Impacts of Controlling Reactivity and Temperature on Advanced Study of Secondary Organic Aerosol Formation

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ISBN 13 : 9781369088045
Total Pages : 131 pages
Book Rating : 4.0/5 (88 download)

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Book Synopsis Impacts of Controlling Reactivity and Temperature on Advanced Study of Secondary Organic Aerosol Formation by : Mary Elizabeth Kacarab

Download or read book Impacts of Controlling Reactivity and Temperature on Advanced Study of Secondary Organic Aerosol Formation written by Mary Elizabeth Kacarab and published by . This book was released on 2016 with total page 131 pages. Available in PDF, EPUB and Kindle. Book excerpt: Secondary organic aerosol (SOA) is formed via the oxidation of volatile organic compounds emitted to the atmosphere from both biogenic and anthropogenic sources. Due to the complexity of atmospheric composition and range of ambient conditions, aerosol models, which are mostly based off observed yields from controlled laboratory chamber experiments, greatly underestimate global SOA formation. To increase the understanding of the formation and properties of ambient SOA, it is imperative to explore ways to improve the complexity of chamber studies while still maintaining a level of control not found outside of the laboratory.

Primärliteratur 1817-1953

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ISBN 13 :
Total Pages : 191 pages
Book Rating : 4.:/5 (256 download)

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Book Synopsis Primärliteratur 1817-1953 by :

Download or read book Primärliteratur 1817-1953 written by and published by . This book was released on 1960 with total page 191 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Environmental Simulation Chambers: Application to Atmospheric Chemical Processes

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Publisher : Springer Science & Business Media
ISBN 13 : 9781402042317
Total Pages : 492 pages
Book Rating : 4.0/5 (423 download)

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Book Synopsis Environmental Simulation Chambers: Application to Atmospheric Chemical Processes by : Ian Barnes

Download or read book Environmental Simulation Chambers: Application to Atmospheric Chemical Processes written by Ian Barnes and published by Springer Science & Business Media. This book was released on 2006-01-13 with total page 492 pages. Available in PDF, EPUB and Kindle. Book excerpt: The book gives in the first instance descriptions of different types of so-called environment chambers or photoreactors used mainly for the simulation and/or investigation of important chemical processes occurring in the atmosphere. The types of reactor described include outdoor and indoor chambers, temperature regulated chambers and glass and Teflon foil chambers The practical use of chambers is demonstrated in contributions by leading scientists in the field of atmospheric chemistry using, in many cases, current results. The types of atmospherically relevant investigations described include the measurement of reactivities, the measurement of radicals, the measurement of photolysis frequencies and products, kinetic and product studies on the oxidation of different types of hydrocarbons by important oxidant species (OH, N03, 03), formation of secondary organic aerosol from hydrocarbon oxidation etc. A special section includes contributions from eastern European countries which highlight some of the environmental research being performed in these countries. An abridged version of a specially commissioned review by the JRC Ispra on the status of environmental research in eastern European countries is also included in this section.

Laboratory Experiments and Modeling for Interpreting Field Studies of Secondary Organic Aerosol Formation Using an Oxidation Flow Reactor

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ISBN 13 :
Total Pages : 46 pages
Book Rating : 4.:/5 (946 download)

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Book Synopsis Laboratory Experiments and Modeling for Interpreting Field Studies of Secondary Organic Aerosol Formation Using an Oxidation Flow Reactor by :

Download or read book Laboratory Experiments and Modeling for Interpreting Field Studies of Secondary Organic Aerosol Formation Using an Oxidation Flow Reactor written by and published by . This book was released on 2016 with total page 46 pages. Available in PDF, EPUB and Kindle. Book excerpt: This grant was originally funded for deployment of a suite of aerosol instrumentation by our group in collaboration with other research groups and DOE/ARM to the Ganges Valley in India (GVAX) to study aerosols sources and processing. Much of the first year of this grant was focused on preparations for GVAX. That campaign was cancelled due to political reasons and with the consultation with our program manager, the research of this grant was refocused to study the applications of oxidation flow reactors (OFRs) for investigating secondary organic aerosol (SOA) formation and organic aerosol (OA) processing in the field and laboratory through a series of laboratory and modeling studies. We developed a gas-phase photochemical model of an OFR which was used to 1) explore the sensitivities of key output variables (e.g., OH exposure, O3, HO2/OH) to controlling factors (e.g., water vapor, external reactivity, UV irradiation), 2) develop simplified OH exposure estimation equations, 3) investigate under what conditions non-OH chemistry may be important, and 4) help guide design of future experiments to avoid conditions with undesired chemistry for a wide range of conditions applicable to the ambient, laboratory, and source studies. Uncertainties in the model were quantified and modeled OH exposure was compared to tracer decay measurements of OH exposure in the lab and field. Laboratory studies using OFRs were conducted to explore aerosol yields and composition from anthropogenic and biogenic VOC as well as crude oil evaporates. Various aspects of the modeling and laboratory results and tools were applied to interpretation of ambient and source measurements using OFR. Additionally, novel measurement methods were used to study gas/particle partitioning. The research conducted was highly successful and details of the key results are summarized in this report through narrative text, figures, and a complete list of publications acknowledging this grant.

