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Using an aerosol flow tube apparatus, we have studied the effects of aliphatic aldehydes (C<sub>3</sub> to C<sub>10</sub>) and ketones (C<sub>3</sub> and C<sub>9</sub>) on ice nucleation in sulfuric acid aerosols. Mixed aerosols were prepared by combining an organic vapor flow with a flow of sulfuric acid aerosols over a small mixing time (~60 s) at room temperature. No acid-catalyzed reactions were observed under these conditions, and physical uptake was responsible for the organic content of the sulfuric acid aerosols. In these experiments, aerosol organic content, determined by a Mie scattering analysis, was found to vary with the partial pressure of organic, the flow tube temperature, and the identity of the organic compound. The physical properties of the organic compounds (primarily the solubility and melting point) were found to play a dominant role in determining the inferred mode of nucleation (homogenous or heterogeneous) and the specific freezing temperatures observed. Overall, very soluble, low-melting organics, such as acetone and propanal, caused a decrease in aerosol ice nucleation temperatures when compared with aqueous sulfuric acid aerosol. In contrast, sulfuric acid particles exposed to organic compounds of eight carbons and greater, of much lower solubility and higher melting temperatures, nucleate ice at temperatures above aqueous sulfuric acid aerosols. Organic compounds of intermediate carbon chain length, C<sub>4</sub>-C<sub>7</sub>, (of intermediate solubility and melting temperatures) nucleated ice at the same temperature as aqueous sulfuric acid aerosols. Interpretations and implications of these results for cirrus cloud formation are discussed.
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Airborne measurements, obtained during the Asian Aerosol Characterisation Experiment (ACE-Asia), of SO<sub>2</sub> and condensation nuclei (CN) concentrations were made in the local environment of a cumulus cloud band. Conserved quantities, wet equivalent potential temperature <i>θ</i><sub>q</sub>, and total water content <i>Q</i>, were used to identify the sources of air detrained on the downwind side of the cumulus band. It was found that ~65% of the detrained air originated from below cloud base and the remainder was air that had been entrained from the free troposphere upwind of the cloud and subsequently been detrained. Calculation of the sources of the detrained air parcels enabled a prediction of the concentration of SO<sub>2</sub> and CN, assuming that SO<sub>2</sub> and CN experienced no processing within cloud. A comparison of the predicted concentration of SO<sub>2</sub> and CN was made with those observed. The concentration of SO<sub>2</sub> observed was less than predicted and the amount of SO<sub>2</sub> scavenged within cloud was calculated. The CN concentration observed was also less than predicted and, moreover, inclusion of the loss of CN to cloud droplets due to Brownian scavenging resulted in an enhanced decrease of the number concentration of CN predicted. Clear air regions around the cloud exhibited no indication of being a major source of new particles. It was concluded that new particles were formed within cloud.
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The aerosol extinction-to-backscatter ratio is an important parameter for inverting LIDAR signals in the LIDAR equation. It is a complicated function of the aerosol microphysical characteristics. In this paper, a method to retrieve the column-averaged aerosol extinction-to-backscatter ratio by constraining the aerosol optical depths (AOD) from a Micro-pulse LIDAR (MPL) by the AOD measurements from the Moderate Resolution Imaging Spectroradiometer (MODIS) is presented. Both measurements were taken on cloud free days between 1 May 2003 and 30 June 2004 over Hong Kong, a coastal city in south China. Simultaneous measurements of aerosol scattering coefficients with a forward scattering visibility sensor are compared with the LIDAR retrieval of aerosol extinction coefficients. The data are then analyzed to determine seasonal trends of the aetrosol extinction-to-backscatter ratio. In addition, the relationships between the extinction-to-backscatter ratio and wind conditions as well as other aerosol microphysical parameters are presented. The mean aerosol extinction-to-backscatter ratio for the whole period was found to be 29.1±5.8 sr, with a minimum of 18 sr in July 2003 and a maximum of 44 sr in March 2004. The ratio is lower in summer because of the dominance of oceanic aerosols in association with the prevailing southwesterly monsoon. In contrast, relatively larger ratios are noted in spring and winter because of the increased impact of local and regional industrial pollutants associated with the northerly monsoon. The extended LIDAR measurements over Hong Kong provide not only a more accurate retrieval of aerosol extinction coefficient profiles, but also significant substantial information for air pollution and climate studies in the region.
