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In the 2002 Antarctic polar vortex enhanced HOCl mixing ratios were detected by the Michelson Interferometer for Passive Atmospheric Sounding both at altitudes of around 35 km (1000 K potential temperature), where HOCl abundances are ruled by gas phase chemistry and at around 18–24 km (475–625 K), which belongs to the altitude domain where heterogeneous chlorine chemistry is relevant. At altitudes of 33 to 40 km polar vortex HOCl mixing ratios were found to be around 0.14 ppbv as long as the polar vortex was intact, centered at the pole, and thus received relatively little sunlight. This is the altitude region where in midlatitudinal and tropic atmospheres peak HOCl mixing ratios significantly above 0.2 ppbv (in terms of daily mean values) are observed. After deformation and displacement of the polar vortex in the course of a major warming, ClO-rich vortex air was more exposed to sunlight, where enhanced HO<sub>x</sub> abundances led to largely increased HOCl mixing ratios (up to 0.3 ppbv), exceeding typical midlatitudinal and tropical amounts significantly. The HOCl increase was preceded by an increase of ClO. Model runs could reproduce these measurements only when the Stimpfle et al. (1979) rate constant for the reaction ClO+HO<sub>2</sub>→HOCl+O<sub>2</sub> was used but not with the current JPL recommendation. At an altitude of 24 km, HOCl mixing ratios of up to 0.15 ppbv were detected. This HOCl enhancement, which is already visible in 18 September data, is attributed to heterogeneous chemistry, which is in agreement with observations of polar stratospheric clouds. The measurements were compared to a model run where no polar stratospheric clouds appeared during the observation period. The fact that HOCl still was produced in the model run suggests that a significant part of HOCl was generated from ClO rather than directly via heterogeneous reaction. Excess ClO, lower ClONO<sub>2</sub> and earlier loss of HOCl in the measurements are attributed to ongoing heterogeneous chemistry which is not reproduced by the model. On 11 October, polar vortex mean daytime mixing ratios were only 0.03 ppbv.
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Ice crystals, also known as diamond dust, are suspended in the boundary layer air under clear sky conditions during most of the Arctic winter in Northern Canada. Occasionally ice crystal events can produce significantly thick layers with optical depths in excess of 2.0 even in the absence of liquid water clouds. Four case studies of high optical depth ice crystal events at Eureka in the Nunavut Territory of Canada during the winter of 2006/07 are presented. They show that the measured ice crystal surface infrared downward radiative forcing ranged from 8 to 36 W m<sup>−2</sup> in the wavelength band from 5.6 to 20 μm for 532 nm optical depths ranging from 0.2 to 1.7. MODIS infrared and visible images and the operational radiosonde wind profile were used to show that these high optical depth events were caused by surface snow being blown off 600 to 800 m high mountain ridges about 20 to 30 km North-West of Eureka and advected by the winds towards Eureka as they settled towards the ground within the highly stable boundary layer. This work presents the first study that demonstrates the important role that surrounding topography plays in determining the occurrence of high optical depth ice crystal events from residual blowing snow that becomes a source of boundary layer ice crystals distinct from the classical diamond dust phenomenon.
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Nitrate compounds have received much attention because of their ability to alter the hygroscopic properties and cloud condensation nuclei (CCN) activity of mineral dust particles in the atmosphere. However, very little is known about specific characteristics of ambient nitrate-coated mineral particles on an individual particle scale. In this study, sample collection was conducted during brown haze and dust episodes between 24 May and 21 June 2007 in Beijing, northern China. Sizes, morphologies, and compositions of 332 mineral dust particles together with their coatings were analyzed using transmission electron microscopy (TEM) coupled with energy-dispersive X-ray (EDX) microanalyses. Structures of some mineral particles were verified using selected-area electron diffraction (SAED). TEM observation indicates that approximately 90% of the collected mineral particles are covered by visible coatings in haze samples whereas only 5% are coated in the dust sample. 92% of the analyzed mineral particles are covered with Ca-, Mg-, and Na-rich coatings, and 8% are associated with K- and S-rich coatings. The majority of coatings contain Ca, Mg, O, and N with minor amounts of S and Cl, suggesting that they are possibly nitrates mixed with small amounts of sulfates and chlorides. These nitrate coatings are strongly correlated with the presence of alkaline mineral components (e.g., calcite and dolomite). CaSO<sub>4</sub> particles with diameters from 10 to 500 nm were also detected in the coatings including Ca(NO<sub>3</sub>)<sub>2</sub> and Mg(NO<sub>3</sub>)<sub>2</sub>. Our results indicate that mineral particles in brown haze episodes were involved in atmospheric heterogeneous reactions with two or more acidic gases (e.g., SO<sub>2</sub>, NO<sub>2</sub>, HCl, and HNO<sub>3</sub>). Mineral particles that acquire hygroscopic nitrate coatings tend to be more spherical and larger, enhancing their light scattering and CCN activity, both of which have cooling effects on the climate.