Chemistry of Secondary Organic Aerosol Formation from Reactions of Alkenes with Ozone and Nitrate Radicals

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ISBN 13 :
Total Pages : 162 pages
Book Rating : 4.3/5 (121 download)

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Book Synopsis Chemistry of Secondary Organic Aerosol Formation from Reactions of Alkenes with Ozone and Nitrate Radicals by : Huiming Gong

Download or read book Chemistry of Secondary Organic Aerosol Formation from Reactions of Alkenes with Ozone and Nitrate Radicals written by Huiming Gong and published by . This book was released on 2003 with total page 162 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Carbonaceous Aerosol Study Using Advanced Particle Instrumentation

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ISBN 13 :
Total Pages : 250 pages
Book Rating : 4.:/5 (729 download)

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Book Synopsis Carbonaceous Aerosol Study Using Advanced Particle Instrumentation by : Li Qi

Download or read book Carbonaceous Aerosol Study Using Advanced Particle Instrumentation written by Li Qi and published by . This book was released on 2010 with total page 250 pages. Available in PDF, EPUB and Kindle. Book excerpt: A study of the evolution of carbonaceous aerosol in the atmosphere was conducted with special focus on primary biomass burning and secondary organic aerosol (SOA) processing. The work is broken down into two major components: the organic aerosol mass released from biomass burning and the evolution of SOA with special emphasis on formation routes. The biomass burning work explored the evolution of organic aerosol emissions as a function of modified combustion efficiency with correlations drawn between levoglucosan emissions and wood-type, combustion type (flaming, mixed, smoldering) using high resolution aerosol mass spectrometry. The SOA work includes insights into the mechanism for SOA formation from aromatics including the impacts of temperature and particle-aging. This work conclusively demonstrates that gas-particle partitioning theory combined with enthalpies of formation are insufficient to model the formation of SOA as a function of time; that the presence of secondary reactions, in both the particle and gas-phase continue to evolve the aerosol beyond that typically simulated in environmental chambers; and that current mechanisms for SOA formation from aromatics fail to explain isotopically labeled experiments while conclusively ruling out the importance of organic nitrate products.

Laboratory Studies on the Formation of Secondary Organic Aerosol from the Atmospheric Oxidation of Alkenes

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ISBN 13 :
Total Pages : 626 pages
Book Rating : 4.3/5 (121 download)

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Book Synopsis Laboratory Studies on the Formation of Secondary Organic Aerosol from the Atmospheric Oxidation of Alkenes by : Kenneth Stephen Docherty

Download or read book Laboratory Studies on the Formation of Secondary Organic Aerosol from the Atmospheric Oxidation of Alkenes written by Kenneth Stephen Docherty and published by . This book was released on 2004 with total page 626 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Anthropogenic Influence on the Fate of Secondary Organic Aerosol

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ISBN 13 :
Total Pages : 0 pages
Book Rating : 4.:/5 (135 download)

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Book Synopsis Anthropogenic Influence on the Fate of Secondary Organic Aerosol by : Dongyu Wang

