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The focus of this contract was to investigate selected aspects of the atmospheric chemistry of volatile organic compounds (VOCs) emitted into the atmosphere from energy-related sources as well as from biogenic sources. The classes of VOCs studied were polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs, the biogenic VOCs isoprene, 2-methyl-3-buten-2-ol and cis-3-hexen-1-ol, alkenes (including alkenes emitted from vegetation) and their oxygenated atmospheric reaction products, and a series of oxygenated carbonyl and hydroxycarbonyl compounds formed as atmospheric reaction products of aromatic hydrocarbons and other VOCs. Large volume reaction chambers were used to investigate the kinetics and/or products of photolysis and of the gas-phase reactions of these organic compounds with hydroxyl (OH) radicals, nitrate (NO3) radicals, and ozone (O3), using an array of analytical instrumentation to analyze the reactants and products (including gas chromatography, in situ Fourier transform infrared spectroscopy, and direct air sampling atmospheric pressure ionization tandem mass spectrometry). The following studies were carried out. The photolysis rates of 1- and 2-nitronaphthalene and of eleven isomeric methylnitronaphthalenes were measured indoors using blacklamp irradiation and outdoors using natural sunlight. Rate constants were measured for the gas-phase reactions of OH radicals, Cl atoms and NO3 radicals with naphthalene, 1- and 2-methylnaphthalene, 1- and 2-ethylnaphthalene and the ten dimethylnaphthalene isomers. Rate constants were measured for the gas-phase reactions of OH radicals with four unsaturated carbonyls and with a series of hydroxyaldehydes formed as atmospheric reaction products of other VOCs, and for the gas-phase reactions of O3 with a series of cycloalkenes. Products of the gas-phase reactions of OH radicals and O3 with a series of biogenically emitted VOCs were identified and quantified. Ambient atmospheric measurements of the concentrations of a number of PAHs, nitro-PAHs, nitrated polycyclic aromatic compounds and biogenic VOCs were carried out in the Los Angeles air basin. In addition to these laboratory and ambient field studies, two literature reviews of VOC atmospheric chemistry and of the kinetics of the reactions of OH radicals with alkanes were also carried out. This research has been reported in 15 peer-reviewed publications.
Every day, large quantities of volatile organic compounds (VOCs) are emitted into the atmosphere from both anthropogenic and natural sources. The formation of gaseous and particulate secondary products caused by oxidation of VOCs is one of the largest unknowns in the quantitative prediction of the earth’s climate on a regional and global scale, and on the understanding of local air quality. To be able to model and control their impact, it is essential to understand the sources of VOCs, their distribution in the atmosphere and the chemical transformations which remove these compounds from the atmosphere. In recent years techniques for the analysis of organic compounds in the atmosphere have been developed to increase the spectrum of detectable compounds and their detection limits. New methods have been introduced to increase the time resolution of those measurements and to resolve more complex mixtures of organic compounds. Volatile Organic Compounds in the Atmosphere describes the current state of knowledge of the chemistry of VOCs as well as the methods and techniques to analyse gaseous and particulate organic compounds in the atmosphere. The aim is to provide an authoritative review to address the needs of both graduate students and active researchers in the field of atmospheric chemistry research.
Interest in volatile organic compounds (VOCs) as air pollutants has increased dramatically in recent years. This book covers a number of very topical issues concerning VOCs, including stratospheric ozone depletion due to CFCs, and the properties of alternative substances; the role of VOCs in the photochemical formation of lower atmosphere (tropospheric) ozone; and the problem of the direct toxicity of VOCs such as benzene and formaldehyde. This Issue reviews our current knowledge of VOCs, drawing upon the expertise of renowned experts and major national and international research programmes. It examines man-made and natural sources, as well as pathways and chemical reactions in the atmosphere. It also looks closely at the sources and concentrations of VOCs indoors, where humans are most likely to be exposed to them. Volatile Organic Compounds in the Atmosphere describes techniques used for the calculation of emissions inventories and strategies for control, and explores the many Government policy matters relating to VOCs. It provides readers with in-depth, clearly explained coverage of the many complex scientific and policy issues surrounding VOCs in the atmosphere.
