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Chemical composition, size, and mixing state of atmospheric particles are critical in determining their effects on the environment. There is growing evidence that soot aerosols play a particularly important role in both climate and human health, but still relatively little is known of their physical and chemical nature. In addition, the atmospheric residence times and removal mechanisms for soot are neither well understood nor adequately represented in regional and global climate models. To investigate the effect of locality and residence time on properties of soot and mixing state in a polluted urban environment, particles of diameter 0.2–2.0 μm were collected in the Mexico City Metropolitan Area (MCMA) during the MCMA-2003 Field Campaign from various sites within the city. Individual particle analysis by different electron microscopy methods coupled with energy dispersed x-ray spectroscopy, and secondary ionization mass spectrometry show that freshly-emitted soot particles become rapidly processed in the MCMA. Whereas fresh particulate emissions from mixed-traffic are almost entirely carbonaceous, consisting of soot aggregates with liquid coatings suggestive of unburned lubricating oil and water, ambient soot particles which have been processed for less than a few hours are heavily internally mixed, primarily with ammonium sulfate. Single particle analysis suggests that this mixing occurs through several mechanisms that require further investigation. In light of previously published results, the internally-mixed nature of processed soot particles is expected to affect heterogeneous chemistry on the soot surface, including interaction with water during wet-removal.
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The IFE-1.6 scientific data set of SCIAMACHY limb ozone profiles is validated for the period August–December 2002. The data set provides ozone profiles over an altitude range of 15–45 km. The main uncertainty in the profiles is the imprecise knowledge of the pointing of the instrument, leading to retrieved profiles that are shifted in altitude direction. To obtain a first order correction for the pointing error and the remaining uncertainties, the retrieved profiles are compared to their a-priori value and ozone sondes based on absolute distance and equivalent latitude criteria. A vertical shift of the satellite profiles with 2 km downward is found to be an appropriate correction for the data set studied. A total root-mean-square difference between limb profiles and sondes of 10–15% remains for the stratospheric ozone profile after application of the correction. Small biases are left above and below the ozone maximum at mid latitudes, where the vertical gradients in the retrieved product are in general too strong.
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Number concentrations of total and non-volatile aerosol particles with size diameters >0.01 μm as well as particle size distributions (0.4–23 μm diameter) were measured in situ in the Arctic lower stratosphere (10–20.5 km altitude). The measurements were obtained during the campaigns European Polar Stratospheric Cloud and Lee Wave Experiment (EUPLEX) and Envisat-Arctic-Validation (EAV). The campaigns were based in Kiruna, Sweden, and took place from January to March 2003. Measurements were conducted onboard the Russian high-altitude research aircraft Geophysica using the low-pressure Condensation Nucleus Counter COPAS (COndensation PArticle Counter System) and a modified FSSP 300 (Forward Scattering Spectrometer Probe). Around 18–20 km altitude typical total particle number concentrations <i>n<sub>t</sub></i> range at 10–20 cm<sup>−3</sup> (ambient conditions). Correlations with the trace gases nitrous oxide (N<sub>2</sub>O) and trichlorofluoromethane (CFC-11) are discussed. Inside the polar vortex the total number of particles >0.01 μm increases with potential temperature while N<sub>2</sub>O is decreasing which indicates a source of particles in the above polar stratosphere or mesosphere. A separate channel of the COPAS instrument measures the fraction of aerosol particles non-volatile at 250°C. Inside the polar vortex a much higher fraction of particles contained non-volatile residues than outside the vortex (~67% inside vortex, ~24% outside vortex). This is most likely due to a strongly increased fraction of meteoric material in the particles which is transported downward from the mesosphere inside the polar vortex. The high fraction of non-volatile residual particles gives therefore experimental evidence for downward transport of mesospheric air inside the polar vortex. It is also shown that the fraction of non-volatile residual particles serves directly as a suitable experimental vortex tracer. Nanometer-sized meteoric smoke particles may also serve as nuclei for the condensation of gaseous sulfuric acid and water in the polar vortex and these additional particles may be responsible for the increase in the observed particle concentration at low N<sub>2</sub>O. The number concentrations of particles >0.4 μm measured with the FSSP decrease markedly inside the polar vortex with increasing potential temperature, also a consequence of subsidence of air from higher altitudes inside the vortex. Another focus of the analysis was put on the particle measurements in the lowermost stratosphere. For the total particle density relatively high number concentrations of several hundred particles per cm<sup>3</sup> at altitudes below ~14 km were observed in several flights. To investigate the origin of these high number concentrations we conducted air mass trajectory calculations and compared the particle measurements with other trace gas observations. The high number concentrations of total particles in the lowermost stratosphere are probably caused by transport of originally tropospheric air from lower latitudes and are potentially influenced by recent particle nucleation.
