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Secondary organic carbon (SOC) is often a significant portion of organic carbon (OC) in ambient particulate matter (PM). The levels and seasonal patterns of SOC in Hong Kong were examined using more than 2000 PM<sub>10</sub> measurements made over a 4.5-year period (1998–2002) in a network of ten air quality monitoring stations. The positive matrix factorization (PMF) model was used to analyze this large data set for source identification and apportioning. SOC was subsequently estimated to be the sum of OC present in the secondary sources, i.e., secondary sulfate, secondary nitrate, and secondary organic aerosol. The annual average SOC as estimated by the PMF method was 4.25 μg C/m<sup>3</sup> while the summer average was 1.66 μg C/m<sup>3</sup> and the winter average was 7.05 μg C/m<sup>3</sup>. In comparison, the method that uses EC as a tracer for primary carbonaceous aerosol sources to derive SOC overestimated SOC by 70–212% for the summer samples and by 4–43% for the winter samples. The overestimation by the EC tracer method resulted from the inability of obtaining a single OC/EC ratio that represented a mixture of primary sources varying in time and space. <P style="line-height: 20px;"> We found that SOC and secondary sulfate had synchronous seasonal variation and were correlated in individual seasons, suggesting common factors that control their formation. Additionally, the presence of SOC was found to be enhanced more than that of secondary sulfate in the winter. We postulate this to be a combined result of favorable partitioning of semivolatile SOC species in the particle phase and more abundant SOC precursors in the winter.
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The hygroscopic growth of ammoniated sulfate particles was studied by measurements and model calculations for particles with varying ammonium-to-sulfate ratio. In the measurements, the ammonium-to-sulfate ratio was adjusted by using mixtures of ammonium sulfate and ammonium bisulfate in generating the solid particles. The hygroscopic growth was measured using a tandem differential mobility analyzer. The measurements were simulated using a thermodynamical equilibrium model. The calculations indicated that the solid phases in particle with ammonium-to-sulfate ratio between 1.5–2, were ammonium sulfate and letovicite. Both in the calculations and in the experiments the hygroscopic growth was initiated at relative humidities less than the theoretical deliquescence relative humidity of these particles. This indicates that the particles were multi-phase particles including solids and liquids. The equilibrium model yielded a satisfactory prediction of the hygroscopic growth of particles generated from a solution with 1:1 mass ratio between dissolved ammonium sulfate and ammonium bisulfate. However, for particles with 3:1 and 10:1 mass ratios, the model predictions overestimated the growth at relative humidities between about 60% and the point of complete deliquescence (close to 80% <I>RH</I>). In contrast, a model, in which letovicite was allowed to dissolve only after complete dissolution of ammonium sulfate, reproduced the observations well. This indicates that the dry particles had a letovicite core surrounded by an ammonium sulfate shell.
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The chemistry climate model MAECHAM4/ CHEM with interactive and prognostic volcanic aerosol and ozone was used to study the initial dispersal and radiative forcing of a possible Northern Hemisphere mid-latitude super eruption. Tropospheric climate anomalies are not analysed since sea surface temperatures are kept fixed. Our experiments show that the global dispersal of a super eruption located at Yellowstone, Wy. is strongly dependent on the season of the eruption. In Northern Hemisphere summer the volcanic cloud is transported westward and preferentially southward, while in Northern Hemisphere winter the cloud is transported eastward and more northward compared to the summer case. Aerosol induced heating leads to a more global spreading with a pronounced cross equatorial transport. For a summer eruption aerosol is transported much further to the Southern Hemisphere than for a winter eruption. In contrast to Pinatubo case studies, strong cooling tendencies appear with maximum peak values of less than −1.6 K/day three months after the eruption in the upper tropical stratosphere. This strong cooling effect weakens with decreasing aerosol density over time and initially prevents the aerosol laden air from further active rising. All-sky net radiative flux changes of less than −32 W/m<sup>2</sup> at the surface are about a factor of 6 larger than for the Pinatubo eruption. Large positive flux anomalies of more than 16 W/m<sup>2</sup> are found in the first months in the tropics and sub tropics. These strong forcings call for a fully coupled ocean/atmosphere/chemistry model to study climate sensitivity to such a super-eruption.
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Ozone levels in Europe are changing. Emissions of ozone precursors from Europe (NO<sub>x</sub>, CO and non-methane hydrocarbons) have been substantially reduced over the last 10–15 years, but changes in ozone levels cannot be explained by changes in European emissions alone. The observed ozone trends at many European sites are only partially reproduced by global or regional photochemistry models, and possible reasons for this are discussed. <P style="line-height: 20px;"> In order to further explain the European trends in ozone since 1990, the EMEP regional photochemistry model has been run for the years 1990 and 1995–2002. The EMEP model is a regional model centred over Europe but the model domain also includes most of the North Atlantic and the polar region. Climatological ozone data are used as initial and lateral boundary concentrations. Model results are compared to measurements over this timespan of 12 years. Possible causes for the measured trends in European surface ozone have been investigated using model sensitivity runs perturbing emissions and lateral boundary concentrations. The increase in winter ozone partially, and the decrease in the magnitude of high ozone episodes, is attributed to the decrease in ozone precursor emissions since 1990 by the model. Furthermore, the model calculations indicate that the emission reductions have resulted in a marked decrease in summer ozone in major parts of Europe, in particular in Germany. Such a trend in summer ozone is likely to be difficult to identify from the measurements alone because of large inter-annual variability.
