The present paper reviews existing knowledge with regard to Organic Aerosol (OA) of importance for global climate modelling and defines critical gaps needed to reduce the involved uncertainties. All pieces required for the representation of OA in a global climate model are sketched out with special attention to Secondary Organic Aerosol (SOA): The emission estimates of primary carbonaceous particles and SOA precursor gases are summarized. The up-to-date understanding of the chemical formation and transformation of condensable organic material is outlined. Knowledge on the hygroscopicity of OA and measurements of optical properties of the organic aerosol constituents are summarized. The mechanisms of interactions of OA with clouds and dry and wet removal processes parameterisations in global models are outlined. This information is synthesized to provide a continuous analysis of the flow from the emitted material to the atmosphere up to the point of the climate impact of the produced organic aerosol. The sources of uncertainties at each step of this process are highlighted as areas that require further studies.

/pdf/organic-aerosol-and-global-climate-modelling-a-review-4ojfzx6x50.pdf

Organic aerosol and global climate modelling: a review

http://krollgroup.mit.edu/papers/Kroll_2008.pdf

Chemistry of secondary organic aerosol: Formation and evolution of low-volatility organics in the atmosphere

Electronic excitation energies are determined using the CAM-B3LYP Coulomb-attenuated functional [T. Yanai et al. Chem. Phys. Lett. 393, 51 (2004)], together with a standard generalized gradient approximation (GGA) and hybrid functional. The degree of spatial overlap between the occupied and virtual orbitals involved in an excitation is measured using a quantity Lambda, and the extent to which excitation energy errors correlate with Lambda is quantified. For a set of 59 excitations of local, Rydberg, and intramolecular charge-transfer character in 18 theoretically challenging main-group molecules, CAM-B3LYP provides by far the best overall performance; no correlation is observed between excitation energy errors and Lambda, reflecting the good quality, balanced description of all three categories of excitation. By contrast, a clear correlation is observed for the GGA and, to a lesser extent, the hybrid functional, allowing a simple diagnostic test to be proposed for judging the reliability of a general excitation from these functionals--when Lambda falls below a prescribed threshold, excitations are likely to be in very significant error. The study highlights the ambiguous nature of the term "charge transfer," providing insight into the observation that while many charge-transfer excitations are poorly described by GGA and hybrid functionals, others are accurately reproduced.

/pdf/excitation-energies-in-density-functional-theory-an-ep38p1jml8.pdf

Excitation energies in density functional theory : an evaluation and a diagnostic test.

The vapour pressures of ice and supercooled water are reviewed with an emphasis on atmospheric applications. Parametrizations are given for the vapour pressure, molar heat capacity, and latent heat of vaporization of both ice and liquid water. For ice, the experimental vapour pressure data are in agreement with a derivation from the Clapeyron equation. Below 200 K cubic ice may affect the vapour pressure of ice both in the atmosphere and in the laboratory. All of the commonly used parametrizations for the vapour pressure of supercooled water are extrapolations that were not originally intended for use below the freezing point. In addition, the World Meteorological Organization definition of the vapour pressure of supercooled water contains an easily overlooked typographical error. Recent data on the molar heat capacity of supercooled water are used to derive its vapour pressure. Nevertheless, the uncertainty is such that measurements of the deliquescence and freezing behaviour of aerosol particles are beginning to be limited by uncertainties in the thermodynamics of supercooled water. Copyright © 2005 Royal Meteorological Society

/pdf/review-of-the-vapour-pressures-of-ice-and-supercooled-water-3m0zwl6nnb.pdf

Review of the vapour pressures of ice and supercooled water for atmospheric applications

Plasma–liquid interactions represent a growing interdisciplinary area of research involving plasma science, fluid dynamics, heat and mass transfer, photolysis, multiphase chemistry and aerosol science. This review provides an assessment of the state-of-the-art of this multidisciplinary area and identifies the key research challenges. The developments in diagnostics, modeling and further extensions of cross section and reaction rate databases that are necessary to address these challenges are discussed. The review focusses on non-equilibrium plasmas.