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Simulations of Arctic denitrification using a 3-D chemistry-microphysics transport model are compared with observations for the winters 1994/95, 1996/97 and 1999/2000. The model of Denitrification by Lagrangian Particle Sedimentation (DLAPSE) couples the full chemical scheme of the 3-D chemical transport model, SLIMCAT, with a nitric acid trihydrate (NAT) growth and sedimentation scheme. We use observations from the Microwave Limb Sounder (MLS) and Improved Limb Atmospheric Sounder (ILAS) satellite instruments, the balloon-borne Michelsen Interferometer for Passive Atmospheric Sounding (MIPAS-B), and the in situ NO<sub>y</sub> instrument on-board the ER-2. As well as directly comparing model results with observations, we also assess the extent to which these observations are able to validate the modelling approach taken. For instance, in 1999/2000 the model captures the temporal development of denitrification observed by the ER-2 from late January into March. However, in this winter the vortex was already highly denitrified by late January so the observations do not provide a strong constraint on the modelled rate of denitrification. The model also reproduces the MLS observations of denitrification in early February 2000. In 1996/97 the model captures the timing and magnitude of denitrification as observed by ILAS, although the lack of observations north of ~67° N in the beginning of February make it difficult to constrain the actual timing of onset. The comparison for this winter does not support previous conclusions that denitrification must be caused by an ice-mediated process. In 1994/95 the model notably underestimates the magnitude of denitrification observed during a single balloon flight of the MIPAS-B instrument. Agreement between model and MLS HNO<sub>3</sub> at 68 hPa in mid-February 1995 is significantly better. Sensitivity tests show that a 1.5 K overall decrease in vortex temperatures, or a factor 4 increase in assumed NAT nucleation rates, produce the best statistical fit to MLS observations. Both adjustments would be required to bring the model into agreement with the MIPAS-B observations. The agreement between the model and observations suggests that a NAT-only denitrification scheme (without ice), which was discounted by previous studies, must now be considered as one mechanism for the observed Arctic denitrification. The timing of onset and the rate of denitrification remain poorly constrained by the available observations.
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Airborne measurements of aerosol particle size distributions were made in the Mexican Intertropical Convergence Zone. The volume concentrations of submicron and super micron particles at cloud base were compared with those in near-cloud regions over a range of altitudes. Of 78 near-cloud regions analyzed, 68% and 45% had enhanced volumes of submicron particles and supermicron particles, respectively. In addition, 35% of these regions had supermicron particles removed, presumably by precipitation. In 61% of the cases the enhancement in volume occurred over the size range from 0.1 to 50 μm whereas only submicron volumes were enhanced in 35% of the cases. In regions near clouds that were formed in air of maritime origin the frequency of volume enhancement decreased with increasing altitude and was twice as frequent on the dissipating side of clouds compared to the growing side. No such differences were found in the regions near clouds formed in air originating from the land. The frequency and average magnitude of volume enhancement are in qualitative and quantitative agreement with previous observational and theoretical studies that relate enhancements in particle mass to the uptake by cloud droplets of SO<sub>2</sub> accompanied by additional growth by droplet coalescence.
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The aerosol in the Amazon basin is dominated throughout the year by organic matter, for the most part soluble in water. In this modeling study, we show how the knowledge of water-soluble organic compounds (WSOC) and the associated physical and chemical properties (e.g. solubility, surface tension, dissociation into ions) affect the hygroscopic growth and activation of the aerosol in this area. The study is based on data obtained during the SMOCC field experiment carried out in Rondônia, Brazil, over a period encompassing the dry (biomass burning) season to the onset of the wet season (September to mid-November, 2002). The comparison of predicted and measured cloud condensation nuclei (CCN) number concentration shows that the knowledge of aerosol WSOC composition in terms of classes of compounds and of their relative molecular weights and acidic properties may be sufficient to predict aerosol activation, without any information on solubility. Conversely, the lack of knowledge on WSOC solubility leads to a high overestimation of the observed diameter growth factors (DGF) by the theory. Moreover, the aerosol water soluble inorganic species fail to predict both DGFs and CCN number concentration. In fact, this study shows that a good reproduction of the measured DGF and CCN concentration is obtained if the chemical composition of aerosol, especially that of WSOC, is appropriately taken into account in the calculations. New parameterizations for the computed CCN spectra are also derived which take into account the variability caused by chemical effects (surface tension, molecular composition, solubility, degree of dissociation of WSOC).