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Numerical experiments were carried out using the Tel-Aviv University 2-D cloud model to investigate the effects of increased concentrations of Cloud Condensation Nuclei (CCN), giant CCN (GCCN) and Ice Nuclei (IN) on the development of precipitation and cloud structure in mixed-phase sub-tropical convective clouds. In order to differentiate between the contribution of the aerosols and the meteorology, all simulations were conducted with the same meteorological conditions. <P style="line-height: 20px;"> The results show that under the same meteorological conditions, polluted clouds (with high CCN concentrations) produce less precipitation than clean clouds (with low CCN concentrations), the initiation of precipitation is delayed and the lifetimes of the clouds are longer. GCCN enhance the total precipitation on the ground in polluted clouds but they have no noticeable effect on cleaner clouds. The increased rainfall due to GCCN is mainly a result of the increased graupel mass in the cloud, but it only partially offsets the decrease in rainfall due to pollution (increased CCN). The addition of more effective IN, such as mineral dust particles, reduces the total amount of precipitation on the ground. This reduction is more pronounced in clean clouds than in polluted ones. <P style="line-height: 20px;"> Polluted clouds reach higher altitudes and are wider than clean clouds and both produce wider clouds (anvils) when more IN are introduced. Since under the same vertical sounding the polluted clouds produce less rain, more water vapor is left aloft after the rain stops. In our simulations about 3.5 times more water evaporates after the rain stops from the polluted cloud as compared to the clean cloud. The implication is that much more water vapor is transported from lower levels to the mid troposphere under polluted conditions, something that should be considered in climate models.
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Leaf and woody plant tissue (<I>Pinus ponderosa</I>, <I>Eucalyptus saligna</I>, <I>Quercus gambelli</I>, <I>Saccharum officinarum</I> and <I>Oriza sativa</I>) were heated from 30 to 300°C and volatile organic compound (VOC) emissions were identified and quantified. Major VOC emissions were mostly oxygenated and included acetic acid, furylaldehyde, acetol, pyrazine, terpenes, 2,3-butadione, phenol and methanol, as well as smaller emissions of furan, acetone, acetaldehyde, acetonitrile and benzaldehyde. Total VOC emissions from distillation and pyrolysis were on the order of 10 gC/kgC dry weight of vegetation, as much as 33% and 44% of CO<sub>2</sub> emissions (gC(VOC)/gC(CO<sub>2</sub>)) measured during the same experiments, in air and nitrogen atmospheres, respectively. <P style="line-height: 20px;"> The emissions are similar in identity and quantity to those from smoldering combustion of woody tissue and of different character than those evolved during flaming combustion. VOC emissions from the distillation of pools and endothermic pyrolysis under low turbulence conditions may produce flammable concentrations near leaves and may facilitate the propagation of wildfires. VOC emissions from charcoal production are also related to distillation and pyrolysis; the emissions of the highly reactive VOCs from production are as large as the carbon monoxide emissions.
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We present the results of an intercomparison exercise between six different radiative transfer (RT) models carried out in the framework of QUILT, an EU funded project based on the exploitation of the Network for the Detection of Stratospheric Change (NDSC). RT modelling is an important step in the interpretation of Differential Optical Absorption Spectroscopy (DOAS) observations. It allows the conversion of slant column densities (SCDs) into vertical column densities (VCDs) using calculated air mass factors (AMFs). The originality of our study resides in comparing SCD simulations in multi-axis (MAX) geometry (trace gases: NO<sub>2</sub> and HCHO) and in taking into account photochemical enhancement for calculating SCDs of rapidly photolysing species (BrO, NO<sub>2</sub>, and OClO) in zenith-sky geometry. Concerning the zenith-sky simulations, the different models agree generally well, especially below 90° SZA. At higher SZA, larger discrepancies are obtained with relative differences ranging between 2% and 14% in some cases. In MAX geometry, good agreement is found between the models with the calculated NO<sub>2</sub> and HCHO SCDs differing by no more than 5% in the elevation and solar zenith angle (SZA) ranges investigated (5°–20° and 35°–85°, respectively). The impacts of aerosol scattering, ground albedo, and relative azimuth on MAX simulations have also been tested. Significant discrepancies appear for the aerosol effect, suggesting differences between models in the treatment of aerosol scattering. A better agreement is found in case of the ground albedo and relative azimuth effects. The complete set of initialization data and results have been made publicly available through the QUILT project web site (<TT><A NAME="tex2html1" HREF="http://nadir.nilu.no/quilt/">http://nadir.nilu.no/quilt/</A></TT>), enabling the testing of other RT codes designed for the calculation of SCDs/AMFs.
