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A total of 834 individual aerosol particles were collected during October and November 2010 in urban Shanghai, China. Particles were sampled under different weather and air quality conditions. Morphologies, compositions and mixing states of carbonaceous aerosols were investigated by transmission electron microscopy (TEM) coupled with energy-dispersive X-ray (EDX). Structures of some particles were verified using selected-area electron diffraction (SAED). Among the aerosol particles observed, carbonaceous aerosols were mainly categorized into four types: polymeric organic compound (POC), soot, tar ball, and biogenic particle. Based on the detailed TEM-EDX analysis, most of the particles were coated with secondary organic aerosols (SOA), which commonly formed through condensation or heterogeneous reactions of precursor gases on pre-existing particles. Aged particles were associated with days with low wind velocities, showed complex structures, and were bigger in size. The internally mixed particles of sulphates, organics and soot were encountered frequently. Such internally mixed particles may be preferentially formed during a stagnated air mass during serious pollution events, such as on 13 November. Although relative number counts varied with different species, sulphates (38–71%) and soot (11–22%) constituted the most dominant species observed in the samples. However, soil-derived particles (68%) were relatively more frequently observed on the sample collected on 12 November during a dust storm.
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From 2006 to 2007, the daily concentrations of major inorganic water-soluble constituents, mineral aerosol, organic carbon (OC) and elemental carbon (EC) in ambient PM<sub>10</sub> samples were investigated from 16 urban, rural and remote sites in various regions of China, and were compared with global aerosol measurements. A large difference between urban and rural chemical species was found, normally with 1.5 to 2.5 factors higher in urban than in rural sites. Optically-scattering aerosols, such as sulfate (~16%), OC (~15%), nitrate (~7%), ammonium (~5%) and mineral aerosol (~35%) in most circumstance, are majorities of the total aerosols, indicating a dominant scattering feature of aerosols in China. Of the total OC, ~55%–60% can be attributed to the formation of the secondary organic carbon (SOC). The absorbing aerosol EC only accounts for ~3.5% of the total PM<sub>10</sub>. Seasonally, maximum concentrations of most aerosol species were found in winter while mineral aerosol peaks in spring. In addition to the regular seasonal maximum, secondary peaks were found for sulfate and ammonium in summer and for OC and EC in May and June. This can be considered as a typical seasonal pattern in various aerosol components in China. Aerosol acidity was normally neutral in most of urban areas, but becomes some acidic in rural areas. Based on the surface visibility observations from 681 meteorological stations in China between 1957 and 2005, four major haze areas are identified with similar visibility changes, namely, (1) Hua Bei Plain in N. China, and the Guanzhong Plain; (2) E. China with the main body in the Yangtze River Delta area; (3) S. China with most areas of Guangdong and the Pearl River Delta area; (4) The Si Chuan Basin in S.W. China. The degradation of visibility in these areas is linked with the emission changes and high PM concentrations. Such quantitative chemical characterization of aerosols is essential in assessing their role in atmospheric chemistry and weather-climate effects, and in validating atmospheric models.
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Energetic cosmic rays are the main source of ionization of the low-middle atmosphere, leading to associated changes in atmospheric properties. Via the hypothetical influence of ionization on aerosol growth and facilitated formation of clouds, this may be an important indirect link relating solar variability to climate. This effect is highly debated, however, since the proposed theoretical mechanisms still remain illusive and qualitative, and observational evidence is inconclusive and controversial. Therefore, important questions regarding the existence and magnitude of the effect, and particularly the fraction of aerosol particles that can form and grow, are still open. Here we present empirical evidence of the possible effect caused by cosmic rays upon polar stratospheric aerosols, based on a case study of an extreme solar energetic particle (SEP) event of 20 January 2005. Using aerosol data obtained over polar regions from different satellites with optical instruments that were operating during January 2005, such as the Stratospheric Aerosol and Gas Experiment III (SAGE III), and Optical Spectrograph and Infrared Imaging System (OSIRIS), we found a significant simultaneous change in aerosol properties in both the Southern and Northern Polar regions in temporal association with the SEP event. We speculate that ionization of the atmosphere, which was abnormally high in the lower stratosphere during the extreme SEP event, might have led to formation of new particles and/or growth of preexisting ultrafine particles in the polar stratospheric region. However, a detailed interpretation of the effect is left for subsequent studies. This is the first time high vertical resolution measurements have been used to discuss possible production of stratospheric aerosols under the influence of cosmic ray induced ionization. The observed effect is marginally detectable for the analyzed severe SEP event and can be undetectable for the majority of weak-moderate events. The present interpretation serves as a conservative upper limit of solar energetic particle effect upon polar stratospheric aerosols.