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MIPAS is a Fourier transform spectrometer, operating onboard of the ENVISAT satellite since July 2002. The online retrieval algorithm produces geolocated profiles of temperature and of volume mixing ratios of six key atmospheric constituents: H<sub>2</sub>O, O<sub>3</sub>, HNO<sub>3</sub>, CH<sub>4</sub>, N<sub>2</sub>O and NO<sub>2</sub>. In the validation phase, oscillations beyond the error bars were observed in several profiles, particularly in CH<sub>4</sub> and N<sub>2</sub>O. <br><br> To tackle this problem, a Tikhonov regularization scheme has been implemented in the retrieval algorithm. The applied regularization is however rather weak in order to preserve the vertical resolution of the profiles. <br><br> In this paper we present a self-adapting and altitude-dependent regularization approach that detects whether the analyzed observations contain information about small-scale profile features, and determines the strength of the regularization accordingly. The objective of the method is to smooth out artificial oscillations as much as possible, while preserving the fine detail features of the profile when related information is detected in the observations. <br><br> The proposed method is checked for self consistency, its performance is tested on MIPAS observations and compared with that of some other regularization schemes available in the literature. In all the considered cases the proposed scheme achieves a good performance, thanks to its altitude dependence and to the constraints employed, which are specific of the inversion problem under consideration. The proposed method is generally applicable to iterative Gauss-Newton algorithms for the retrieval of vertical distribution profiles from atmospheric remote sounding measurements.
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Binary heterogeneous nucleation of water-succinic/glutaric/malonic/adipic acid on nanometer-sized particles is investigated within the frame of classical heterogeneous nucleation theory. Homogeneous nucleation is also included for comparison. It is found that the nucleation probabilities depend on the contact angle and on the size of the seed particles. New thermodynamical properties, such as saturation vapor pressure, density and surface tension for all the dicarboxylic acid aqueous solutions are included in the calculations. While the new surface tension and density formulations do not bring any significant difference in the computed nucleation rate for homogeneous nucleation for succinic and glutaric acids, the use of the newly derived equations for the vapor pressure decrease the acid concentrations in gas phase by 3 orders of magnitude. According to our calculations, the binary heterogeneous nucleation of succinic acid-water and glutaric acid-water – although it requires a 3–4 orders of magnitude lower vapor concentrations than the homogeneous nucleation – cannot take place under atmospheric conditions. On the other hand binary homogeneous nucleation of adipic acid-water systems might be possible under conditions occuring in upper boundary layer. However, a more detailed characterization of the interaction between the surface and the molecules of the nucleating vapor should be considered in the future.
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Ships modify cloud microphysics by adding cloud condensation nuclei (CCN) to a developing or existing cloud. These create lines of larger reflectance in cloud fields that are observed in satellite imagery. An algorithm has been developed to automate the detection of ship tracks in Along Track Scanning Radiometer 2 (ATSR-2) imagery. The scheme has been integrated into the Global Retrieval of ATSR Cloud Parameters and Evaluation (GRAPE) processing chain. The algorithm firstly identifies intensity ridgelets in clouds which have the potential to be part of a ship track. This identification is done by comparing each pixel with its surrounding ones. If the intensity of three adjacent pixels is greater than the intensity of their neighbours, then it is classified as a ridgelet. These ridgelets are then connected together, according to a set of connectivity rules, to form tracks which are classed as ship tracks if they are long enough. The algorithm has been applied to two years of ATSR-2 data. Ship tracks are most frequently seen off the west coast of California, and the Atlantic coast of both West Africa and South-Western Europe. The global distribution of ship tracks shows strong seasonality, little inter-annual variability and a similar spatial pattern to the distribution of ship emissions.
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Classification of Australian continental aerosol types resulting from episodes of enhanced source activity, such as smoke plumes and dust outbreaks, is carried out via cluster analysis of optical properties obtained from inversion of sky radiance distributions at Australian aerosol ground stations using data obtained over the last decade. The cluster analysis distinguishes four significant classes, which are identified on the basis of their optical properties and provenance as determined by satellite imagery and back-trajectory analysis. The four classes are identified respectively as aged smoke, fresh smoke, coarse dust and a super-absorptive aerosol. While the first three classes show similarities with comparable aerosol types identified elsewhere, the super-absorptive aerosol has no obvious foreign prototype. The class identified as coarse dust shows a prominent depression in single scattering albedo in the blue spectral region due to absorption by hematite, which is shown to be more abundant in central Australian dust relative to the "dust belt"of the Northern Hemisphere. The super-absorptive class is distinctive in view of its very low single scattering albedo (~0.7 at 500 nm) and variable enhanced absorption at 440 nm. The strong absorption by this aerosol requires a high black carbon content while the enhanced blue-band absorption may derive from organic compounds emitted during the burning of specific vegetation types. This aerosol exerts a positive radiative forcing at the top of atmosphere (TOA), with a large deposition of energy in the atmosphere per unit aerosol optical depth. This contrasts to the other three classes where the TOA forcing is negative. Optical properties of the four types will be used to improve the representation of Australian continental aerosol in climate models, and to enhance the accuracy of satellite-based aerosol retrievals over Australia.
