Secondary organic aerosol (SOA) accounts for a significant fraction of ambient tropospheric aerosol and a detailed knowledge of the formation, properties and transformation of SOA is therefore required to evaluate its impact on atmospheric processes, climate and human health. The chemical and physical processes associated with SOA formation are complex and varied, and, despite considerable progress in recent years, a quantitative and predictive understanding of SOA formation does not exist and therefore represents a major research challenge in atmospheric science. This review begins with an update on the current state of knowledge on the global SOA budget and is followed by an overview of the atmospheric degradation mechanisms for SOA precursors, gas-particle partitioning theory and the analytical techniques used to determine the chemical composition of SOA. A survey of recent laboratory, field and modeling studies is also presented. The following topical and emerging issues are highlighted and discussed in detail: molecular characterization of biogenic SOA constituents, condensed phase reactions and oligomerization, the interaction of atmospheric organic components with sulfuric acid, the chemical and photochemical processing of organics in the atmospheric aqueous phase, aerosol formation from real plant emissions, interaction of atmospheric organic components with water, thermodynamics and mixtures in atmospheric models. Finally, the major challenges ahead in laboratory, field and modeling studies of SOA are discussed and recommendations for future research directions are proposed.

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The formation, properties and impact of secondary organic aerosol: current and emerging issues

. As part of a series of papers on the sources, distribution and potential impact of biological particles in the atmosphere, this paper introduces and summarizes the potential role of biological particles in atmospheric clouds. Biological particles like bacteria or pollen may be active as both cloud condensation nuclei (CCN) and heterogeneous ice nuclei (IN) and thereby can contribute to the initial cloud formation stages and the development of precipitation through giant CCN and IN processes. The paper gives an introduction to aerosol-cloud processes involving CCN and IN in general and provides a short summary of previous laboratory, field and modelling work which investigated the CCN and IN activity of bacterial cells and pollen. Recent measurements of atmospheric ice nuclei with a continuous flow diffusion chamber (CFDC) and of the heterogeneous ice nucleation efficiency of bacterial cells are also briefly discussed. As a main result of this overview paper we conclude that a proper assessment of the impact of biological particles on tropospheric clouds needs new laboratory, field and modelling work on the abundance of biological particles in the atmosphere and their CCN and heterogeneous IN properties.

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Microbiology and atmospheric processes: the role of biological particles in cloud physics

Ice in the troposphere affects a variety of processes, including the formation of precipitation, and cloud lifetime, albedo, dynamics, and electrification. A lack of understanding of the ways in which ice is created and multiplied hampers progress in understanding all of these processes. We survey the state of knowledge, starting with homogeneous nucleation, where current formulations for freezing from both pure water and solutions have considerable predictive power. However, debate still exists on the underlying mechanisms of nucleation. Using the concepts and framework that homogeneous nucleation provides, heterogeneous nucleation, where neither a commonly agreed upon theory nor even standard measurement technique exists, is considered. Investigators have established the ice-nucleating characteristics of broad classes of substances, such as mineral dust and soot, which are important ice nuclei in t he atmosphere, but a coherent theory of why these substances act as they do has yet to emerge. All ice in ...

Production of Ice in Tropospheric Clouds: A Review.

Prevention of ice accretion and adhesion on surfaces is relevant to many applications, leading to improved operation safety, increased energy efficiency, and cost reduction. Development of passive nonicing coatings is highly desirable, since current antiicing strategies are energy and cost intensive. Superhydrophobicity has been proposed as a lead passive nonicing strategy, yet the exact mechanism of delayed icing on these surfaces is not clearly understood. In this work, we present an in-depth analysis of ice formation dynamics upon water droplet impact on surfaces with different wettabilities. We experimentally demonstrate that ice nucleation under low-humidity conditions can be delayed through control of surface chemistry and texture. Combining infrared (IR) thermometry and high-speed photography, we observe that the reduction of water–surface contact area on superhydrophobic surfaces plays a dual role in delaying nucleation: first by reducing heat transfer and second by reducing the probability of het...