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The wintertime ozone buildup over the Northern Hemisphere (NH) midlatitudes and its connection with the mean meridional circulation in the stratosphere are examined statistically on a monthly basis from October to March (1980–2002). The ozone buildup begins locally in October with positive total ozone tendencies over the North Pacific, which spread eastward and westward in November and finally cover all midlatitudes in December. The local onset of the buildup in October is not evident in zonal mean ozone tendency, which is close to zero. From November to March, zonal mean total ozone tendency (50°–60° N) shows a strong correlation (|r|=0.7) with several zonal mean parameters associated to the mean meridional circulation, namely: eddy heat flux, temperature tendency, the vertical residual velocity and the residual streamfunction. At the same time, on the latitude-altitude cross section, correlation patterns between ozone tendency and widely used eddy heat flux are not uniform during winter. The strongest correlations are located equatorward (almost throughout the stratosphere) or poleward (only in the lower stratosphere) of the edge of the polar vortex. Such distribution may depend on the existence of the midlatitude and polar waveguides which defined refraction of upward propagating waves from the troposphere either to the midlatitude stratosphere or to the polar stratosphere. As a consequence of the nonuniform correlation patterns, heat flux averaged over the common region 45°–75° N, 100 hPa is not always an optimum proxy for statistical models describing total ozone variability in midlatitudes. Other parameters approximating the strength of the mean meridional circulation have more uniform and stable correlation patterns with ozone tendency during winter. We show that the NH midlatitude ozone buildup has a stable statistical relationship with the mean meridional circulation in all months from October to March and half of the interannual variability in monthly ozone tendencies can be explained by applying different proxies of the mean meridional circulation.
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Laboratory absorption spectra of peroxyacetyl nitrate (PAN, CH<sub>3</sub>C(O)OONO<sub>2</sub>) vapour have been measured in the mid-infrared range 550 cm<sup>-1</sup> to 1400 cm<sup>-1</sup> (18.2 to 7.14 µm) at both 250 K and 273 K, using a Fourier transform infrared spectrometer at a nominal spectral resolution of 0.25 cm<sup>-1</sup> (unapodised). In addition, the 1600 cm<sup>-1</sup> to 2200 cm<sup>-1</sup> (6.25 to 4.54 µm) spectral region has been measured at 250 K. Cross-sectional data at each temperature, as well as integrated band intensities and peak infrared absorptivities for nine absorption bands of PAN in this spectral range, have been derived from a total of twelve separately measured PAN transmission spectra. A general increase in the peak absorption cross-section for all bands is noted with decreasing temperature, with cross-sectional increases in the range 6% (for the 1842 cm<sup>-1</sup> band) and 30% (for the 991 cm<sup>-1</sup> band) at 250K, relative to those previously reported at 295K. Differences in integrated band intensities range from -22% to +16% for the 1741 cm<sup>-1</sup> and 991 cm<sup>-1</sup> bands respectively over the same temperature range. These new absorption cross-sections for PAN are the first to be reported at temperatures below 295 K, allowing the possibility of improved retrievals of the atmospherically important PAN species from remotely sensed infrared spectra of the cold upper troposphere. These new cross-sectional data accompany this paper as an electronic supplement.
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This paper presents an inverse method for inferring trace gas fluxes at high temporal (daily) and spatial (model grid) resolution from continuous atmospheric concentration measurements. The method is designed for regional applications and for use in intensive campaigns. We apply the method to a one month inversion of fluxes over Europe. We show that the information added by the measurements depends critically on the smoothness constraint assumed among the source components. We show that the initial condition affects the inversion for 20 days, provided one has enough observing sites to constrain regional fluxes. We show that the impact of the far-field fluxes grows throughout the inversion and hence a reasonable global flux field is a prerequisite for a regional inversion.
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The European PartEmis project (Measurement and prediction of emissions of aerosols and gaseous precursors from gas turbine engines) was focussed on the characterisation and quantification of exhaust emissions from a gas turbine engine. The combustion aerosol characterisation included on-line measurements of mass and number concentration, size distribution, mixing state, thermal stability of internally mixed particles, hygroscopicity, cloud condensation nuclei (CCN) activation potential, and off-line analysis of chemical composition. Based on this extensive data set, the role of sulphuric acid coating and of the organic fraction of the combustion particles for the CCN activation was investigated. Modelling of CCN activation was conducted using microphysical and chemical properties obtained from the measurements as input data. Coating the combustion particles with water-soluble sulphuric acid, increases the potential CCN activation, or lowers the activation diameter, respectively. The adaptation of a Köhler model to the experimental data yielded coatings from 0.1 to 3 vol-% of water-soluble matter, which corresponds to an increase in the fraction of CCN-activated combustion particles from ≤10<sup>−4</sup> to ≌10<sup>−2</sup> at a water vapour saturation ratio S<sub>w</sub>=1.006. Additional particle coating by coagulation of combustion particles and aqueous sulphuric acid particles formed by nucleation further reduces the CCN activation diameter. In contrast, particles containing a large fraction of non-volatile organic compounds grow significantly less at high relative humidity than particles with a lower content of non-volatile OC. The resulting reduction in the potential CCN activation with an increasing fraction of non-volatile OC becomes visible as a trend in the experimental data. While a coating of water-soluble sulphuric acid increases the potential CCN activation, or lowers the activation diameter, respectively, the non-volatile organic compounds, mainly found at lower combustion temperatures, can partially compensate this sulphuric acid-related enhancement of CCN activation of carbonaceous combustion aerosol particles.