Download or read book Anthropogenic Influence on the Fate of Secondary Organic Aerosol written by Dongyu Wang and published by . This book was released on 2018 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: Oxidation of volatile organic compounds (VOC) in the atmosphere leads to the formation of secondary organic aerosol (SOA), which can have extensive impacts on air quality, health, and climate. Existing air quality models used to describe the fate of ambient organic aerosol tend to underpredict the aerosol oxidation state. In addition, modeled concentrations of nitrogen oxides (NO [subscript x]) and other reactive nitrogen compounds (NO [subscript y]), including alkyl nitrates, often deviate from field observations. Certain SOA formation pathways, SOA ageing mechanisms, and alkyl nitrate decay mechanisms may be missing. Recent field studies show that NO [subscript x]-mediated heterogeneous production of nitryl chloride, ClNO2, could provide a ubiquitous source for chlorine atoms. Little is known about the role of chlorine atoms in SOA formation and ageing, or their interaction with other anthropogenic emissions found in polluted environments, where alkane oxidation chemistry is important. Environmental chamber experiments are carried out to address knowledge gaps in atmospheric chlorine and alkane oxidation chemistry. Results show that chlorine-initiated oxidation of isoprene leads to SOA formation, organic chloride formation, and possibly secondary HO [subscript x] chemistry. Alkane-derived alkyl nitrate compounds are found not to hydrolyze appreciably in humid environments or in the presence of acidic aerosol. Uptake of inorganic nitrate and inorganic chloride are observed in the presence of deliquescent particles. Chlorine-initiated oxidation of linear alkanes is shown to result in prompt SOA formation and delayed organic chloride formation, which is enabled by the addition of chlorine radical to dihydrofuran, a heterogeneously produced multi-generational oxidation product. Improvements are made for the detection of organic chloride using aerosol mass spectrometry, and for aerosol volatility measurements using temperature programmed thermal desorption techniques. A two-dimensional thermogram framework is developed to visualize aerosol composition, aerosol volatility, and thermal fragmentation simultaneously

Formation and Chemical Evolution of Secondary Organic Aerosol from Aqueous-phase Reactions of Atmospheric Phenols

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ISBN 13 : 9781339824093
Total Pages : pages
Book Rating : 4.8/5 (24 download)

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Book Synopsis Formation and Chemical Evolution of Secondary Organic Aerosol from Aqueous-phase Reactions of Atmospheric Phenols by : Lu Yu

