Size-resolved cloud condensation nuclei (CCN) spectra measured for various aerosol types at a non-urban site in Germany showed that CCN concentrations are mainly determined by the aerosol number size ...distribution. Distinct variations of CCN activation with particle chemical composition were observed but played a secondary role. When the temporal variation of chemical effects on CCN activation is neglected, variation in the size distribution alone explains 84 to 96% of the variation in CCN concentrations. Understanding that particles' ability to act as CCN is largely controlled by aerosol size rather than composition greatly facilitates the treatment of aerosol effects on cloud physics in regional and global models.
We report the development and first field deployment of a new version of the Aerosol Mass Spectrometer (AMS), which is capable of measuring non-refractory aerosol mass concentrations, chemically ...speciated mass distributions and single particle information. The instrument was constructed by interfacing the well-characterized Aerodyne AMS vacuum system, particle focusing, sizing, and evaporation/ionization components, with a compact TOFWERK orthogonal acceleration reflectron time-of-flight mass spectrometer. In this time-of-flight aerosol mass spectrometer (TOF-AMS) aerosol particles are focused by an aerodynamic lens assembly as a narrow beam into the vacuum chamber. Non-refractory particle components flash-vaporize after impaction onto the vaporizer and are ionized by electron impact. The ions are continuously guided into the source region of the time-of-flight mass spectrometer, where ions are extracted into the TOF section at a repetition rate of 83.3 kHz. Each extraction generates a complete mass spectrum, which is processed by a fast (sampling rate 1 Gs/s) data acquisition board and a PC. Particle size information is obtained by chopping the particle beam followed by time-resolved detection of the particle evaporation events. Due to the capability of the time-of-flight mass spectrometer of measuring complete mass spectra for every extraction, complete single particle mass spectra can be collected. This mode provides quantitative information on single particle composition. The TOF-AMS allows a direct measurement of internal and external mixture of non-refractory particle components as well as sensitive ensemble average particle composition and chemically resolved size distribution measurements. Here we describe for the first time the TOF-AMS and its operation as well as results from its first field deployment during the PM
2.5
Technology Assessment and Characterization Study-New York (PMTACS-NY) Winter Intensive in January 2004 in Queens, New York. These results show the capability of the TOF-AMS to measure quantitative aerosol composition and chemically resolved size distributions of the ambient aerosol. In addition it is shown that the single particle information collected with the instrument gives direct information about internal and external mixture of particle components.
Slightly soluble atmospherically relevant organic compounds may influence particle CCN activity and therefore cloud formation. Adipic acid is a frequently employed surrogate for such slightly soluble ...organic materials. The 11 published experimental studies on the CCN activity of adipic acid particles are not consistent with each other nor do they, in most cases, agree with the Köhler theory. The CCN activity of adipic acid aerosol particles was studied over a significantly wider range of conditions than in any previous single study. The work spans the conditions of the previous studies and also provides alternate methods for producing "wet" (deliquesced solution droplets) and dry adipic acid particles without the need to produce them by atomization of aqueous solutions. The experiments suggest that the scatter in the previously published CCN measurements is most likely due to the difficulty of producing uncontaminated adipic acid particles by atomization of solutions and possibly also due to uncertainties in the calibration of the instruments. The CCN activation of the small (dm<150 nm) initially dry particles is subject to a deliquescence barrier, while for the larger particles the activation follows the Köhler curve. Wet adipic acid particles follow the Köhler curve over the full range of particle diameters studied. In addition, the effect of adipic acid coatings on the CCN activity of both soluble and insoluble particles has also been studied. When a water-soluble core is coated by adipic acid, the CCN-hindering effect of particle phase is eliminated. An adipic acid coating on hydrophobic soot yields a CCN active particle. If the soot particle is relatively small (dcore≤102 nm), the CCN activity of the coated particles approaches the deliquescence line of adipic acid, suggesting that the total size of the particle determines CCN activation and the soot core acts as a scaffold.