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This study reports the first global measurements of acetone (C<sub>3</sub>H<sub>6</sub>O) in the upper troposphere (UT). Profiles were obtained between 9 km and 15 km from measurements made by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) onboard Envisat in August 2003. Errors per profile are lower than 40 % between 180 hPa and 350 hPa. We report strong hemispheric differences in the acetone volume mixing ratios (VMRs), with average concentrations highest in the Northern Hemisphere (NH) mid-latitude UT, between 1000 pptv and 1600 pptv with maxima up to 2300 pptv. Our results show a strong enhancement of acetone relative to CO, particularly over Europe (7 pptv ppbv<sup>−1</sup>), confirming aircraft studies. Ten-day backward trajectories from these high European values show strong contributions from air flows over North America (56 %) and 25 % from Southernmost Asia. Enhanced acetone is also observed over Greenland, Siberia and biomass burning regions of Africa. Zonal distributions show that acetone VMRs decrease rapidly with increasing altitude (decreasing pressure), particularly in the NH. Poleward of 45° S, acetone VMRs remain fairly consistent with average VMRs between 400 pptv and 500 pptv. In 5-day averages at 9 km, NH VMRs poleward of 45° N are consistently higher than Southern Hemisphere observations poleward of 45° S, by between 750 pptv and 1100 pptv. The results show a clear influence of mid-latitude and transport processes on the acetone summertime distribution.
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Dust storms and associated mineral aerosol transport are driven primarily by meso- and synoptic-scale atmospheric processes. It is therefore essential that the dust aerosol process and background atmospheric conditions that drive dust emissions and atmospheric transport are represented with sufficiently well-resolved spatial and temporal features. The effects of airborne dust interactions with the environment determine the mineral composition of dust particles. The fractions of various minerals in aerosol are determined by the mineral composition of arid soils; therefore, a high-resolution specification of the mineral and physical properties of dust sources is needed. <br></br> Several current dust atmospheric models simulate and predict the evolution of dust concentrations; however, in most cases, these models do not consider the fractions of minerals in the dust. The accumulated knowledge about the impacts of the mineral composition in dust on weather and climate processes emphasizes the importance of including minerals in modeling systems. Accordingly, in this study, we developed a global dataset consisting of the mineral composition of the current potentially dust-producing soils. In our study, we (a) mapped mineral data to a high-resolution 30 s grid, (b) included several mineral-carrying soil types in dust-productive regions that were not considered in previous studies, and (c) included phosphorus.