Download or read book Formation and Chemical Evolution of Secondary Organic Aerosol from Aqueous-phase Reactions of Atmospheric Phenols written by Lu Yu and published by . This book was released on 2016 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Secondary organic aerosol (SOA) is formed and transformed in atmospheric aqueous phases (e.g., cloud and fog droplets and deliquesced airborne particles containing small amounts of water) through a multitude of chemical and physical processes. Understanding the formation and transformation processes of SOA via aqueous-phase reactions is important for properly presenting its atmospheric evolution pathways in models and for elucidating its climate and health effects. Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the formation and evolution of phenol (C6H6O), guaiacol (C7H8O2; 2-methoxyphenol) and syringol (C8H10O3; 2,6-dimethoxyphenol) and with two major aqueous phase oxidants -- the triplet excited state of an aromatic carbonyl (3C*) and hydroxyl radical (·OH) - and interpret the reaction mechanisms. In addition, given that dissolved organic matter (DOM) is an important component of fog and cloud water and that it can undergo aqueous reactions to form more oxidized, less volatile species, we further investigate the photochemical processing of DOM in fog water to gain insights into the aqueous-phase processing of organic aerosol (OA) in the atmosphere. In Chapter 2, we thoroughly characterize the bulk chemical and molecular compositions of phenolic aqSOA formed at half-life (t[subscript 1/2]), and interpret the formation mechanisms. We find that phenolic aqSOA formed at t[subscript 1/2] is highly oxygenated with atomic oxygen-to-carbon ratio (O/C) in the range of 0.85-1.23. Dimers, higher oligomers (up to hexamers), functionalized monomers and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acids are detected. Compared with ·OH-mediated reactions, reactions mediated by 3C* are faster and produce more oligomers and hydroxylated species at t[subscript1/2]. We also find that aqSOA shows enhanced light absorption in the UV-vis region, suggesting that aqueous-phase reactions of phenols are an important source of secondary brown carbon in the atmosphere, especially in regions impacted by biomass burning. In Chapter 3, we investigate the chemical evolution of phenolic aqSOA via aqueous-phase reactions on the molecular level and interpret the aging mechanisms. Our results indicate that oligomerization is an important aqueous reaction pathway for phenols, especially during the initial stage of photooxidation. Functionalization and fragmentation become dominant at later stages, forming a variety of functionalized aromatic and ring-opening products with higher carbon oxidation states. Fragmentation reactions eventually dominate the photochemical evolution of phenolic aqSOA, forming a large number of highly oxygenated ring-opening molecules. In addition, phenolic aqSOA has a wide range of saturation vapor pressures (C*), varying from 10−20 [mu]g m−3 for functionalized phenolic oligomers to 10 [mu]g m−3 for ring-opening species with number of carbon less than 6. The detection of abundant extremely low volatile organic compounds (ELVOC) indicates that aqueous reactions of phenolic compounds are likely an important source of ELVOC in the atmosphere. Chapter 3 investigates the molecular transformation with aging based on the characterization of three aqSOA filter samples collected at the defined time intervals of the photoreaction. However, the chemical evolution of aqSOA products with hours of illumination at a higher time resolution is largely unknown. In Chapter 4, we investigate the chemical evolution of aqSOA at a 1-min time resolution based on high-resolution aerosol mass spectrometer (AMS) analysis. This is important for understanding the continuous evolution of phenolic aqSOA with aging as well as for elucidating the formation and transformation of different generations of products. Our results suggest that dimer and higher-order oligomers (trimers, tetramers, etc.) are formed continuously during the first 1-2 hours of photoreaction but show a gradual decrease afterwards. Functionalized derivatives grow at a later time and then gradually decrease. Highly oxidized ring-opening species continuously increase over the course of reactions. Positive matrix factorization (PMF) analysis of the AMS spectra of phenolic aqSOA identifies multiple factors, representing different generations of products. The 1st-generation products include dimers, higher-order oligomers and their oxygenated derivatives. The 2nd-generation products include oxygenated monomeric derivatives. The 3rd-generation products include highly oxidized ring-opening species. In Chapter 5, we investigate the evolution of dissolved organic matter (DOM) in fog water. Our results show that the mass concentration of DOM[subscript OA] (i.e., low-volatility DOM in fog water) is enhanced over the course of illumination, with continuous increase of O/C and atomic nitrogen-to-carbon ratio (N/C). The increase of DOM[subscript OA] is due to the incorporation of oxygen- and nitrogen-containing functional groups into the molecules. The aqueous aging of DOM[subscript OA] can be modeled as a linear combination of the dynamic variations of 3 factors using PMF analysis. Factor 1 is chemically similar to the DOM[subscript OA] before illumination, which is quickly reacted away. Factor 2 is representative of an intermediate component, which is first formed and then transformed, and O/C of Factor 2 is intermediate between that of Factor 1 and Factor 3. Factor 3 represents highly oxidized final products, which is continuously formed during illumination. Fog DOM absorbs significantly in the tropospheric sunlight wavelengths, but this absorption behavior stays almost constant over the course of illumination, despite the significant change in chemical composition.

Secondary Organic Aerosol Formation from Radical-initiated Reactions of Alkenes

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ISBN 13 :
Total Pages : 289 pages
Book Rating : 4.:/5 (567 download)

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Book Synopsis Secondary Organic Aerosol Formation from Radical-initiated Reactions of Alkenes by : Aiko Matsunaga