The chemical composition and chemically resolved size distributions of fine aerosol particles were measured at high time resolution (5
min) with a time-of-flight aerosol mass spectrometer (TOF-AMS) ...during the New Year's 2005 fireworks in Mainz, central Germany. In addition, particle number concentrations and trace gas concentrations were measured using a condensation particle counter (CPC) and a proton transfer reaction mass spectrometer (PTR-MS). The main non-refractory components of the firework aerosol were potassium, sulfate, total organics and chloride. Increased trace gas mixing ratios of methanol, acetonitrile, acetone and acetaldehyde were observed. Aerosol nitrate and ammonium concentrations were not significantly affected by the fireworks as well as the measured aromatic trace gases. The sub-micron aerosol concentrations peaked about 20
min after midnight with total mass concentrations larger than 600
μg
m
−3. The trace gas concentrations peaked about 30
min later. Using the sulfur-to-potassium concentration ratio measured in another fireworks aerosol, it was for the first time possible to estimate the relative ionization efficiency of aerosol potassium, measured with the TOF-AMS. Here we found a value of RIE
K=2.9.
The Aerodyne aerosol mass spectrometer (Q-AMS) was coupled with a counterflow virtual impactor (CVI) for the first time to measure cloud droplet residuals of warm tropospheric clouds on Mt. Åreskutan ...in central Sweden in July 2003. Operating the CVI in different operational modes generated mass concentration and species-resolved mass distribution data for non-refractory species of the ambient, interstitial, and residual aerosol. The ambient aerosol measurements revealed that the aerosol at the site was mainly influenced by long-range transport and regional photochemical generation of nitrate and organic aerosol components. Four different major air masses were identified for the time interval of the experiment. While two air masses that approached the site from northeastern Europe via Finland showed very similar aerosol composition, the other two air masses from polar regions and the British Islands had a significantly different composition. During cloud events the larger aerosol particles were found to be activated into cloud droplets. On a mass basis the activation cut-off diameter was approximately 150 nm for nitrate and organics dominated particles and 200 nm for sulfate dominated particles. Generally nitrate and organics were found to be activated into cloud droplets with higher efficiency than sulfate. While a significant fraction of the nitrate in ambient particles was organic nitrates or nitrogen-containing organic species, the nitrate found in the cloud droplet residuals was mainly ammonium nitrate. After passage of clouds the ambient aerosol size distribution had shifted to smaller particle sizes due to the predominantly activation of larger aerosol particles without a significant change in the relative composition of the ambient aerosol.PUBLICATION ABSTRACT
The Feldberg Aerosol Characterization Experiment (FACE-2004) took place from July 13-August 4, 2004 at the Taunus Observatory on the "Kleiner Feldberg" (825 m a.m.s.l.) in Central Germany. The ...experiment included (amongst others) size-resolved chemical characterization of non-refractory aerosol components. One of the experiment's objectives was to better understand and to characterize recently developed aerosol measurement instrumentation by intercomparison with other co-located instruments. One of these instruments was the Aerodyne Time-of-Flight Aerosol Mass Spectrometer (ToF-AMS).
Here we compare the datasets obtained by the ToF-AMS with those obtained by the well-characterized co-located Quadrupole Aerosol Mass Spectrometer (Q-AMS). A good agreement between the recently developed ToF-AMS with the established Q-AMS is reported here for all species measured with the two instruments for a time period where both instruments operated under well-calibrated conditions. During measurements with reduced detector gain after a pump failure changed species concentrations were measured with the ToF-AMS that did not agree with those measured with the Q-AMS. These changes were different for the individual species and could be attributed to the influence of the ion detection threshold as was shown by model calculations.
For efficient and user-friendly processing of ToF-AMS raw data a data processing software package was developed. Since this is the first time this software was used for field data, it is described in some detail here.
The Aerodyne quadrupole aerosol mass spectrometer was deployed on the Falcon twin jet research aircraft operated by Deutsches Zentrum für Luft- und Raumfahrt (DLR). This was the first deployment of ...an AMS in a jet aircraft. Aerosol mass concentration measurements in the troposphere up to altitudes of about 11
km were performed within two measurement flights on 12 and 14 May 2003 over southern Germany. Background aerosol data were gained up to 6
km, while aircraft exhaust aerosol was be sampled at higher altitudes on 14 May, indicating the presence of sulfuric acid and unburned hydrocarbons in the exhaust particles. The boundary layer aerosol on 12 May was found to be composed of 49% organics, 12% sulfate, 15% ammonium, and 24% nitrate by mass. The upper edge of the boundary layer was marked by a sharp decrease of nitrate and ammonium at an altitude of 3
km, while sulfate and organics decreased to a much lesser degree. On 14 May, the boundary layer aerosol was composed of 23% organics, 20% sulfate, 24% ammonium, and 33% nitrate by mass, and the boundary layer reached up to about 5000
m and had no sharp upper edge. The size distributions indicated internal mixtures of ammonium sulfate and –nitrate in the boundary layer, while the organics were externally mixed. Additionally, a smaller mode consisting only of ammonium sulfate, was detected. This bimodal structure of ammonium sulfate was also detected above the boundary layer in 6
km altitude on 14 May.
