Physical and chemical processes of air masses in the Aegean Sea during Etesians: Aegean-GAME airborne campaign.

High-resolution measurements of gas and aerosols' chemical composition along with meteorological and turbulence parameters were performed over the Aegean Sea (AS) during an Etesian outbreak in the framework of the Aegean-GAME airborne campaign. This study focuses on two distinct Etesian patterns, with similarities inside the Marine Atmospheric Boundary Layer (MABL) and differences at higher levels. Under long-range transport and subsidence the pollution load is enhanced (by 17% for CO, 11% for O3, 28% for sulfate, 62% for organic mass, 47% for elemental carbon), compared to the pattern with a weaker synoptic system. Sea surface temperature (SST) was a critical parameter for the MABL structure, turbulent fluxes and pollutants' distribution at lower levels. The MABL height was below 500 m asl over the eastern AS (favoring higher accumulation), and deeper over the western AS. The most abundant components of total PM1 were sulfate (40-50%) and organics (30-45%). Higher average concentrations measured over the eastern AS (131 ± 76 ppbv for CO, 62.5 ± 4.1 ppbv for O3, 5.0 ± 1.1 µg m(-3) for sulfate, 4.7 ± 0.9 µg m(-3) for organic mass and 0.5 ± 0.2 µg m(-3) for elemental carbon). Under the weaker synoptic system, cleaner but more acidic air masses prevailed over the eastern part, while distinct aerosol layers of different signature were observed over the western part. The Aitken and accumulation modes contributed equally during the long-range transport, while the Aitken modes dominated during local or medium range transport.

The atmospheric chemistry of trace gases and particulate matter emitted by different land uses in Borneo.

We report measurements of atmospheric composition over a tropical rainforest and over a nearby oil palm plantation in Sabah, Borneo. The primary vegetation in each of the two landscapes emits very different amounts and kinds of volatile organic compounds (VOCs), resulting in distinctive VOC fingerprints in the atmospheric boundary layer for both landscapes. VOCs over the Borneo rainforest are dominated by isoprene and its oxidation products, with a significant additional contribution from monoterpenes. Rather than consuming the main atmospheric oxidant, OH, these high concentrations of VOCs appear to maintain OH, as has been observed previously over Amazonia. The boundary-layer characteristics and mixing ratios of VOCs observed over the Borneo rainforest are different to those measured previously over Amazonia. Compared with the Bornean rainforest, air over the oil palm plantation contains much more isoprene, monoterpenes are relatively less important, and the flower scent, estragole, is prominent. Concentrations of nitrogen oxides are greater above the agro-industrial oil palm landscape than over the rainforest, and this leads to changes in some secondary pollutant mixing ratios (but not, currently, differences in ozone). Secondary organic aerosol over both landscapes shows a significant contribution from isoprene. Primary biological aerosol dominates the super-micrometre aerosol over the rainforest and is likely to be sensitive to land-use change, since the fungal source of the bioaerosol is closely linked to above-ground biodiversity.

Evolution of organic aerosols in the atmosphere.

Organic aerosol (OA) particles affect climate forcing and human health, but their sources and evolution remain poorly characterized. We present a unifying model framework describing the atmospheric evolution of OA that is constrained by high-time-resolution measurements of its composition, volatility, and oxidation state. OA and OA precursor gases evolve by becoming increasingly oxidized, less volatile, and more hygroscopic, leading to the formation of oxygenated organic aerosol (OOA), with concentrations comparable to those of sulfate aerosol throughout the Northern Hemisphere. Our model framework captures the dynamic aging behavior observed in both the atmosphere and laboratory: It can serve as a basis for improving parameterizations in regional and global models.

The influence of small aerosol particles on the properties of water and ice clouds.

In this paper, results are presented of the influence of small organic- and soot-containing particles on the formation of water and ice clouds. There is strong evidence that these particles have grown from nano particle seeds produced by the combustion of oil products. Two series of field experiments are selected to represent the observations made. The first is the CLoud-Aerosol Characterisation Experiment (CLACE) series of experiments performed at a high Alpine site (Jungfraujoch), where cloud was in contact with the ground and the measuring station. Both water and ice clouds were examined at different times of the year. The second series of experiments is the CLOud Processing of regional Air Pollution advecting over land and sea (CLOPAP) series, where ageing pollution aerosol from UK cities was observed, from an airborne platform, to interact with warm stratocumulus cloud in a cloud-capped atmospheric boundary layer. Combining the results it is shown that aged pollution aerosol consists of an internal mixture of organics, sulfate, nitrate and ammonium, the organic component is dominated by highly oxidized secondary material. The relative contributions and absolute loadings of the components vary with location and season. However, these aerosols act as Cloud Condensation Nuclei (CCN) and much of the organic material, along with the other species, is incorporated into cloud droplets. In ice and mixed phase cloud, it is observed that very sharp transitions (extending over just a few metres) are present between highly glaciated regions and regions consisting of supercooled water. This is a unique finding; however, aircraft observations in cumulus suggest that this kind of structure may be found in these cloud types too. It is suggested that this sharp transition is caused by ice nucleation initiated by oxidised organic aerosol coated with sulfate in more polluted regions of cloud, sometimes enhanced by secondary ice particle production in these regions.