Download or read book Secondary Organic Aerosol Formation from Radical-initiated Reactions of Alkenes written by Aiko Matsunaga and published by . This book was released on 2009 with total page 289 pages. Available in PDF, EPUB and Kindle. Book excerpt: The products and mechanisms of secondary organic aerosol (SOA) formation from reactions of 1-alkenes, internal alkenes, and 2-methyl-1-alkenes with OH radicals in the presence of NO[subscript x] were investigated in an environmental chamber and the results used to develop quantitative models for SOA formation. Aerosol chemical composition was analyzed using a thermal desorption particle beam mass spectrometer (TDPBMS), and multifunctional organic nitrate products were quantified using a high-performance liquid chromatograph with UV-vis detector and identified using the TDPBMS and 1H NMR. The major products observed in reactions of linear alkenes were [beta]-hydroxynitrates, dihydroxynitrates, cyclic hemiacetals, dihydrofurans, and dimers formed from dihydroxycarbonyls. Trihydroxynitrates and trihydroxycarbonyls were observed in reactions of 2-methyl-1-alkenes, in addition to the products listed above. Dimers were not observed, apparently because electron donation by the additional methyl group (compared to linear 1-alkenes) reduces the driving force for hemiacetal formation. The measured yields of [beta]-hydroxynitrates, dihydroxynitrates, and trihydroxynitrates were used to calculate relative ratios of 1.0:1.9:4.3 for forming primary, secondary, and tertiary [beta]-hydroxyalkyl radicals by OH radical addition to the C=C double bond, and branching ratios of 0.12, 0.15, and 0.25 for forming [beta]-hydroxynitrates from reactions of primary, secondary, and tertiary â-hydroxyperoxy radicals with NO. The trends are consistent with expected relative stabilities of [beta]-hydroxyalkyl radicals and ß-hydroxyperoxy radical-NO complexes. It should be possible to use these values to estimate product yields from similar reactions of other alkenes. Comparison of measured and model-calculated SOA yields showed that in some cases the models provide accurate predictions of SOA yields, but that uncertainties in gas- and particle-phase chemistry and gas-particle partitioning can lead to significant discrepancies. More limited environmental chamber studies were also carried out on SOA formation from reactions of linear alkenes with NO3 radicals. The major products were [beta]-hydroxynitrates, [beta]-carbonylnitrates, dihydroxynitrates, and hydroxy- and oxo- dinitrooxytetrahydrofurans, which had not been observed previously. It was observed that isomerization of [delta]-hydroxycarbonyls to cyclic hemiacetals, followed by dehydration to highly reactive dihydrofurans that can be further oxidized, can be important sources of SOA from reactions of alkenes with OH and NO3 radicals.

Chemistry of Secondary Organic Aerosol

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ISBN 13 :
Total Pages : 466 pages
Book Rating : 4.:/5 (98 download)

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Book Synopsis Chemistry of Secondary Organic Aerosol by : Lindsay Diana Yee

Download or read book Chemistry of Secondary Organic Aerosol written by Lindsay Diana Yee and published by . This book was released on 2013 with total page 466 pages. Available in PDF, EPUB and Kindle. Book excerpt: The photooxidation of volatile organic compounds (VOCs) in the atmosphere can lead to the formation of secondary organic aerosol (SOA), a major component of fine particulate matter. Improvements to air quality require insight into the many reactive intermediates that lead to SOA formation, of which only a small fraction have been measured at the molecular level. This thesis describes the chemistry of secondary organic aerosol (SOA) formation from several atmospherically relevant hydrocarbon precursors. Photooxidation experiments of methoxyphenol and phenolic compounds and C12 alkanes were conducted in the Caltech Environmental Chamber. These experiments include the first photooxidation studies of these precursors run under sufficiently low NOx levels, such that RO2 + HO2 chemistry dominates, an important chemical regime in the atmosphere. Using online Chemical Ionization Mass Spectrometery (CIMS), key gas-phase intermediates that lead to SOA formation in these systems were identified. With complementary particle-phase analyses, chemical mechanisms elucidating the SOA formation from these compounds are proposed. Three methoxyphenol species (phenol, guaiacol, and syringol) were studied to model potential photooxidation schemes of biomass burning intermediates. SOA yields (ratio of mass of SOA formed to mass of primary organic reacted) exceeding 25% are observed. Aerosol growth is rapid and linear with the organic conversion, consistent with the formation of essentially non-volatile products. Gas and aerosol-phase oxidation products from the guaiacol system show that the chemical mechanism consists of highly oxidized aromatic species in the particle phase. Syringol SOA yields are lower than that of phenol and guaiacol, likely due to unique chemistry dependent on methoxy group position. The photooxidation of several C12 alkanes of varying structure n-dodecane, 2-methylundecane, cyclododecane, and hexylcyclohexane) were run under extended OH exposure to investigate the effect of molecular structure on SOA yields and photochemical aging. Peroxyhemiacetal formation from the reactions of several multifunctional hydroperoxides and aldehyde intermediates was found to be central to organic growth in all systems, and SOA yields increased with cyclic character of the starting hydrocarbon. All of these studies provide direction for future experiments and modeling in order to lessen outstanding discrepancies between predicted and measured SOA.

