, suggesting underestimated emissions, especially in eastern Asia. However, a better understanding of the consistency and possible biases between the MOPITT and SCIAMACHY CO is necessary for a quantitative evaluation. Underestimated emissions, and possibly too low lofting and underestimated chemical production in the model, lead to an underestimate of the export to the free troposphere, as highlighted by comparisons with MOPITT and ACE-FTS. Both instruments observe large trans-Pacific transport extending from ~20° N to ~60° N, with high upper tropospheric CO observed by ACE-FTS above the eastern Pacific (with values of up to 300 ppbv around 50° N at 500 hPa and up to ~200 ppbv around 30° N at 300 hPa). The low vertical and horizontal resolutions of the global model do not allow the simulation of the strong enhancements in the observed plumes. However, the transport patterns are well captured, and are mainly attributed to export from eastern Asia, with increasing contributions from South Asia and Indonesia towards the tropics. Additional measurements of C<sub>2</sub>H<sub>2</sub>, C<sub>2</sub>H<sub>6</sub> and HCN by ACE-FTS provide further information on the plume history. C<sub>2</sub>H<sub>2</sub> and C<sub>2</sub>H<sub>6</sub> enhancements are well correlated with the CO plumes, indicating common sources and rapid trans-Pacific transport. HCN observations show that the biomass burning contributes mainly at latitudes lower than ~40° N. This study provides a first step towards a full combination of complementary observations, but also highlights the need for a better evaluation of consistency between the datasets in order to allow precise quantitative analyses.
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A new process is presented by which water soluble organics might influence ice nucleation, ice growth, chemical reactions and water uptake of aerosols in the upper troposphere: the formation of glassy aerosol particles. Glasses are disordered amorphous (non-crystalline) solids that form when a liquid is cooled without crystallization until the viscosity increases exponentially and molecular diffusion practically ceases. The glass transition temperatures, <i>T</i><sub>g</sub>, homogeneous ice nucleation temperatures, <i>T</i><sub>hom</sub>, and ice melting temperatures, <i>T</i><sub>m</sub>, of various aqueous inorganic, organic and multi-component solutions are investigated with a differential scanning calorimeter. The investigated solutes are: various polyols, glucose, raffinose, levoglucosan, an aromatic compound, sulfuric acid, ammonium bisulfate and mixtures of dicarboxylic acids (M5), of dicarboxylic acids and ammonium sulfate (M5AS), of two polyols, of glucose and ammonium nitrate, and of raffinose and M5AS. The results indicate that aqueous solutions of the investigated inorganic solutes show <i>T</i><sub>g</sub> values that are too low to be of atmospheric importance. In contrast, aqueous organic and multi-component solutions readily form glasses at low but atmospherically relevant temperatures (≤230 K). To apply the laboratory data to the atmospheric situation, the measured phase transition temperatures were transformed from a concentration to a water activity scale by extrapolating water activities determined between 252 K and 313 K to lower temperatures. The obtained state diagrams reveal that the higher the molar mass of the aqueous organic or multi-component solutes, the higher <i>T</i><sub>g</sub> of their respective solutions at a given water activity. To a lesser extent, <i>T</i><sub>g</sub> also depends on the hydrophilicity of the organic solutes. Therefore, aerosol particles containing larger (≳150 g mol<sup>−1</sup>) and more hydrophobic organic molecules are more likely to form glasses at intermediate to high relative humidities in the upper troposphere. Our results suggest that the water uptake of aerosols, heterogeneous chemical reactions in aerosol particles, as well as ice nucleation and ice crystal growth can be significantly impeded or even completely inhibited in organic-enriched aerosols at upper tropospheric temperatures with implications for cirrus cloud formation and upper tropospheric relative humidity.
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In the tropics, deep convection is the major source of uncertainty in water vapor transport to the upper troposphere and into the stratosphere. Although accurate measurements in this region would be of first order importance to better understand the processes that govern stratospheric water vapor concentrations and trends in the context of a changing climate, they are sparse because of instrumental shortcomings and observational challenges. Therefore, the Falcon research aircraft of the Deutsches Zentrum für Luft- und Raumfahrt (DLR) flew a zenith-viewing water vapor differential absorption lidar (DIAL) during the Tropical Convection, Cirrus and Nitrogen Oxides Experiment (TROCCINOX) in 2004 and 2005 in Brazil. The measurements were performed alternatively on three water vapor absorption lines of different strength around 940 nm. These are the first aircraft DIAL measurements in the tropical upper troposphere and in the mid-latitudes lower stratosphere. Sensitivity analyses reveal an accuracy of 5% between altitudes of 8 and 16 km. This is confirmed by intercomparisons with the Fast In-situ Stratospheric Hygrometer (FISH) and the Fluorescent Advanced Stratospheric Hygrometer (FLASH) onboard the Russian M-55 Geophysica research aircraft during five coordinated flights. The average relative differences between FISH and DIAL amount to −3%±8% and between FLASH and DIAL to −8%±14%, negative meaning DIAL is more humid. The average distance between the probed air masses was 129 km. The DIAL is found to have no altitude- or latitude-dependent bias. A comparison with the balloon ascent of a laser absorption spectrometer gives an average difference of 0%±19% at a distance of 75 km. Six tropical DIAL under-flights of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on board ENVISAT reveal a mean difference of −8%±49% at an average distance of 315 km. While the comparison with MIPAS is somewhat less significant due to poorer comparison conditions, the agreement with the in-situ hygrometers provides evidence of the excellent quality of FISH, FLASH and DIAL. Most DIAL profiles exhibit a smooth exponential decrease of water vapor mixing ratio in the tropical upper troposphere to lower stratosphere transition. The hygropause with a minimum mixing ratio of 2.5 µmol/mol is found between 15 and 17 km. A high-resolution (2 km horizontal, 0.2 km vertical) DIAL cross section through the anvil outflow of tropical convection shows that the ambient humidity is increased by a factor of three across 100 km.