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Airborne high resolution in situ measurements of a large set of trace gases including ozone (O<sub>3</sub>) and total water (H<sub>2</sub>O) in the upper troposphere and the lowermost stratosphere (UT/LMS) have been performed above Europe within the SPURT project. SPURT provides an extensive data coverage of the UT/LMS in each season within the time period between November 2001 and July 2003. <P style="line-height: 20px;"> In the LMS a distinct spring maximum and autumn minimum is observed in O<sub>3</sub>, whereas its annual cycle in the UT is shifted by 2–3 months later towards the end of the year. The more variable H<sub>2</sub>O measurements reveal a maximum during summer and a minimum during autumn/winter with no phase shift between the two atmospheric compartments. <P style="line-height: 20px;"> For a comprehensive insight into trace gas composition and variability in the UT/LMS several statistical methods are applied using chemical, thermal and dynamical vertical coordinates. In particular, 2-dimensional probability distribution functions serve as a tool to transform localised aircraft data to a more comprehensive view of the probed atmospheric region. It appears that both trace gases, O<sub>3</sub> and H<sub>2</sub>O, reveal the most compact arrangement and are best correlated in the view of potential vorticity (PV) and distance to the local tropopause, indicating an advanced mixing state on these surfaces. Thus, strong gradients of PV seem to act as a transport barrier both in the vertical and the horizontal direction. The alignment of trace gas isopleths reflects the existence of a year-round extra-tropical tropopause transition layer. The SPURT measurements reveal that this layer is mainly affected by stratospheric air during winter/spring and by tropospheric air during autumn/summer. <P style="line-height: 20px;"> Normalised mixing entropy values for O<sub>3</sub> and H<sub>2</sub>O in the LMS appear to be maximal during spring and summer, respectively, indicating highest variability of these trace gases during the respective seasons.
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Surface-atmosphere exchange fluxes of CO<sub>2</sub>, estimated by an interannual atmospheric transport inversion from atmospheric mixing ratio measurements, are affected by several sources of errors, one of which is experimental errors. Quantitative information about such measurement errors can be obtained from regular co-located measurements done by different laboratories or using different experimental techniques. The present quantitative assessment is based on intercomparison information from the CMDL and CSIRO atmospheric measurement programs. We show that the effects of systematic measurement errors on inversion results are very small compared to other errors in the flux estimation (as well as compared to signal variability). As a practical consequence, this assessment justifies the merging of data sets from different laboratories or different experimental techniques (flask and in-situ), if systematic differences (and their changes) are comparable to those considered here. This work also highlights the importance of regular intercomparison programs.
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SCIAMACHY, on board Envisat, has been in operation now for almost three years. This UV/visible/NIR spectrometer measures the solar irradiance, the earthshine radiance scattered at nadir and from the limb, and the attenuation of solar radiation by the atmosphere during sunrise and sunset, from 240 to 2380 nm and at moderate spectral resolution. Vertical columns and profiles of a variety of atmospheric constituents are inferred from the SCIAMACHY radiometric measurements by dedicated retrieval algorithms. With the support of ESA and several international partners, a methodical SCIAMACHY validation programme has been developed jointly by Germany, the Netherlands and Belgium (the three instrument providing countries) to face complex requirements in terms of measured species, altitude range, spatial and temporal scales, geophysical states and intended scientific applications. This summary paper describes the approach adopted to address those requirements. <P style="line-height: 20px;"> Since provisional releases of limited data sets in summer 2002, operational SCIAMACHY processors established at DLR on behalf of ESA were upgraded regularly and some data products – level-1b spectra, level-2 O<sub>3</sub>, NO<sub>2</sub>, BrO and clouds data – have improved significantly. Validation results summarised in this paper and also reported in this special issue conclude that for limited periods and geographical domains they can already be used for atmospheric research. Nevertheless, current processor versions still experience known limitations that hamper scientific usability in other periods and domains. Free from the constraints of operational processing, seven scientific institutes (BIRA-IASB, IFE/IUP-Bremen, IUP-Heidelberg, KNMI, MPI, SAO and SRON) have developed their own retrieval algorithms and generated SCIAMACHY data products, together addressing nearly all targeted constituents. Most of the UV-visible data products – O<sub>3</sub>, NO<sub>2</sub>, SO<sub>2</sub>, H<sub>2</sub>O total columns; BrO, OClO slant columns; O<sub>3</sub>, NO<sub>2</sub>, BrO profiles – already have acceptable, if not excellent, quality. Provisional near-infrared column products – CO, CH<sub>4</sub>, N<sub>2</sub>O and CO<sub>2</sub> – have already demonstrated their potential for a variety of applications. Cloud and aerosol parameters are retrieved, suffering from calibration with the exception of cloud cover. In any case, scientific users are advised to read carefully validation reports before using the data. It is required and anticipated that SCIAMACHY validation will continue throughout instrument lifetime and beyond and will accompany regular processor upgrades.