The Influence of Formation Temperature on Secondary Organic Aerosol Volatility

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ISBN 13 : 9780355967500
Total Pages : pages
Book Rating : 4.9/5 (675 download)

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Book Synopsis The Influence of Formation Temperature on Secondary Organic Aerosol Volatility by : Katherine Smith

Download or read book The Influence of Formation Temperature on Secondary Organic Aerosol Volatility written by Katherine Smith and published by . This book was released on 2018 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: The volatility of secondary organic aerosol (SOA) formed from the dark ozonolysis of [alpha]-pinene in a flow tube at temperatures ranging from 275 to 298 K has been characterized by thermally induced evaporation. The SOA was heated from the formation temperature (T[subscript f]) in a thermodenuder and the temperature-dependent volume loss was measured. The resulting thermograms for the SOA formed at the different temperatures were nearly identical when considered as a function of [delta]T (= T – T[subscript f]), rather than absolute temperature. A kinetic model of aerosol evaporation was used to derive T[subscript f]-specific effective volatility distributions for the SOA. The derived distributions indicate SOA formed at lower temperatures is composed of compounds having higher effective volatilities compared to that formed at higher temperatures. However, the increased abundance of compounds having higher effective volatilities at lower T[subscript f] cannot be explained solely due to increased partitioning into the particle phase due to a decrease in vapor pressures. Instead, much of the dependence on T[subscript f] likely results from T-dependent changes in the fraction of the particles that is monomers versus dimers (or higher order oligomers). The relatively short formation time (

Biogenic-Anthropogenic Interactions in Secondary Organic Aerosol Formation and Health Effects of Atmospheric Organic Aerosol

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ISBN 13 :
Total Pages : pages
Book Rating : 4.:/5 (133 download)

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Book Synopsis Biogenic-Anthropogenic Interactions in Secondary Organic Aerosol Formation and Health Effects of Atmospheric Organic Aerosol by : Jianhuai Ye

Download or read book Biogenic-Anthropogenic Interactions in Secondary Organic Aerosol Formation and Health Effects of Atmospheric Organic Aerosol written by Jianhuai Ye and published by . This book was released on 2017 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:

Chemistry of Secondary Organic Aerosol Formation from the Reaction of Hydroxyl Radicals with Aromatic Compounds

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ISBN 13 : 9781303507403
Total Pages : 185 pages
Book Rating : 4.5/5 (74 download)

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Book Synopsis Chemistry of Secondary Organic Aerosol Formation from the Reaction of Hydroxyl Radicals with Aromatic Compounds by : Christen Michelle Strollo Gordon

Download or read book Chemistry of Secondary Organic Aerosol Formation from the Reaction of Hydroxyl Radicals with Aromatic Compounds written by Christen Michelle Strollo Gordon and published by . This book was released on 2013 with total page 185 pages. Available in PDF, EPUB and Kindle. Book excerpt: Secondary Organic Aerosol (SOA) can have significant impacts on visibility, human health, and global climate, and a more detailed understanding of the roles of both gas-phase and heterogeneous/multiphase chemistry is needed to develop air quality models that accurately represent the formation of SOA from the oxidation of aromatic hydrocarbons. The objective of this dissertation is to investigate the mechanisms and products of SOA formation from the OH radical-initiated reaction of aromatics in an environmental chamber. This is done using a combination of thermal desorption particle beam mass spectrometry, functional group and CHON elemental analysis, and UV spectroscopy. Chapter 2 investigates the variability of SOA yields measured for reactions of m-xylene and other methylbenzenes as a function of humidity, seed particle, OH source, NO x concentration, light intensity, and mass loading. The most significant factor that determined SOA yields was the amount of m -xylene reacted. The chapter concludes with a discussion of a series of experiments conducted to isolate the contribution to SOA formation of specific primary gas-phase products of the m -xylene reaction. Chapter 3 examines the formation of SOA from the oxidation of 3-methylfuran, which produces among other compounds an [Alpha, Beta]-unsaturated dicarbonyl that is also a major product of the oxidation of m -xylene. We have determined that SOA forms from the heterogeneous/multiphase oligomerization of primary reaction products to form esters, hemiacetals, and acetals, and not through second-generation reactions. Chapter 4 discusses the chemical composition of SOA formed from the reaction of m -xylene and how the variables detailed in Chapter 2 affect the composition. Experiments were carried out with deuterated m-xylene to confirm that SOA is dominated by hemiacetals formed from C8 ring-opened primary products and their second-generation products. Finally, Chapter 5 shows that SOA formed from the oxidation of benzaldehyde in the absence of NOx is largely composed of oligomeric products formed through heterogeneous/multiphase reactions involving benzoic acid, peroxybenzoic acid, phenol, and benzaldehyde.