Chemical and microphysical characterization of ambient aerosols with the aerodyne aerosol mass spectrometer.

The application of mass spectrometric techniques to the real-time measurement and characterization of aerosols represents a significant advance in the field of atmospheric science. This review focuses on the aerosol mass spectrometer (AMS), an instrument designed and developed at Aerodyne Research, Inc. (ARI) that is the most widely used thermal vaporization AMS. The AMS uses aerodynamic lens inlet technology together with thermal vaporization and electron-impact mass spectrometry to measure the real-time non-refractory (NR) chemical speciation and mass loading as a function of particle size of fine aerosol particles with aerodynamic diameters between approximately 50 and 1,000 nm. The original AMS utilizes a quadrupole mass spectrometer (Q) with electron impact (EI) ionization and produces ensemble average data of particle properties. Later versions employ time-of-flight (ToF) mass spectrometers and can produce full mass spectral data for single particles. This manuscript presents a detailed discussion of the strengths and limitations of the AMS measurement approach and reviews how the measurements are used to characterize particle properties. Results from selected laboratory experiments and field measurement campaigns are also presented to highlight the different applications of this instrument. Recent instrumental developments, such as the incorporation of softer ionization techniques (vacuum ultraviolet (VUV) photo-ionization, Li+ ion, and electron attachment) and high-resolution ToF mass spectrometers, that yield more detailed information about the organic aerosol component are also described.

Secondary organic aerosols from anthropogenic and biogenic precursors.

Secondary organic aerosol (SOA) formation from the photooxidation of an anthropogenic (1,3,5-trimethylbenzene) and a biogenic (alpha-pinene) precursor was investigated at the new PSI smog chamber. The chemistry of the gas phase was followed by proton transfer reaction mass spectrometry, while the aerosol chemistry was investigated with aerosol mass spectrometry, ion chromatography, laser desorption ionization mass spectrometry, and infrared spectroscopy, along with volatility and hygroscopicity studies. Evidence for oligomer formation for SOA from both precursors was given by an increasing abundance of compounds with a high molecular weight (up to 1000 Da) and by an increasing thermal stability with increasing aging time. The results were compared to data obtained from ambient aerosol samples, revealing a number of similar features.

Measurements and modelling of cloudwater deposition to moorland and forests.

The objective of the study was to measure the size dependence of cloudwater deposition and associated average ionic fluxes to vegetated surfaces. Measurements were made over a forest canopy at Dunslair heights in south Scotland and a moorland site, Great Dun Fell, in northern England. Measurements were made using the gradient and eddy correlation techniques. Eddy correlation measurements were made using an ultrasonic anemometer, a Knollenberg forward scattering spectrometer probe (to measure liquid water fluxes and fluxes of droplets in 1 microm size intervals) and a GSI particulate volume monitor (to measure liquid-water fluxes). Measurements were made at Great Dun Fell of the size dependence of droplet deposition velocity, using the gradient technique with two Knollenberg probes. Simultaneous gradient and eddy correlation measurements were also made at Great Dun Fell of average cloud-water fluxes, together with chemical analysis of cloud water composition, using a continuous analysis system. At Dunslair Heights, eddy correlation measurements were made using both the Knollenberg and Gerber Scientific Instruments (GSI) probes, while simultaneous gradient measurements using two GSI probes were also attempted. Samples of cloud water were collected at Dunslair Heights, using passive string collectors for chemical analysis by ion chromatography. The major findings of the study were: 1. The droplet deposition velocities measured by the two techniques were similar. 2. The deposition velocities were a strong function of droplet size. Considerable resistance to deposition was evident for droplets of less than 5 microm radius. Deposition velocities for particles from about 6 to 8 microm exceeded those for momentum. 3. Except when the droplets were very small or the winds very light, bulk cloud-water deposition velocities were about 80% or more of the momentum deposition velocities to forests.