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A series of 1,3,5-trimethylbenzene (TMB) photo-oxidation experiments was performed in the 27-m<sup>3</sup> Paul Scherrer Institute environmental chamber under various NO<sub>x</sub> conditions. A University of Innsbruck prototype high resolution Proton Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-TOF) was used for measurements of gas and particulate phase organics. The gas phase mass spectrum displayed ~200 ion signals during the TMB photo-oxidation experiments. Molecular formulas C<sub>m</sub>H<sub>n</sub>N<sub>o</sub>O<sub>p</sub> were determined and ion signals were separated and grouped according to their C, O and N numbers. This allowed to determine the time evolution of the O:C ratio and of the average carbon oxidation state <span style="border-top: 1px solid #000; color: #000;">OS</span><sub>C</sub> of the reaction mixture. Both quantities were compared with master chemical mechanism (MCMv3.1) simulations. The O:C ratio in the particle phase was about twice the O:C ratio in the gas phase. Average carbon oxidation states of secondary organic aerosol (SOA) samples <span style="border-top: 1px solid #000; color: #000;">OS</span><sub>C</sub><sup>SOA</sup> were in the range of −0.34 to −0.31, in agreement with expected average carbon oxidation states of fresh SOA (<span style="border-top: 1px solid #000; color: #000;">OS</span><sub>C</sub> = −0.5–0).
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Carbon monoxide (CO) and ozone (O<sub>3</sub>) have been measured in the Western Pacific (43° N to 35° S) during a ship campaign with Research Vessel Sonne in fall 2009. Observations have been performed using ship-based solar absorption Fourier Transform infrared spectrometry, flask sampling, balloon sounding, and in-situ Fourier Transform infrared analysis. The results obtained are compared to the GEOS-Chem global 3-D chemistry transport model for atmospheric composition. In general, a very good agreement is found between the GEOS-Chem model and all instruments. The CO and O<sub>3</sub> distributions show a comparable variability suggesting an impact from the same source regions. <br><br> Tagged-CO simulations implemented in the GEOS-Chem model make it possible to differentiate between different source processes and source regions. The source regions are verified with HYSPLIT backward trajectory calculations. In the Northern Hemisphere fossil fuel combustion in Asia is the dominant source. European and North American fossil fuel combustion also contribute to Northern Hemispheric CO pollution. In the Southern Hemisphere contributions from biomass burning and fossil fuel combustion are dominant; African biomass burning has a significant impact on Western Pacific CO pollution. Furthermore, in the tropical Western Pacific enhanced upper tropospheric CO within the tropical tropopause layer mainly originates from Indonesian fossil fuel combustion and can be transported into the stratosphere. <br><br> The source regions of the measured O<sub>3</sub> pollution are simulated with a tagged-O<sub>3</sub> simulation implemented in the GEOS-Chem model. Similar source regions compared to the tagged-CO simulations are identified by the model. In the Northern Hemisphere contributions from Asia, Europe, and North America are significant. In the Southern Hemisphere emissions from South America, south-east Africa, and Oceania significantly contribute to the measured O<sub>3</sub> pollution.
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Previous experiments have demonstrated that the aqueous OH radical oxidation of methylglyoxal produces low volatility products including pyruvate, oxalate and oligomers. These products are found predominantly in the particle phase in the atmosphere, suggesting that methylglyoxal is a precursor of secondary organic aerosol (SOA). Acetic acid plays a central role in the aqueous oxidation of methylglyoxal and it is a ubiquitous product of gas phase photochemistry, making it a potential "aqueous" SOA precursor in its own right. However, the fate of acetic acid upon aqueous-phase oxidation is not well understood. In this research, acetic acid (20 μM–10 mM) was oxidized by OH radicals, and pyruvic acid and methylglyoxal experimental samples were analyzed using new analytical methods, in order to better understand the formation of SOA from acetic acid and methylglyoxal. Glyoxylic, glycolic, and oxalic acids formed from acetic acid and OH radicals. In contrast to the aqueous OH radical oxidation of methylglyoxal, the aqueous OH radical oxidation of acetic acid did not produce succinic acid and oligomers. This suggests that the methylgloxal-derived oligomers do not form through the acid catalyzed esterification pathway proposed previously. Using results from these experiments, radical mechanisms responsible for oligomer formation from methylglyoxal oxidation in clouds and wet aerosols are proposed. The importance of acetic acid/acetate as an SOA precursor is also discussed. We hypothesize that this and similar chemistry is central to the daytime formation of oligomers in wet aerosols.