Slightly soluble atmospherically relevant organic compounds, such as adipic acid, may influence particle CCN activity and therefore cloud formation. The 11 published experimental studies on the CCN ...activity of adipic acid particles are not consistent with each other nor do they in most cases agree with the Koehler theory. The CCN activity of adipic acid aerosol particles was studied over a significantly wider range of conditions than in any previous single study. The work spans the conditions of the previous studies and also provides alternate methods for producing wet and dry adipic acid particles without the need to produce them by atomization of aqueous solutions. The CCN effect of adipic acid coatings on both soluble and insoluble particles has also been studied. The CCN activation of the small (d sub(m)<150 nm) initially dry particles is subject to a deliquescence barrier, while for the larger particles the activation follows the Koehler curve. Adipic acid particles prepared in a wet state follow the Koehler curve over the full range of particle diameters studied. The experiments suggest that the scatter in the previously published CCN measurements is most likely due to the difficulty of producing uncontaminated adipic acid particles by atomization of solutions and possibly also due to uncertainties in the calibration of the instruments. The addition of a hydrophilic soluble compound to dry adipic acid eliminates the effect of particle phase, that is, the effect of the deliquescence barrier to CCN activation. An adipic acid coating on hydrophobic soot yields a CCN active particle. For the relatively small soot particles (d sub(core)=88 and 102 nm) the CCN activity of the coated particles approaches the deliquescence line of adipic acid, suggesting that the total size of the particle determines CCN activation and the soot core acts as a scaffold. Discussion Paper (PDF, 1787 KB) Interactive Discussion (Closed, 4 Comments) Final Revised Paper (ACP) Citation: Hings, S. S., Wrobel, W. C., Cross, E. S., Worsnop, D. R., Davidovits, P., and Onasch, T. B.: CCN activation experiments with adipic acid: effect of particle phase and adipic acid coatings on soluble and insoluble particles, Atmos. Chem. Phys. Discuss., 8, 4439-4482, 2008. Bibtex EndNote Reference Manager
During June and July 2003 the Sources and Origins of Atmospheric Cloud Droplets experiment (SOACED) was carried out on a mountain-top site in central Sweden. The main objective of the experiment was ...to characterise the microphysical and chemical properties of cloud droplet residuals and interstitial aerosol particles in continental clouds and to understand the processes controlling cloud properties at this location.
Interstitial and residual aerosol size distributions, cloud liquid water content and species- and size-resolved aerosol mass concentrations are the main variables employed to address questions pertaining to the cloud droplet number concentration and scavenging efficiency during a stratocumulus cloud event observed on July 28, 2003. In this cloud event, about 56% of the aerosol mass was associated with organic species, whilst SO
4 accounted for 23% and NH
4 for 14%. NO
3 and Cl made up about 7% of the total mass.
The partitioning of the aerosol particles between cloud droplets and interstitial air has been studied in terms of their microphysical properties. The scavenging efficiency, defined as the fraction of particles activated into cloud elements compared to the total amount of particles, was investigated as a function of size. The scavenging efficiency curves displayed different shapes during the cloud event, from an
S-shaped curve, with low scavenging efficiency in the Aitken mode and larger scavenging efficiency in the accumulation mode, to more unusual shapes where Aitken-mode particles were either solely activated or activated in addition to accumulation-mode particles.
This study suggests that alterations of the aerosol chemical composition occurred during the measurement period, changing the hygroscopic nature of the CCN and decreasing their activation diameter. It is also hypothesized that entrainment of drier air aloft may have introduced inhomogeneities in the supersaturation field and modified the
S-shaped scavenging curves.
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