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Vehicular emission is an important source of air pollutants in urban cities in the Pearl River Delta (PRD) region of South China. In order to study the impact of evaporative loss of vehicular fuel on air quality, several commonly used fuel samples were collected in four main cities in the PRD region – Hong Kong, Guangzhou, Macau and Zhuhai, and analyzed for their volatile organic compounds (VOCs) composition. Source profiles of vapors of the vehicular fuels used in these cities were constructed and are believed to be the first reported for the PRD region. The C<sub>8</sub>-C<sub>10</sub> hydrocarbons were the main constituents of diesel. Different from diesel, gasoline used in the PRD region was mainly comprised of lighter C<sub>4</sub>-C<sub>7</sub> hydrocarbons, with toluene and i-pentane being the two most abundant species. The toluene content in the Hong Kong and Macau gasoline samples were higher than that in Guangzhou and Zhuhai, while the reverse was true for the benzene content. The benzene levels in Guangzhou and Zhuhai exceeded the maximum allowable benzene levels for Mainland China unleaded gasoline. Liquefied Petroleum Gas (LPG) samples were collected only in Hong Kong and were comprised mainly of n-butane, propane and i-butane. Traffic samples indicated that evaporative loss and vehicular combustion were the primary contributors to elevated VOC levels in roadside atmospheres. Significant i-pentane and toluene concentrations were observed in roadside atmospheres in all four cities. Ratio of i-pentane in gasoline vapors to that in roadside samples were calculated and this showed that the degree of evaporative loss were higher in Guangzhou and Zhuhai than that in Hong Kong and Macau. We suggest the difference is due to the better maintenance and more new cars in Hong Kong and Macau. From tunnel samples collected in Hong Kong in two different years, we found that the relative amount of propane, i-butane, and n-butane increased between 2001 to 2003, consistent with the 40% increase in LPG fueled vehicles. Propane to butanes ratios were calculated for LPG samples and tunnels samples, and the comparable ratios illustrated the LPG leakages from LPG fueled vehicles crossing the tunnel.
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Aerosol chemical and optical properties are extensively investigated for the first time over the Paris Basin in July 2000 within the ESQUIF project. The measurement campaign offers an exceptional framework to evaluate the performances of the chemistry-transport model CHIMERE in simulating concentrations of gaseous and aerosol pollutants, as well as the aerosol-size distribution and composition in polluted urban environments against ground-based and airborne measurements. A detailed comparison of measured and simulated variables during the second half of July with particular focus on 19 and 31 pollution episodes reveals an overall good agreement for gas-species and aerosol components both at the ground level and along flight trajectories, and the absence of systematic biases in simulated meteorological variables such as wind speed, relative humidity and boundary layer height as computed by the MM5 model. A good consistency in ozone and NO concentrations demonstrates the ability of the model to reproduce the plume structure and location fairly well both on 19 and 31 July, despite an underestimation of the amplitude of ozone concentrations on 31 July. The spatial and vertical aerosol distributions are also examined by comparing simulated and observed lidar vertical profiles along flight trajectories on 31 July and confirm the model capacity to simulate the plume characteristics. The comparison of observed and modeled aerosol components in the southwest suburb of Paris during the second half of July indicates that the aerosol composition is rather correctly reproduced, although the total aerosol mass is underestimated by about 20%. The simulated Parisian aerosol is dominated by primary particulate matter that accounts for anthropogenic and biogenic primary particles (40%), and inorganic aerosol fraction (40%) including nitrate (8%), sulfate (22%) and ammonium (10%). The secondary organic aerosols (SOA) represent 12% of the total aerosol mass, while the mineral dust accounts for 8%. The comparison demonstrates the absence of systematic errors in the simulated sulfate, ammonium and nitrates total concentrations. However, for nitrates the observed partition between fine and coarse mode is not reproduced. In CHIMERE there is a clear lack of coarse-mode nitrates. This calls for additional parameterizations in order to account for the heterogeneous formation of nitrate onto dust particles. Larger discrepancies are obtained for the secondary organic aerosols due to both inconsistencies in the SOA formation processes in the model leading to an underestimation of their mass and large uncertainties in the determination of the measured aerosol organic fraction. The observed mass distribution of aerosols is not well reproduced, although no clear explanation can be given.
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In aerosol chamber experiments optical properties of resuspended mineral dust samples of defined size distributions were measured. Extinction coefficients (b<sub>ext</sub>) and mass specific extinction cross sections (σ<sub>ext</sub>) were determined for Saharan dust samples from different locations. The results for σ<sub>ext</sub> were not very sensitive to the type of dust and varied at λ=550 nm between 3.3±0.4 m<sup>2</sup> g<sup>−1</sup> and 3.7±0.4 m<sup>2</sup> g<sup>−1</sup>. The absorption coefficients (b<sub>abs</sub>) and mass specific absorption cross sections (σ<sub>abs</sub>) were determined with a novel multi-wavelength photo-acoustic absorption spectrometer (PAS). The single scattering albedo was close to 1 (0.98 to 0.99) at 532 nm and 1064 nm, but significantly lower (0.63 to 0.76) at 266 nm. Additionally the chemical and mineralogical composition of the dust samples were analysed with special regard to the iron oxide phases hematite and goethite. At λ=266 nm the mineral dust sample without any detectable iron oxides showed a significantly higher SSA compared to the sample with a hematite content of 0.6 wt-%.
