ALBERT

Description: The volatile and hygroscopic properties of ammonium sulphate seeded and un-seeded secondary organic aerosol (SOA) derived from the photo-oxidation of atmospherically relevant concentrations of α-pinene were studied. The seed particles were electrospray generated ammonium sulphate ((NH4)2SO4) having diameters of approximately 33 nm with a quasi-mono-disperse size distribution (geometric standard deviation σg=1.3). The volatile and hygroscopic properties of both seeded and unseeded SOA were simultaneously measured with a VH-TDMA (volatility – hygroscopicity tandem differential mobility analyzer). VH-TDMA measurements of unseeded SOA show a decrease in the hygroscopic growth (HGF) factor for increased volatilisation temperatures such that the more volatile compounds appear to be more hygroscopic. This is opposite to the expected preferential evaporation of more volatile but less hygroscopic material, but could also be due to enhanced oligomerisation occurring at the higher temperature in the thermodenuder. In addition, HGF measurements of seeded SOA were measured as a function of time at two relative humidities, below (RH 75%) and above (RH 85%) the deliquescence relative humidity (DRH) of the pure ammonium sulphate seeds. As these measurements were conducted during the onset phase of photo-oxidation, during particle growth, they enabled us to find the dependence of the HGF as a function of the volume fraction of the SOA coating. HGF's measured at RH of 85% showed a continuous decrease as the SOA coating thickness increased. The measured growth factors show good agreements with ZSR predictions indicating that, at these RH values, there are only minor solute-solute interactions. At 75% RH, as the SOA fraction increased, a rapid increase in the HGF was observed indicating that an increasing fraction of the (NH4)2SO4 is subject to a phase transition, going into solution, with an increasing volume fraction of SOA. To our knowledge this is the first time that SOA derived from photo-oxidised α-pinene has been shown to affect the equilibrium water content of inorganic aerosols below their DRH. For SOA volume fractions above ~0.3 the measured growth factor followed roughly parallel to the ZSR prediction based on fully dissolved (NH4)2SO4 although with a small difference that was just larger than the error estimate. Both incomplete dissolution and negative solute-solute interactions could be responsible for the lower HGF observed compared to the ZSR predictions.

Description: Residential wood combustion has only recently been recognized as a major contributor to air pollution in Switzerland and in other European countries. A source apportionment method using the aethalometer light absorption parameters was applied to five winter campaigns at three sites in Switzerland: a village with high wood combustion activity in winter, an urban background site and a highway site. The particulate mass from traffic (PMtraffic) and wood burning (PMwb) emissions obtained with this model compared fairly well with results from the 14C source apportionment method. PMwb from the model was also compared to well known wood smoke markers such as anhydrosugars (levoglucosan and mannosan) and fine mode potassium, as well as to a marker recently suggested from the Aerodyne aerosol mass spectrometer (mass fragment m/z 60). Additionally the anhydrosugars were compared to the 14C results and were shown to be comparable to literature values from wood burning emission studies using different types of wood (hardwood, softwood). The levoglucosan to PMwb ratios varied much more strongly between the different campaigns (4–13%) compared to mannosan to PMwb with a range of 1–1.5%. Possible uncertainty aspects for the various methods and markers are discussed.

Description: Atmospheric aerosols are often mixtures of inorganic and organic material. Organics can represent a large fraction of the total aerosol mass and are comprised of water-soluble and insoluble compounds. Increasing attention was paid in the last decade to the capability of mixed inorganic/organic aerosol particles to take up water (hygroscopicity). We performed hygroscopicity measurements of internally mixed particles containing ammonium sulfate and carboxylic acids (citric, glutaric, adipic acid) in parallel with an electrodynamic balance (EDB) and a hygroscopicity tandem differential mobility analyzer (HTDMA). The organic compounds were chosen to represent three distinct physical states. During hygroscopicity cycles covering hydration and dehydration measured by the EDB and the HTDMA, pure citric acid remained always liquid, adipic acid remained always solid, while glutaric acid could be either. We show that the hygroscopicity of mixtures of the above compounds is well described by the Zdanovskii-Stokes-Robinson (ZSR) relationship as long as the two-component particle is completely liquid in the ammonium sulfate/citric acid and in the ammonium sulfate/glutaric acid cases. However, we observe significant discrepancies compared to what is expected from bulk thermodynamics when a solid component is present. We explain this in terms of a complex morphology resulting from the crystallization process leading to veins, pores, and grain boundaries which allow for water sorption in excess of bulk thermodynamic predictions caused by the inverse Kelvin effect on concave surfaces.