/pdf/plasma-liquid-interactions-a-review-and-roadmap-4kfoerpjnh.pdf

Plasma-liquid interactions: A review and roadmap

We suggest a chemical model for the composition, structure, and atmospheric processing of organic aerosols. This model is stimulated by recent field measurements showing that organic compounds are a significant component of atmospheric aerosols. The proposed model organic aerosol is an "inverted micelle" consisting of an aqueous core that is encapsulated in an inert, hydrophobic organic monolayer. The organic materials that coat the aerosol particles are surfactants of biological origin. We propose a chemical mechanism by which the organic surface layer will be processed by reactions with atmospheric radicals. The net result of an organic aerosol being exposed to an oxidizing atmosphere is the transformation of an inert hydrophobic film to a reactive, optically active hydrophilic layer. Consequently, processed organic aerosols can grow by water accretion and form cloud condensation nuclei, influencing atmospheric radiative transfer. Radiative transfer may be affected directly by the chromophores left on the surface of the aerosol after chemical transformation. The chemical model yields certain predictions which are testable by observations. Among them is a curve of the percent organic material as a function of particle diameter which predicts that a high fraction of the mass of the upper tropospheric aerosol will be organic. Atmospheric processing of organic aerosols will lead to the release of small organic fragments into the troposphere which will play a subsequent role in homogeneous chemistry. Organic aerosols are likely to act as a transport vehicle of organics and other water insoluble compounds into the atmosphere. We speculate that biomass burning will produce a similar coating of surfactants derived from land sources. Finally, it is pointed out that the radical-induced transformation of the surface layer of aerosol particles from hydrophobic to hydrophilic offers an additional means by which the biosphere, through atmospheric chemistry, can affect the radiative balance.

https://agupubs.onlinelibrary.wiley.com/doi/pdf/10.1029/1999JD900073

Atmospheric processing of organic aerosols

The influence of organic films at the air-aqueous boundary on atmospheric processes.

The importance of water in atmospheric and environmental chemistry initiated recent studies with results documenting catalysis, suppression and anti-catalysis of thermal and photochemical reactions due to hydrogen bonding of reagents with water. Water, even one water molecule in binary complexes, has been shown by quantum chemistry to stabilize the transition state and lower its energy. However, new results underscore the need to evaluate the relative competing rates between reaction and dissipation to elucidate the role of water in chemistry. Water clusters have been used successfully as models for reactions in gas-phase, in aqueous condensed phases and at aqueous surfaces. Opportunities for experimental and theoretical chemical physics to make fundamental new discoveries abound. Work in this field is timely given the importance of water in atmospheric and environmental chemistry.

Perspective: Water cluster mediated atmospheric chemistry

Aerosol particles in the atmosphere have recently been found to contain a large number of chemical elements and a high content of organic material. The latter property is explicable by an inverted micelle model. The aerosol sizes with significant atmospheric lifetimes are the same as those of single-celled organisms, and they are predicted by the interplay of aerodynamic drag, surface tension, and gravity. We propose that large populations of such aerosols could have afforded an environment, by means of their ability to concentrate molecules in a wide variety of physical conditions, for key chemical transformations in the prebiotic world. We also suggest that aerosols could have been precursors to life, since it is generally agreed that the common ancestor of terrestrial life was a single-celled organism. The early steps in some of these initial transformations should be accessible to experimental investigation.

https://www.pnas.org/content/pnas/97/22/11864.full.pdf

Atmospheric aerosols as prebiotic chemical reactors

[1] An extraordinary episode of fine particles (diameter mainly <2.5 μm) occurred in Helsinki, southern Finland, at the end of February 1998. The air masses came from the North Atlantic Ocean and passed over France, Germany, and southern Scandinavia. Particles were collected during the episode as well as before and after it. Uncoated particle samples were adhered to an indium substrate and were studied by a scanning electron microscope (SEM) coupled with an energy dispersive X-ray microanalyzer (EDX). A great proportion of the particles behaved differently than aerosols previously studied by microscopic techniques. The particles (size mainly 0.5–1 μm) did not exhibit solid shape. They were “bubbling” or “pulsating” continually, enlarging in one part and shrinking in another. Some particles were broken down, especially when the beam of the electron microscope was focused on them. EDX analyses showed that the particles contained much carbon together with oxygen, sulfur, and sodium. Ion analyses by ion chromatography revealed high concentrations of sodium, sulfate, nitrate, and ammonium. The particles were identified as marine sea-salt aerosols, which had accumulated anthropogenic emissions and lost chloride during their flow through continental polluted air. The shape fluctuations and the high carbon content observed by SEM/EDX led to the conclusion that the aerosols were enclosed by an organic membrane. Direct insertion probe/mass spectrometry investigations showed remarkable amounts of fragmented aliphatic hydrocarbons, which were considered as an evidence of a lipid membrane on the surface of the particles. The impact of the posited organic film on the properties of sea-salt particles, as well as on Earth's climate, is discussed.

https://agupubs.onlinelibrary.wiley.com/doi/pdf/10.1029/2000JD000282

Veronica Vaida

Papers

Atmospheric processing of organic aerosols

The influence of organic films at the air-aqueous boundary on atmospheric processes.

Perspective: Water cluster mediated atmospheric chemistry

Atmospheric aerosols as prebiotic chemical reactors

New evidence of an organic layer on marine aerosols