Towards closing the gap between hygroscopic growth and CCN activation for secondary organic aerosols-Part 3: Influence of the chemical composition on the hygroscopic properties and volatile fractions of aerosols

The influence of varying levels of water mixing ratio,r during the formation of secondary organic aerosol (SOA) from the ozonolysis of α-pinene on the SOA hygroscopicity and volatility was investigated. The reaction proceeded and aerosols were generated in a mixing chamber and the hygroscopic characteristics of the SOA were determined with the Leipzig Aerosol Cloud Interaction Simulator (LACIS) and a Cloud Condensation Nuclei counter (CCNc). In parallel, a High-Resolution Time-of-Flight Aerodyne Aerosol Mass Spectrometer (HR-ToF-AMS) located downstream of a thermodenuder (TD) sampling from the mixing chamber, to collect mass spectra of particles from the volatile and less-volatile fractions of the SOA. Results showed that both hygroscopic growth and the volatile fraction of the SOA increased with increases in r inside the mixing chamber during SOA generation. An effective density of 1.40 g cm-3 was observed for the generated SOA when the reaction proceeded with <1 g kg-1. Changes in the concentrations of the fragment CO2+ and the sum of CxH+y(short name CHO) and CxH+y (short name CH) fragments as measured by the HR-ToF-AMS were used to estimate changes in the oxidation level of the SOA with reaction conditions, using the ratios CO2 + to CH and CHO to CH. Under humid conditions, both ratios increased, corresponding to the presence of more oxygenated functional groups (i.e., multifunctional carboxylic acids). This result is consistent with the α-pinene ozonolysis mechanisms which suggest that water interacts with the stabilized Criegee intermediate. The volatility and the hygroscopicity results show that SOA generation via ozonolysis of &alpha;-pinene in the presence of water vapour (r <16.9 g kg-1) leads to the formation of more highly oxygenated compounds that are more hygroscopic and more volatile than compounds formed under dry conditions. © 2010 Author(s)

Towards closing the gap between hygroscopic growth and activation for secondary organic aerosol: Part 1 – Evidence from measurements

Secondary Organic Aerosols (SOA) studied in previous laboratory experiments generally showed only slight hygroscopic growth, but a much better activity as a CCN (Cloud Condensation Nucleus) than indicated by the hygroscopic growth. This discrepancy was examined at LACIS (Leipzig Aerosol Cloud Interaction Simulator), using a portable generator that produced SOA particles from the ozonolysis of α-pinene, and adding butanol or butanol and water vapor during some of the experiments. The light scattering signal of dry SOA-particles was measured by the LACIS optical particle spectrometer and was used to derive a refractive index for SOA of 1.45. LACIS also measured the hygroscopic growth of SOA particles up to 99.6% relative humidity (RH), and a CCN counter was used to measure the particle activation. SOA-particles were CCN active with critical diameters of e.g. 100 nm and 55 nm at super-saturations of 0.4% and 1.1%, respectively. But only slight hygroscopic growth with hygroscopic growth factors ≤1.05 was observed at RH98%, the hygroscopic growth increased stronger than would be expected if a constant hygroscopicity parameter for the particle/droplet solution was assumed. An increase of the hygroscopicity parameter by a factor of 4–6 was observed in the RH-range from below 90% to 99.6%, and this increase continued for increasingly diluted particle solutions for activating particles. This explains an observation already made in the past: that the relation between critical super-saturation and dry diameter for activation is steeper than what would be expected for a constant value of the hygroscopicity. Combining measurements of hygroscopic growth and activation, it was found that the surface tension that has to be assumed to interpret the measurements consistently is greater than 55 mN/m, possibly close to that of pure water, depending on the different SOA-types produced, and therefore only in part accounts for the discrepancy between hygroscopic growth and CCN activity observed for SOA particles in the past

Development and testing of an aerosol/stratus cloud parameterization scheme for middle and high latitudes. Year 3 technical progress report, November 1, 1996--August 31, 1997

At the present time, general circulation models (GCMs) poorly represent clouds, to the extent that they cannot be relied upon to simulate the climatic effects of increasing concentrations of greenhouse gases, or of anthropogenic perturbations to concentrations of cloud condensation nuclei (CCN) or ice nuclei (IN). The net radiative forcing of clouds varies strongly with latitude. Poleward of 30 degrees in both hemispheres, low-level clouds create a net cooling effect corresponding to radiative divergences of {minus}50 to {minus}100 W/m{sup 2}. It is likely that a combination of fogs, boundary-layer stratocumulus, and stratus clouds are the main contributors to this forcing. Models of the response of the microphysical and radiative properties of clouds to changes in aerosol abundance, for a variety of large-scale meteorological forcings, are important additions to GCMs used for the study of the role of Arctic systems in global climate. The overall objective of this research is the development of an aerosol/cloud microphysics parameterization of mixed-phase stratus and boundary-layer clouds which responds to variations in CCN and IN. The parameterization is to be designed for ultimate use in GCM simulations as a tool in understanding the role of CCN, IN, and Arctic clouds in radiation budgets. Several versions of the CSU RAMS (Regional Atmospheric Modeling System) will be used during the course of this work. The parameterizations developed in this research are intended for application in a single-column cloud model, designed as an adaptive grid model which can interface into a GCM vertical grid through distinct layers of the troposphere where the presence of layer clouds is expected

Towards closing the gap between hygroscopic growth and activation for secondary organic aerosol - Part 2: Theoretical approaches

We examine the hygroscopic properties of secondary organic aerosol particles generated through the reaction of α-pinene and ozone using a continuous flow reaction chamber. The water activity versus composition relationship is calculated from measurements of growth factors at relative humidities up to 99.6% and from measurements of cloud condensation nuclei activity. The observed relationships are complex, suggesting highly non-ideal behavior for aerosol water contents at relative humidities less than 98%. We present two models that may explain the observed water activity-composition relationship equally well. The first model assumes that the aerosol is a pseudo binary mixture of infinitely water soluble compounds and sparingly soluble compounds that gradually enter the solution as dilution increases. The second model is used to compute the Gibbs free energy of the aerosol-water mixture and shows that the aerosol behaves similarly to what can be expected for single compounds that contain a certain fraction of oxygenated and non-polar functional groups

Irreversible loss of ice nucleation active sites in mineral dust particles caused by sulphuric acid condensation

During the FROST-2 (FReezing Of duST) measurement campaign conducted at the Leipzig Aerosol Cloud Interaction Simulator (LACIS), we investigated changes in the ice nucleation properties of 300 nm Arizona Test Dust mineral particles following thermochemical processing by varying amounts and combinations of exposure to sulphuric acid vapour, ammonia gas, water vapour, and heat. The processed particles' heterogeneous ice nucleation properties were determined in both the water subsaturated and supersaturated humidity regimes at −30 °C and −25 °C using Colorado State University's continuous flow diffusion chamber. The amount of sulphuric acid coating material was estimated by an aerosol mass spectrometer and from CCN-derived hygroscopicity measurements. The condensation of sulphuric acid decreased the dust particles' ice nucleation ability in proportion to the amount of sulphuric acid added. Heating the coated particles in a thermodenuder at 250 °C – intended to evaporate the sulphuric acid coating – reduced their freezing ability even further. We attribute this behaviour to accelerated acid digestion of ice active surface sites by heat. Exposing sulphuric acid coated dust to ammonia gas produced particles with similarly poor freezing potential; however a portion of their ice nucleation ability could be restored after heating in the thermodenuder. In no case did any combination of thermochemical treatments increase the ice nucleation ability of the coated mineral dust particles compared to unprocessed dust. These first measurements of the effect of identical chemical processing of dust particles on their ice nucleation ability under both water subsaturated and mixed-phase supersaturated cloud conditions revealed that ice nucleation was more sensitive to all coating treatments in the water subsaturated regime. The results clearly indicate irreversible impairment of ice nucleation activity in both regimes after condensation of concentrated sulphuric acid. This implies that the sulphuric acid coating caused permanent chemical and/or physical modification of the ice active surface

Hygroscopicity of particles at two rural, urban influenced sites during Pacific 2001: Comparison with estimates of water uptake from particle composition

Hygroscopicity of particles was measured at Langley (rural) and Eagle Ridge (semi-rural) as part of the Pacific 2001 field campaign. The measured growth factors at the two sites were comparable. However, differences in particle composition as measured by an Aerosol Mass Spectrometer were evident at these two sites. Sulphate mass concentration was found to be similar at the two sites, while higher nitrate and organic mass were observed at Eagle Ridge. Higher growth factors were observed when the air mass was impacted by SO2 sources, while lower growth factors were observed when the air mass was affected by urban emissions. To examine the hygroscopic role of the different particle components, expected growth factors were calculated from the composition data and compared to measured growth factors. Calculations were done using the Zdanovskii, Stokes and Robinson (ZSR) mixing rule. Sulphate fraction played a dominant role in particle hygroscopicity at both sites. Calculated growth factors were within the uncertainty of the measurements, except when the nitrate fraction was high. The results imply that particulate nitrate takes up much less water than ammonium nitrate, indicating that the ZSR mixing rule fails for nitrate. Small variations of organic growth factors with source regions suggest that secondary organic matter is more hygroscopic than primary organic matter