This companion provides a collection of frequently needed numerical data as a convenient desk-top or pocket reference for atmospheric scientists as well as a concise source of information for others interested in this matter. The material contained in this book was extracted from the recent and the past scientific literature; it covers essentially all aspects of atmospheric chemistry. The data are presented primarily in the form of annotated tables while any explanatory text is kept to a minimum. In this condensed form of presentation, the volume may serve also as a supplement to many textbooks used in teaching the subject at various universities. Peter Warneck, a physical chemist specializing in atmospheric chemistry, received the diploma in 1954 and the doctorate in 1956 at the university in Bonn, Germany. In 1959, following several postdoctoral assignments, he joined the GCA Corporation in Bedford, Massachusetts, where he explored elementary processes in the atmospheres of the earth and other planets. He returned to Germany in 1970 to head the chemical kinetics group in the Air Chemistry Division of the Max-Planck-Institute for Chemistry in Mainz. In 1974 he also became professor of physical chemistry at the university in Mainz. In 1991, following German reunification, Warneck was appointed the founding director of the new Institute for Tropospheric Research in Leipzig. He served in this position parallel to his activities in Mainz until official retirement. Warneck’s research included laboratory studies of chemical mechanisms and photochemistry as well as the development of analytical techniques for field measurements. Since 1990, his interests are focused on chemical reactions in clouds. Jonathan Williams is an atmospheric chemist. He received his BSc in Chemistry and French and his Ph.D. in Environmental Science from the University of East Anglia, England. Between 1995-1997 he worked as a postdoctoral researcher at the NOAA Aeronomy laboratory in Boulder, USA, and from 1998 to present as a member of staff at the Max Planck Institute for Chemistry, Mainz, Germany. He has participated in many international field measurement campaigns on aircraft, ships and at ground stations. Dr Williams is currently an editor on three atmospheric chemistry journals. His present research involves investigating the chemistry of reactive organic species in the atmosphere, in particular over forested ecosystems and in the marine boundary layer. Dr Williams leads a research group focussed specifically on Volatile Organic Compounds (VOC) at the Max Planck Institute and in 2008 he was made an honorary Reader at the University of East Anglia, UK.
The uncertainties in the aerosol effects on radiative forcing limit our knowledge of climate change, presenting us with an important research challenge. Aerosols in Atmospheric Chemistry introduces basic concepts about the characterization, formation, and impacts of ambient aerosol particles as an introduction to graduate students new to the field. Each chapter also provides an up-to-date synopsis of the latest knowledge of aerosol particles in atmospheric chemistry.
Chemical Compounds in the Atmosphere deals with the chemistry of organic and inorganic compounds found in the atmosphere, including rare gases and compounds of oxygen and hydrogen, halogenated aromatic compounds, and organometallic compounds. The sources and concentrations of atmospheric trace gases are discussed, along with their chemical reactions and ultimate fates. The compounds are divided into groups on the basis of chemical constituent or chemical structure. Comprised of 10 chapters, this book opens with an overview of atmospheric composition and atmospheric chemistry, followed by a discussion on inorganic compounds present in the troposphere such as rare gases and compounds containing nitrogen, sulfur, and halogens. The next chapters focus on hydrocarbons such as alkanes, alkenes, and alkynes; carbonyl compounds such as ketones and aldehydes; oxygenated and nitrogen- and sulfur-containing organic compounds; organic halogenated compounds such as mercaptans and thiocyanates; and organometallic compounds such as organophosphorus pesticides. The final chapter is a synthesis of data on atmospheric compounds mentioned in this text, with emphasis on their occurrence, sources, oxidation, and lifetimes. The chemistry of acid rain is also considered. This monograph will be of value to those engaged in atmospheric measurements, theoretical and laboratory studies of chemical parameters relevant to the atmosphere, and air quality assessments.