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The study investigates the sources of fine organic aerosol (OA) in the boreal forest, based on measurements including both filter sampling (PM<sub>1</sub>) and online methods and carried out during a one-month campaign held in Hyytiälä, Finland, in spring 2007. Two aerosol mass spectrometers (Q-AMS, ToF-AMS) were employed to measure on-line concentrations of major non-refractory aerosol species, while the water extracts of the filter samples were analyzed by nuclear magnetic resonance (NMR) spectroscopy for organic functional group characterization of the polar organic fraction of the aerosol. AMS and NMR spectra were processed separately by non-negative factorization algorithms, in order to apportion the main components underlying the submicrometer organic aerosol composition and depict them in terms of both mass fragmentation patterns and functional group compositions. <br><br> The NMR results supported the AMS speciation of oxidized organic aerosol (OOA) into two main fractions, which could be generally labelled as more and less oxidized organics. The more oxidized component was characterized by a mass spectrum dominated by the <i>m/z</i> 44 peak, and in parallel by a NMR spectrum showing aromatic and aliphatic backbones highly substituted with oxygenated functional groups (carbonyls/carboxyls and hydroxyls). Such component, contributing on average 50% of the OA mass throughout the observing period, was associated with pollution outbreaks from the Central Europe. The less oxidized component was enhanced in concomitance with air masses originating from the North-to-West sector, in agreement with previous investigations conducted at this site. NMR factor analysis was able to separate two distinct components under the less oxidized fraction of OA. One of these NMR-factors was associated with the formation of terrestrial biogenic secondary organic aerosol (BSOA), based on the comparison with spectral profiles obtained from laboratory experiments of terpenes photo-oxidation. The second NMR factor associated with western air masses was linked to biogenic marine sources, and was enriched in low-molecular weight aliphatic amines. Such findings provide evidence of at least two independent sources originating biogenic organic aerosols in Hyytiälä by oxidation and condensation mechanisms: reactive terpenes emitted by the boreal forest and compounds of marine origin, with the latter relatively more important when predominantly polar air masses reach the site. <br><br> This study is an example of how spectroscopic techniques, such as proton NMR, can add functional group specificity for certain chemical features (like aromatics) of OA with respect to AMS. They can therefore be profitably exploited to complement aerosol mass spectrometric measurements in organic source apportionment studies.
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Large-scale production of feedstock crops for biofuels will lead to land use changes. We quantify the effects of realistic land use change scenarios for biofuel feedstock production on isoprene emissions and hence atmospheric composition and chemistry using the HadGEM2 model. Two feedstocks are considered: oil palm for biodiesel in the tropics and short rotation coppice (SRC) in the mid-latitudes. In total, 69 Mha of oil palm and 9 Mha of SRC are planted, each sufficient to replace just over 1% of projected global fossil fuel demand in 2020. Both planting scenarios result in increases in total global annual isoprene emissions of about 1%. In each case, changes in surface concentrations of ozone and biogenic secondary organic aerosol (bSOA) are substantial at the regional scale, with implications for air quality standards. However, the changes in tropospheric burden of ozone and the OH radical, and hence effects on global climate, are negligible. Over SE Asia, one region of oil palm planting, increases in annual mean surface ozone and bSOA concentrations reach over 3 ppbv (+11%) and 0.4 μg m<sup>−3</sup> (+10%) respectively for parts of Borneo, with monthly mean increases of up to 6.5 ppbv (+25%) and 0.5 μg m<sup>−3</sup> (+12%). Under the SRC scenario, Europe experiences monthly mean changes of over 0.6 ppbv (+1%) and 0.1 μg m<sup>−3</sup> (+5%) in June and July, with peak increases of over 2 ppbv (+3%) and 0.5 μg m<sup>−3</sup> (+8 %). That appreciable regional atmospheric impacts result from low level planting scenarios demonstrates the need to include changes in emissions of reactive trace gases such as isoprene in life cycle assessments performed on potential biofuel feedstocks.