Description: We use observations of total particle number concentration at 36 worldwide sites and a global aerosol model to quantify the primary and secondary sources of particle number. We show that emissions of primary particles can reasonably reproduce the spatial pattern of observed condensation nuclei (CN) (R2=0.51) but fail to explain the observed seasonal cycle at many sites (R2=0.1). The modeled CN concentration in the free troposphere is biased low (normalised mean bias, NMB=−88%) unless a secondary source of particles is included, for example from binary homogeneous nucleation of sulfuric acid and water (NMB=−25%). Simulated CN concentrations in the continental boundary layer (BL) are also biased low (NMB=−74%) unless the number emission of anthropogenic primary particles is increased or an empirical BL particle formation mechanism based on sulfuric acid is used. We find that the seasonal CN cycle observed at continental BL sites is better simulated by including a BL particle formation mechanism (R2=0.3) than by increasing the number emission from primary anthropogenic sources (R2=0.18). Using sensitivity tests we derive optimum rate coefficients for this nucleation mechanism, which agree with values derived from detailed case studies at individual sites.

Description: During the ICARTT-ITOP Experiment in summer 2004 plumes from large wildfires in North America were transported to Central Europe at 3–8 km altitude above sea level (a.s.l.). These plumes were studied with the DLR (Deutsches Zentrum fuer Luft- und Raumfahrt) research aircraft Falcon which was equipped with an extensive set of in situ aerosol and trace gas instruments. Analyses by the Lagrangian dispersion model FLEXPART provided source regions, transport times and horizontal extent of the fire plumes. Results from the general circulation model ECHAM/MADE and data from previous aerosol studies over Central Europe provided reference vertical profiles of black carbon (BC) mass concentrations for year 2000 conditions with forest fire activities below the long-term average. Smoke plume observations yielded a BC mass fraction of total aerosol mass with respect to PM2.5 of 3–10%. The ratio of BC mass to excess CO was 3–7.5 mg BC (g CO)−1. Even after up to 10 days of atmospheric transport, both characteristic properties were of the same order as for fresh emissions. This suggests an efficient lifting of BC from forest fires to higher altitudes with only minor scavenging removal of particulate matter. Maximum aerosol absorption coefficient values were 7–8×10–6m−1 which is about two orders of magnitude above the average European free tropospheric background value. Forest fire aerosol size distributions were characterised by a strong internally mixed accumulation mode centred at modal diameters of 0.25–0.30 μm with an average distribution width of 1.30. Nucleation and small Aitken mode particles were almost completely depleted. Even after more than one week of atmospheric transport, no steady state of the size distribution was observed.

Description: We present comprehensive results on continuous atmospheric cluster and particle measurements in the size range ~1–42 nm within the European Integrated project on Aerosol Cloud Climate and Air Quality interactions (EUCAARI) project. We focused on characterizing the spatial and temporal variation of new-particle formation events and relevant particle formation parameters across Europe. Different types of air ion and cluster mobility spectrometers were deployed at 12 field sites across Europe from March 2008 to May 2009. The measurements were conducted in a wide variety of environments, including coastal and continental locations as well as sites at different altitudes (both in the boundary layer and the free troposphere). New-particle formation events were detected at all of the 12 field sites during the year-long measurement period. From the data, nucleation and growth rates of newly-formed particles were determined for each environment. In a case of parallel ion and neutral cluster measurements, we could also estimate the relative contribution of ion-induced and neutral nucleation to the total particle formation. The formation rates of charged particles at 2 nm accounted for 1–30% of the respective total particle formation rates. As a significant new result, we found out that the total particle formation rate varied much more between the different sites than the formation rate of charged particles. This work presents, so far, the most comprehensive effort to experimentally characterize nucleation and growth of atmospheric molecular clusters and nanoparticles at ground-based observation sites on a continental scale.

Description: Aerosol nucleation is an important source of atmospheric particles which have an effect both on the climatic system and on human health. The new particle formation (NPF) process is an ubiquitous phenomenon, yet poorly understood despite the many studies performed on this topic using various approaches (observation, experimentation in smog chambers and modeling). In this work, we investigate the formation of secondary charged aerosols and its climatology at Jungfraujoch, a high altitude site in Swiss Alps (3580 m a.s.l.). Charged particles and clusters (0.5–1.8 nm) were measured within the EUCAARI program from April 2008 to April 2009 and allowed the detection of nucleation events. We found that the aerosol concentration, which is dominated by cluster size class, shows a strong diurnal pattern and that the aerosol size distribution and concentration are strongly influenced by the presence of clouds either during daytime or nighttime conditions. New particle formation events have been investigated and it appears that new particle formation occurs 17.5% of measured days and that the nucleation frequency is strongly linked to air mass origin and path and negatively influenced by cloud presence. In fact, we show that NPF events depend on the occurrence of high concentration VOCs air masses which allowed clusters growing by condensation of organic vapors rather than nucleation of new clusters. Furthermore, the contribution of ions to nucleation process was studied and we found that ion-mediated nucleation (IMN) contribute to 26% of the total nucleation so that ions play an important role in the new particle formation and growth at Jungfraujoch.