Investigation of Fundamental Processes Governing Secondary Organic Aerosol Formation in Laboratory Chambers

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ISBN 13 :
Total Pages : 562 pages
Book Rating : 4.:/5 (919 download)

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Book Synopsis Investigation of Fundamental Processes Governing Secondary Organic Aerosol Formation in Laboratory Chambers by : Xuan Zhang

Download or read book Investigation of Fundamental Processes Governing Secondary Organic Aerosol Formation in Laboratory Chambers written by Xuan Zhang and published by . This book was released on 2015 with total page 562 pages. Available in PDF, EPUB and Kindle. Book excerpt: Our understanding of the processes and mechanisms by which secondary organic aerosol (SOA) is formed is derived from laboratory chamber studies. In the atmosphere, SOA formation is primarily driven by progressive photooxidation of SOA precursors, coupled with their gas-particle partitioning. In the chamber environment, SOA-forming vapors undergo multiple chemical and physical processes that involve production and removal via gas-phase reactions; partitioning onto suspended particles vs. particles deposited on the chamber wall; and direct deposition on the chamber wall. The main focus of this dissertation is to characterize the interactions of organic vapors with suspended particles and the chamber wall and explore how these intertwined processes in laboratory chambers govern SOA formation and evolution. A Functional Group Oxidation Model (FGOM) that represents SOA formation and evolution in terms of the competition between functionalization and fragmentation, the extent of oxygen atom addition, and the change of volatility, is developed. The FGOM contains a set of parameters that are to be determined by fitting of the model to laboratory chamber data. The sensitivity of the model prediction to variation of the adjustable parameters allows one to assess the relative importance of various pathways involved in SOA formation. A critical aspect of the environmental chamber is the presence of the wall, which can induce deposition of SOA-forming vapors and promote heterogeneous reactions. An experimental protocol and model framework are first developed to constrain the vapor-wall interactions. By optimal fitting the model predictions to the observed wall-induced decay profiles of 25 oxidized organic compounds, the dominant parameter governing the extent of wall deposition of a compound is identified, i.e., wall accommodation coefficient. By correlating this parameter with the molecular properties of a compound via its volatility, the wall-induced deposition rate of an organic compound can be predicted based on its carbon and oxygen numbers in the molecule. Heterogeneous transformation of delta-hydroxycarbonyl, a major first-generation product from long-chain alkane photochemistry, is observed on the surface of particles and walls. The uniqueness of this reaction scheme is the production of substituted dihydrofuran, which is highly reactive towards ozone, OH, and NO3, thereby opening a reaction pathway that is not usually accessible to alkanes. A spectrum of highly-oxygenated products with carboxylic acid, ester, and ether functional groups is produced from the substituted dihydrofuran chemistry, thereby affecting the average oxidation state of the alkane-derived SOA. The vapor wall loss correction is applied to several chamber-derived SOA systems generated from both anthropogenic and biogenic sources. Experimental and modeling approaches are employed to constrain the partitioning behavior of SOA-forming vapors onto suspended particles vs. chamber walls. It is demonstrated that deposition of SOA-forming vapors to the chamber wall during photooxidation experiments can lead to substantial and systematic underestimation of SOA. Therefore, it is likely that a lack of proper accounting for vapor wall losses that suppress chamber-derived SOA yields contribute substantially to the underprediction of ambient SOA concentrations in atmospheric models.

Chamber Studies of Secondary Organic Aerosol Formation

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ISBN 13 :
Total Pages : 972 pages
Book Rating : 4.:/5 (437 download)

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Book Synopsis Chamber Studies of Secondary Organic Aerosol Formation by : Nga Lee Ng

Download or read book Chamber Studies of Secondary Organic Aerosol Formation written by Nga Lee Ng and published by . This book was released on 2007 with total page 972 pages. Available in PDF, EPUB and Kindle. Book excerpt:

NO2 Effects on Nighttime Secondary Organic Aerosol (SOA) Formation

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ISBN 13 :
Total Pages : 95 pages
Book Rating : 4.:/5 (845 download)

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Book Synopsis NO2 Effects on Nighttime Secondary Organic Aerosol (SOA) Formation by : Danielle C. Draper

Download or read book NO2 Effects on Nighttime Secondary Organic Aerosol (SOA) Formation written by Danielle C. Draper and published by . This book was released on 2013 with total page 95 pages. Available in PDF, EPUB and Kindle. Book excerpt: