Atmospheric Cloud Droplets Research Articles

Cloud Activation Potentials for Atmospheric α-Pinene and β-Caryophyllene Ozonolysis Products.

The formation of atmospheric cloud droplets due to secondary organic aerosol (SOA) particles is important for quantifying the Earth’s radiative balance under future, possibly warmer, climates, yet is only poorly understood. While cloud activation may be parametrized using the surface tension depression that coincides with surfactant partitioning to the gas–droplet interface, the extent to which cloud activation is influenced by both the chemical structure and reactivity of the individual molecules comprising this surfactant pool is largely unknown. We report herein considerable differences in the surface tension depression of aqueous pendant droplets that contain synthetically prepared ozonolysis products derived from α-pinene and β-caryophyllene, the most abundant of the monoterpenes and sesquiterpenes, respectively, that are emitted over the planet’s vast forest ecosystems. Oxidation products derived from β-caryophyllene were found to exhibit significantly higher surface activity than those prepared from α-pinene, with the critical supersaturation required for cloud droplet activation reduced by 50% for β-caryophyllene aldehyde at 1 mM. These considerable reductions in the critical supersaturation were found to coincide with free energies of adsorption that exceed ∼25 kJ/mol, or just one hydrogen bond equivalent, depending on the ammonium sulfate and oxidation product concentration in the solution. Additional experiments showed that aldehyde-containing oxidation products exist in equilibrium with hydrated forms in aqueous solution, which may modulate their bulk solubility and surface activity. Equilibration time scales on the order of 10–5 to 10–4 s calculated for micrometer-sized aerosol particles indicate instantaneous surface tension depression in the activation processes leading to cloud formation in the atmosphere. Our findings highlight the underlying importance of molecular structure and reactivity when considering cloud condensation activity in the presence of SOA particles.

Laboratory Studies of Scattering Properties of Polluted Cloud Droplets: Implications for FSSP Measurements

Abstract Laboratory experiments were conducted in the Mainz vertical wind tunnel to study the effects of pollutants dissolved or suspended in cloud droplets on the droplet size measurements of a Forward Scattering Spectrometer Probe (FSSP). The FSSP is a widely used instrument to derive microphysical properties of atmospheric clouds. Individual droplets of different well-defined sizes were freely falling at their terminal velocities in the wind tunnel while the intensity of radiation emitted by the He–Ne laser of the FSSP and scattered by the droplets was measured. For this purpose, the FSSP was adapted and mounted to the wind tunnel. The intensity of radiation scattered by the droplets in the FSSP measurement is principally used to derive the droplet size. The droplets contained soluble ammonium sulfate or suspended absorbent graphite particles as pollutants in concentrations that were higher than usually found in atmospheric cloud droplets. The results of the measurements and corresponding simulations indicate that for high pollutant concentrations, the scattered laser radiation detected by the FSSP depends significantly on the refractive index of the droplet (i.e., on the concentration of soluble or insoluble pollutants). However, for the lower pollutant concentrations usually observed in atmospheric cloud droplets, the need for correcting the droplet sizes measured with the FSSP for the effects of the pollutions can be avoided.

Effect of soot on immersion freezing of water and possible atmospheric implications

More than 3000 water droplets with soot particles immersed were monitored individually to identify the effect of heterogeneous freezing and establish the link between soot properties and freezing efficiency. A set of soot samples from many combustion sources, including an aircraft engine combustor were examined. The list of key soot properties affecting freezing were determined. It appears that soot effectiveness in causing the droplets to freeze mainly depends on the soot behaviour in water defined by the mass density of soot agglomerates, size and wetting. When large mass particles were homogeneously distributed through droplets and were stable to sedimentation effects median freezing temperatures of such droplets were significantly warmer than pure water droplets. The long-term presence of large soot agglomerates in water leads to an increase in the freezing efficiency over time because of the slow kinetics of wetting. Small sizes of soot agglomerates stimulate aggregative instability in droplets with large soot mass which decreases the total soot surface area and the freezing temperature. The highest freezing efficiency is found for homogeneously distributed soot agglomerates of high porosity. A gradual increase of the freezing temperature in correspondence with number density of active oxygen-containing sites is observed for soots having surfaces of low or intermediate polarity. However, highly soluble surface compounds, such as sulfates, may be easily dissolved in water leading to a decrease in the potential freezing efficiency. This was the case found for aircraft engine combustor generated soot. Therefore relatively hydrophobic soot with a significant number of oxygen-containing functional groups but not covered totally by hydrophilic sites and soluble compounds is proposed to act as the most efficient immersion freezing nuclei in the atmospheric cloud droplets.

Microphysical and chemical characteristics of cloud droplet residuals and interstitial particles in continental stratocumulus clouds

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.