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The lightest Non Methane HydroCarbon (NMHC), i.e., acetylene (C<sub>2</sub>H<sub>2</sub>) is found to form secondary organic aerosol (SOA). Contrary to current belief, the number of carbon atoms, <i>n</i>, for a NMHC to act as SOA precursor is lowered to <i>n</i>=2 here. The OH-radical initiated oxidation of C<sub>2</sub>H<sub>2</sub> forms glyoxal (CHOCHO) as the highest yield product, and >99% of the SOA from C<sub>2</sub>H<sub>2</sub> is attributed to CHOCHO. SOA formation from C<sub>2</sub>H<sub>2</sub> and CHOCHO was studied in a photochemical and a dark simulation chamber. Further, the experimental conditions were varied with respect to the chemical composition of the seed aerosols, mild acidification with sulphuric acid (SA, 3<pH<4), and relative humidity (10<RH<90%). The rate of SOA formation is found enhanced by several orders of magnitude in the photochemical system. The SOA yields (<i>Y</i><sub>SOA</sub>) ranged from 1% to 24% and did not correlate with the organic mass portion of the seed, but increased linearly with liquid water content (LWC) of the seed. For fixed LWC, <i>Y</i><sub>SOA</sub> varied by more than a factor of five. Water soluble organic carbon (WSOC) photochemistry in the liquid water associated with internally mixed inorganic/WSOC seed aerosols is found responsible for this seed effect. WSOC photochemistry enhances the SOA source from CHOCHO, while seeds containing amino acids (AA) and/or SA showed among the lowest of all <i>Y</i><sub>SOA</sub> values, and largely suppress the photochemical enhancement on the rate of CHOCHO uptake. Our results give first evidence for the importance of heterogeneous photochemistry of CHOCHO in SOA formation, and identify a potential bias in the currently available <i>Y</i><sub>SOA</sub> data for other SOA precursor NMHCs. We demonstrate that SOA formation via the aqueous phase is not limited to cloud droplets, but proceeds also in the absence of clouds, i.e., does not stop once a cloud droplet evaporates. Atmospheric models need to be expanded to include SOA formation from WSOC photochemistry of CHOCHO, and possibly other α-dicarbonyls, in aqueous aerosols.
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We conducted measurements of Hg<sup>0</sup> and RGM at two inland sites, Thompson Farm (TF) and Pac Monadnock (PM), and a marine site (Appledore Island (AI)) from the UNH AIRMAP observing network in New Hampshire in 2007. Measurements of other important trace gases and meteorological variables were used to help understand influences on the atmospheric Hg budget in New England. Seasonal variation in both species observed at TF and PM is attributable to such factors as seasonal variation in deposition strength, meteorological conditions and biogenic emissions. Hg<sup>0</sup> and RGM varied diurnally at TF, particularly in spring, following the trend in air temperature and <i>j</i>NO<sub>2</sub> and suggesting photochemical production of RGM. The diurnal patterns of Hg<sup>0</sup> and RGM at AI during summer were nearly opposite in phase, with Hg<sup>0</sup> decreasing through late afternoon, suggesting more significant photochemical oxidation of Hg<sup>0</sup> to RGM in the marine environment, likely due to the presence of marine halogen compounds. A significant relationship of RGM with SO<sub>2</sub> at TF suggests a strong contribution of RGM from anthropogenic sources. Significant levels of halogen compounds measured at TF in previous studies, as well as similar Hg<sup>0</sup> levels and Hg<sup>0</sup>-CO ratios at TF and AI may suggest that similar air masses are prevalent at these sites.
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Mixing ratios and fluxes of six selected volatile organic compounds (VOCs) were measured above the city of Manchester (UK) during the summer of 2006. A proton transfer reaction-mass spectrometer was used for the measurement of mixing ratios, and fluxes were calculated from these using both the disjunct and the virtual disjunct eddy covariance techniques. The two flux systems, which operated in alternate half hours, showed good agreement, with <i>R<sup>2</sup></i> values ranging between 0.74 and 0.9 for the individual analytes. On average, fluxes measured in the disjunct mode were approximately 20% lower than those measured in the virtual mode. This difference is due to both the dampening of the VOC signal by the disjunct flux sampler and carry over from one sample to the next. Correcting for these effects reduced the difference to less than 7%. Observed fluxes are thought to be largely controlled by anthropogenic sources, with vehicle emissions the major contributor. However, both evaporative and biogenic emissions may account for some of the VOCs present. Concentrations and fluxes of the oxygenated compounds were highest on average, ranging between 0.15 to 1 mg m<sup>−2</sup> h<sup>−1</sup>; the fluxes of aromatic compounds were lower, between 0.12 to 0.28 mg m<sup>−2</sup> h<sup>−1</sup>. The observed fluxes were up-scaled to give city wide emission estimates for each compound and the results compared to estimates made by the National Atmospheric Emission Inventory (NAEI) for the same flux footprint. Fluxes of toluene and benzene compared most closely differing by approximately 50%, while in contrast the oxygenated fluxes were found to be between 3.6–6.3 times larger than the annual average predicted by the NAEI.
