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Mechanisms of Atmospheric Oxidation of the Oxygenates$
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Jack Calvert, Abdelwahid Mellouki, John Orlando, Michael Pilling, and Timothy Wallington

Print publication date: 2011

Print ISBN-13: 9780199767076

Published to Oxford Scholarship Online: November 2020

DOI: 10.1093/oso/9780199767076.001.0001

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PRINTED FROM OXFORD SCHOLARSHIP ONLINE (oxford.universitypressscholarship.com). (c) Copyright Oxford University Press, 2021. All Rights Reserved. An individual user may print out a PDF of a single chapter of a monograph in OSO for personal use. date: 19 January 2022

The Influence of Oxygenates on the Atmospheric Chemistry of Urban, Rural, and Global Environments

The Influence of Oxygenates on the Atmospheric Chemistry of Urban, Rural, and Global Environments

(p.1358) X The Influence of Oxygenates on the Atmospheric Chemistry of Urban, Rural, and Global Environments
Mechanisms of Atmospheric Oxidation of the Oxygenates

Jack Calvert

Abdelwahid Mellouki

John Orlando

Michael Pilling

Timothy Wallington

Oxford University Press

One cannot overestimate the importance of oxygenated organic compounds in atmospheric chemistry. As discussed in the previous chapters of this book and elsewhere (e.g., Wayne, 1991; Seinfeld and Pandis, 1998; Brasseur et al., 1999; Finlayson-Pitts and Pitts, 2000; Calvert et al., 2000, 2002, 2008) the atmosphere is an oxidizing environment and all organic compounds emitted into the atmosphere are converted into oxygenated organic compounds. The first-generation products are oxidized further. As an example, the oxidation of ethane gives CH3CHO, C2H5OH, and C2H5OOH as first-generation products and CH3OH, CH3OOH, CH2O, and HC(O)OH as second-generation products. An understanding of the chemistry of oxygenated organic compounds is central to unraveling the complex processes in the atmosphere. In this chapter we discuss the representation of oxygenates in atmospheric models, their participation in secondary organic aerosol formation, contribution to HOx chemistry in the upper troposphere, role in the transport of pollutants, and use as proxies for volatile organic compound (VOC) emissions. A major application of the chemical kinetics and mechanisms of VOC oxidation is the development of an understanding of the chemistry occurring in the troposphere and the use of that understanding to predict and develop strategies which help to mitigate adverse changes in air quality and climate change. Such applications depend on the development of models that assess chemical impacts; chemical mechanisms lie at the heart of such models. The mechanisms can be very detailed, often termed explicit, in models where the aim is to understand the chemistry occurring in a small volume of air, for example, in an analysis of processes determining radical concentrations in field measurements. Such a mechanistic approach can also be used, with increased computer resources, when a trajectory approach is used to assess the coupled impacts of atmospheric transport and chemistry. An Eulerian approach to modeling both regional and global processes presents greater problems, because the chemical rate equations have to be solved for each species at each spatial grid point in the model; this severely limits the number of chemical species that can be incorporated realistically in the model.

Keywords:   global budgets for, importance of in atmospheric chemistry, observation of, in the remote troposphere, representation of in chemical mechanisms, explicit or near-explicit mechanisms, lumped chemical mechanisms, carbon bond mechanism, GEOS-Chem, MOZART, proxies for VOC emissions, transport of pollutants

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