Description: Ambient continental-rural fine aerosol (K-puszta, Hungary, PM1.5) was sampled on quartz fibre filters in winter and summer 2001. Water-soluble matter (WSM) was extracted in MilliQ-water, and, in a second step, solid phase extraction was used to isolate the less hydrophilic fraction (ISOM) of the water-soluble organic matter (WSOM) from remaining inorganic salts and "most" hydrophilic organic matter (MHOM). This approach allowed ISOM, which constitutes the major fraction of WSOM, to be isolated from ambient aerosols and investigated in pure form. Hygroscopic properties of both WSM and ISOM extracts as well as of aquatic reference fulvic and humic acids were investigated using a Hygroscopicity Tandem Differential Mobility Analyser (H-TDMA). ISOM deliquesced between 30% and 60% relative humidity (RH), and hygroscopic growth factors at 90% RH ranged from 1.08 to 1.17. The hygroscopicity of ISOM is comparable to secondary organic aerosols obtained in smog chamber experiments, but lower than the hygroscopicity of highly soluble organic acids. The hygroscopic behaviour of investigated fulvic and humic acids had similarities to ISOM, but hygroscopic growth factors were slightly smaller and deliquescence was observed at higher RH (75-85% and 85-95% RH for fulvic acid and humic acid, respectively). These differences probably originate from larger average molecular mass and lower solubility of fulvic and humic acids. Inorganic composition data, measured ISOM hygroscopicity, and a presumed value for the hygroscopicity of the small remaining MHOM fraction were used to predict hygroscopic growth of WSM extracts. Good agreement between model prediction and measured water uptake was observed with differences (by volume) ranging from +1% to -18%. While deliquescence properties of WSM extracts were mainly determined by the inorganic salts (42-53 wt % of WSM), the WSOM accounted for a significant fraction of particulate water. At 90% RH, according to model predictions and measurements, about 80-62% of particulate water in the samples are associated with inorganic salts and about 20-38% with WSOM. The relative contributions of both distinguished WSOM fractions, ISOM and MHOM, remains uncertain since MHOM was not available in isolated form, but the results suggest that the less abundant MHOM is also important due to its presumably larger hygroscopicity.

Description: Particle emissions from ship engines and their atmospheric transformation in the marine boundary layer (MBL) were investigated in engine test bed studies and in airborne measurements of expanding ship plumes. During the test rig studies, detailed aerosol microphysical and chemical properties were measured in the exhaust gas of a serial MAN B&W seven-cylinder four-stroke marine diesel engine under various load conditions. The emission studies were complemented by airborne aerosol transformation studies in the plume of a large container ship in the English Channel using the DLR aircraft Falcon 20 E-5. Observations from emission studies and plume studies combined with a Gaussian plume dispersion model yield a consistent picture of particle transformation processes from emission to atmospheric processing during plume expansion. Particulate matter emission indices obtained from plume measurements are 8.8±1.0×1015(kg fuel)−1 by number for non-volatile particles and 174±43 mg (kg fuel)−1 by mass for Black Carbon (BC). Values determined for test rig conditions between 85 and 110% engine load are of similar magnitude. For the total particle number including volatile compounds no emission index can be derived since the volatile aerosol fraction is subject to rapid transformation processes in the plume. Ship exhaust particles occur in the size range Dp

Description: The volatile and hygroscopic properties of ammonium sulphate seeded and unseeded secondary organic aerosol (SOA) derived from the photo-oxidation of atmospherically relevant concentrations of α-pinene were studied. The seed particles were electrospray generated ammonium sulphate ((NH4)2SO4) having diameters of approximately 33 nm with a quasi-mono-disperse size distribution (geometric standard deviation σg=1.3). The volatile and hygroscopic properties of both seeded and unseeded SOA were simultaneously measured with a VH-TDMA (volatility – hygroscopicity tandem differential mobility analyzer). VH-TDMA measurements of unseeded SOA show a decrease in the hygroscopic growth (HGF) factor for increased volatilisation temperatures such that the more volatile compounds appear to be more hygroscopic. This is opposite to the expected preferential evaporation of more volatile but less hygroscopic material, but could also be due to enhanced oligomerisation occurring at the higher temperature in the thermodenuder. In addition, HGF measurements of seeded SOA were measured as a function of time at two relative humidities, below (RH 75%) and above (RH 85%) the deliquescence relative humidity (DRH) of the pure ammonium sulphate seeds. As these measurements were conducted during the onset phase of photo-oxidation, during particle growth, they enabled us to find the dependence of the HGF as a function of the volume fraction of the SOA coating. HGF's measured at RH of 85% showed a continuous decrease as the SOA coating thickness increased. The measured growth factors show good agreements with ZSR predictions indicating that, at these RH values, there are only minor solute-solute interactions. At 75% RH, as the SOA fraction increased, a rapid increase in the HGF was observed indicating that an increasing fraction of the (NH4)2SO4 is subject to a phase transition, going into solution, with an increasing volume fraction of SOA. To our knowledge this is the first time that SOA derived from photo-oxidised α-pinene has been shown to affect the equilibrium water content of inorganic aerosols below their DRH. For SOA volume fractions above ~0.3 the measured growth factor followed roughly parallel to the ZSR prediction based on fully dissolved (NH4)2SO4 although with a small difference that was just larger than the error estimate. Both incomplete dissolution and negative solute-solute interactions could be responsible for the lower HGF observed compared to the ZSR predictions.