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The Royal Society expedition to Antarctica established a base at Halley Bay, in support of the International Geophysical Year of 1957–1958. Surface ozone was measured during 1958 only, using a prototype Brewer-Mast sonde. The envelope of maximum ozone was an annual cycle from 10 ppbv in January to 22 ppbv in August. These values are 35% less at the start of the year and 15% less at the end than modern values from Neumayer, also a coastal site. This may reflect a general increase in surface ozone since 1958 and differences in summer at the less windy site of Halley, or it may reflect ozone loss on the inlet together with long-term conditioning. There were short periods in September when ozone values decreased rapidly to near-zero, and some in August when ozone values were rapidly halved. Such ozone-loss episodes, catalysed by bromine compounds, became well-known in the Artic in the 1980s, and were observed more recently in the Antarctic. In 1958, very small ozone values were recorded for a week in midwinter during clear weather with light winds. The absence of similar midwinter reductions at Neumayer, or at Halley in the few measurements during 1987, means we must remain suspicious of these small values, but we can find no obvious reason to discount them. The dark reaction of ozone and seawater ice observed in the laboratory may be fast enough to explain them if the salinity and surface area of the ice is sufficiently amplified by frost flowers.
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A size dependent parameterization for the removal of aerosol particles by falling rain droplets is developed. Scavenging coefficients are calculated explicitly as a function of aerosol particle size and precipitation intensity including the full interaction of rain droplet size distribution and aerosol particles. The actual parameterization is a simple and accurate three-parameter fit through these pre-calculated scavenging coefficients. The parameterization is applied in the global chemistry transport model TM4 and the importance of below-cloud scavenging relative to other removal mechanisms is investigated for sea salt aerosol. For a full year run (year 2000), we find that below-cloud scavenging accounts for 12% of the total removal of super-micron aerosol. At mid-latitudes of both hemispheres the fractional contribution of below-cloud scavenging to the total removal of super-micron sea salt is about 30% with regional maxima exceeding 50%. Below-cloud scavenging reduces the global average super-micron aerosol lifetime from 2.47 to 2.16 days in our simulations. Despite large uncertainties in precipitation, relative humidity, and water uptake by aerosol particles, we conclude that below cloud scavenging is likely an important sink for super-micron sized sea salt aerosol particles that needs to be included in size-resolved aerosol models.
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Using a simplified model of in-orbit radiance acquisition by the Advanced Microwave Sounding Unit (AMSU-A), we derive three-dimensional temperature weighting functions for Channel 9 measurements (peaking at ~60–90 hPa) at all 30 cross-track beam positions and use them to investigate the sensitivity of these radiances to gravity waves. The vertical widths of the weighting functions limit detection to waves with vertical wavelengths of ≳10 km, with slightly better vertical wavelength sensitivity at the outermost scan angles due to the limb effect. Fourier Transforms of two-dimensional cross-track weighting functions reveal optimal sensitivity to cross-track wavelengths at the near-nadir scan angles, where horizontal measurement footprints are smallest. This sensitivity is greater for the AMSU-A on the Aqua satellite than for the identical instruments on the NOAA meteorological satellites, due to a lower orbit altitude and thus smaller horizontal footprints from antenna spreading. Small cross-track asymmetries in the radiance response to gravity waves are found that peak at the mid-range scan angles, with more symmetric responses at near-nadir and far off-nadir scan angles. Three-dimensional simulations show gravity wave oscillations imaged in horizontal AMSU-A radiance maps swept out by the scan pattern and satellite motion. A distorting curvature is added to imaged wave phase lines due to vertical variations in weighting function peaks with cross-track scan angle. This wave distortion is analogous to the well-known "limb darkening" and "limb brightening" of microwave radiances acquired from purely vertical background temperature profiles by cross-track scanners. Waves propagating along track are more visible in these images at the outermost scan angles than those propagating cross track, due to oversampling and narrower widths of the horizontal measurement footprints in the along track direction. Based on nominal noise floors and representative lower stratospheric wave temperature amplitudes, our modeling indicates that Channel 9 AMSU-A radiances can resolve and horizontally image gravity waves with horizontal wavelengths of ≳150 km and vertical wavelengths of ≳10 km.
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Aerosol chemical composition was measured over the Atlantic Ocean in November–December 1999 and at the Finnish Antarctic research station Aboa in January 2000. The concentrations of all anthropogenic aerosol compounds decreased clearly from north to south. An anthropogenic influence was still evident in the middle of the tropical South Atlantic, background values were reached south of Cape Town. Chemical mass apportionment was calculated for high volume filter samples (D<sub><i>p</i></sub><3 μm). North of the equator 70–80% of the aerosol consisted of non-sea-salt species. The contribution of sea salt was ~25% in the polluted latitudes, >80% in the Southern Ocean, and <10% at Aboa. The contribution of organic carbon was >10% in most samples, also at Aboa. The correlation of biomass-burning-related aerosol components with <sup>210</sup>Pb was very high compared with that between nss calcium and <sup>210</sup>Pb which suggests that <sup>210</sup>Pb is a better tracer for biomass burning than for Saharan dust. The ratio of the two clear tracers for biomass burning, nss potassium and oxalate, was different in European and in African samples, suggesting that this ratio could be used as an indicator of biomass burning type. The concentrations of continent-related particles decreased exponentially with the distance from Africa. The shortest half-value distance, ~100 km, was for nss calcium. The half-value distance of particles that are mainly in the submicron particles was ~700±200 km. The MSA to nss sulfate ratio, R, increased faster than MSA concentration with decreasing anthropogenic influence, indicating that the R increase could largely be explained by the decrease of anthropogenic sulfate.