Dynamics of Ice Nucleation on Water Repellent Surfaces

From the frontiers of research on ice dynamics in its broadest sense, this review surveys the structures of ice, the patterns or morphologies it may assume, and the physical and chemical processes in which it is involved. Open questions in the various fields of ice research in nature are highlighted, ranging from terrestrial and oceanic ice on Earth, to ice in the atmosphere, to ice on other Solar System bodies and in interstellar space.

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Ice structures, patterns, and processes: A view across the icefields

The process by which liquid cloud droplets homogeneously crystallize into ice is still not well understood. The ice nucleation process based on the standard and classical theory of homogeneous freezing initiates within the interior volume of a cloud droplet. Current experimental data on homogeneous freezing rates of ice in droplets of supercooled water, both in air and emulsion oil samples, show considerable scatter. For example, at −33°C, the reported volume-based freezing rates of ice in supercooled water vary by as many as 5 orders of magnitude, which is well outside the range of measurement uncertainties. Here, we show that the process of ice nucleus formation at the air (or oil)-liquid water interface may help to explain why experimental results on ice nucleation rates yield different results in different ambient phases. Our results also suggest that surface crystallization of ice in cloud droplets can explain why low amounts of supercooled water have been observed in the atmosphere near −40°C.

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Surface crystallization of supercooled water in clouds

We attempt to explain the experimental and molecular dynamics simulation evidence that suggests that the freezing of atmospheric aerosols occurs beginning at the droplet surface By using the capillarity approximation, we derive the reversible work of formation of a crystal nucleus in the cases where it forms homogeneously within a (supercooled) bulk liquid and where it forms “pseudoheterogeneously” at the surface Comparing the works of formation in these two cases, one obtains a condition that must hold in order for pseudoheterogeneous (surface) crystallization to be thermodynamically more favorable than homogeneous (bulk) crystallization This condition is satisfied when at least one crystal facet is only partially wettable by its own melt 1 Surface versus Bulk Nucleation This paper may be regarded as a sequel to the preceding paper, 1 in which the analysis of existing laboratory data on the freezing of droplets of aqueous HNO3 into NAT and NAD particles suggests a nucleation process that is surface based Here, we present a theoretical analysis to determine conditions under which the surface-stimulated mode of crystallization is thermodynamically favored over the volume-based mode

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Thermodynamic Conditions for the Surface-Stimulated Crystallization of Atmospheric Droplets

Nitric acid-containing cloud particles, known as polar stratospheric clouds, play an important role in the springtime ozone destruction over the polar regions. Nitric acid initially condenses in the polar stratosphere to form supercooled solution droplets of mainly nitric acid and water with trace amounts of sulfuric acid. Nitric acid dihydrate (NAD) and nitric acid trihydrate (NAT) later crystallize from this supercooled solution phase to form solid polar stratospheric cloud particles. Until now, experimental data on this crystallization process has been analyzed under the assumption that NAD and NAT nucleation took place in the interior volume of a cloud droplet. However, in this paper, reanalysis of experimental data on the homogeneous freezing rates of concentrated aqueous nitric acid solution droplets provides substantial support for the occurrence of nucleation “pseudoheterogeneously” at the air -aqueous nitric acid solution interface of the droplet. Furthermore, in a following paper, theory that provides compelling evidence for such interfacial nucleation is developed. Together, the reanalysis of laboratory data in this paper and the supporting theoretical arguments in the following paper suggest that the homogeneous nucleation process occurring in atmospheric droplets may be a surface- rather than a volume-related rate process.

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Y. S. Djikaev

Papers

Surface crystallization of supercooled water in clouds

Thermodynamic Conditions for the Surface-Stimulated Crystallization of Atmospheric Droplets

Laboratory Evidence for Surface Nucleation of Solid Polar Stratospheric Cloud Particles