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Measuring and Modeling the Composition of Secondary Organic Aerosol

Measuring and Modeling the Composition of Secondary Organic Aerosol PDF Author: Michael James Apsokardu
Publisher:
ISBN:
Category :
Languages : en
Pages : 220

Book Description
The modeling and measurement approaches discussed in this dissertation are tools that future members of our research group will be able to utilize for studies of measuring and modeling the composition of secondary organic aerosol. Both current and future projects using measurement and modeling approaches are discussed at the conclusion of this dissertation.

Measuring and Modeling the Composition of Secondary Organic Aerosol

Measuring and Modeling the Composition of Secondary Organic Aerosol PDF Author: Michael James Apsokardu
Publisher:
ISBN:
Category :
Languages : en
Pages : 220

Book Description
The modeling and measurement approaches discussed in this dissertation are tools that future members of our research group will be able to utilize for studies of measuring and modeling the composition of secondary organic aerosol. Both current and future projects using measurement and modeling approaches are discussed at the conclusion of this dissertation.

Determination of Secondary Organic Aerosol Sources, Precursors, and Properties Using Novel Measurement and Modeling Techniques

Determination of Secondary Organic Aerosol Sources, Precursors, and Properties Using Novel Measurement and Modeling Techniques PDF Author: Giulia Stefenelli
Publisher:
ISBN:
Category :
Languages : en
Pages :

Book Description


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

Laboratory Experiments and Modeling for Interpreting Field Studies of Secondary Organic Aerosol Formation Using an Oxidation Flow Reactor PDF Author:
Publisher:
ISBN:
Category :
Languages : en
Pages : 46

Book Description
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.

Molecular Composition, Volatility, and Formation Mechanisms of Biogenic Secondary Organic Aerosol

Molecular Composition, Volatility, and Formation Mechanisms of Biogenic Secondary Organic Aerosol PDF Author: Emma Louise D'Ambro
Publisher:
ISBN:
Category :
Languages : en
Pages : 129

Book Description


Fundamentals of Chemical Reaction Engineering

Fundamentals of Chemical Reaction Engineering PDF Author: Mark E. Davis
Publisher: Courier Corporation
ISBN: 0486291316
Category : Technology & Engineering
Languages : en
Pages : 385

Book Description
Appropriate for a one-semester undergraduate or first-year graduate course, this text introduces the quantitative treatment of chemical reaction engineering. It covers both homogeneous and heterogeneous reacting systems and examines chemical reaction engineering as well as chemical reactor engineering. Each chapter contains numerous worked-out problems and real-world vignettes involving commercial applications, a feature widely praised by reviewers and teachers. 2003 edition.

Chemistry of Secondary Organic Aerosol

Chemistry of Secondary Organic Aerosol PDF Author: Lindsay Diana Yee
Publisher:
ISBN:
Category : Electronic dissertations
Languages : en
Pages : 466

Book Description
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.

Real-time Measurements of Secondary Organic Aerosol Formation and Aging from Ambient Air in an Oxidation Flow Reactor in the Los Angeles Area

Real-time Measurements of Secondary Organic Aerosol Formation and Aging from Ambient Air in an Oxidation Flow Reactor in the Los Angeles Area PDF Author:
Publisher:
ISBN:
Category :
Languages : en
Pages : 23

Book Description


Developing Models of Aerosol Representation to Investigate Composition, Evolution, Optical Properties, and CCN Spectra Using Measurements of Size-resolved Hygroscopicity

Developing Models of Aerosol Representation to Investigate Composition, Evolution, Optical Properties, and CCN Spectra Using Measurements of Size-resolved Hygroscopicity PDF Author: Roberto Gasparini
Publisher:
ISBN:
Category :
Languages : en
Pages :

Book Description
A Differential Mobility Analyzer/Tandem Differential Mobility Analyzer (DMA/TDMA) was used to measure size distributions, hygroscopicity, and volatility during the May 2003 Aerosol Intensive Operational Period at the Central Facility of the Atmospheric Radiation Measurement Southern Great Plains site. Hygroscopic growth factor distributions for particles at eight dry diameters ranging from 0.012 [mu]m to 0.600 [mu]m were measured. These measurements, along with backtrajectory clustering, were used to infer aerosol composition and evolution. The hygroscopic growth of the smallest and largest particles analyzed was typically less than that of particles with dry diameters of about 0.100 [mu]m. Condensation of secondary organic aerosol on nucleation mode particles may be responsible for the minimal growth observed at the smallest sizes. Growth factor distributions of the largest particles typically contained a non-hygroscopic mode believed to be composed of dust. A model was developed to characterize the hygroscopic properties of particles within a size distribution mode through analysis of the fixed-size hygroscopic growth measurements. This model was used to examine three cases in which the sampled aerosol evolved over a period of hours or days. Additionally, size and hygroscopicity information were combined to model the aerosol as a population of multi-component particles. With this model, the aerosol hygroscopic growth factor f(RH), relating the submicron scattering at high RH to that at low RH, is predicted. The f(RH) values predicted when the hygroscopic fraction of the aerosol is assumed to be metastable agree better with measurements than do those predicted under the assumption of crystalline aerosol. Agreement decreases at RH greater than 65%. This multi-component aerosol model is used to derive cloud condensation nuclei (CCN) spectra for comparison with spectra measured directly with two Desert Research Institute (DRI) CCN spectrometers. Among the 1490 pairs of DMA/TDMA-predicted and DRI-measured CCN concentrations at various critical supersaturations from 0.02-1.05%, the sample number-weighted mean R2 value is 0.74. CCN concentrations are slightly overpredicted at both the lowest (0.02-0.04%) and highest (0.80-1.05%) supersaturations measured. Overall, this multi-component aerosol model based on size distributions and size-resolved hygroscopicity yields reasonable predictions of the humidity-dependent optical properties and CCN spectra of the aerosol.

Mathematical Modeling of Secondary Organic Aerosol Formation from [delta]3-carene

Mathematical Modeling of Secondary Organic Aerosol Formation from [delta]3-carene PDF Author: Christopher James Colville
Publisher:
ISBN:
Category : Aerosols
Languages : en
Pages : 272

Book Description


A Molecular Characterization of Biogenic Secondary Organic Aerosol by High-resolution Time-of-flight Mass Spectrometry

A Molecular Characterization of Biogenic Secondary Organic Aerosol by High-resolution Time-of-flight Mass Spectrometry PDF Author: Felipe Daniel Lopez-Hilfiker
Publisher:
ISBN:
Category :
Languages : en
Pages : 178

Book Description
The guiding question to this research is: To what extent and by what mechanisms do biogenic volatile organic compounds contribute to atmospheric aerosol mass? To address this question we need to understand the chemistry that produces condensable vapors which when in the presence of particles may partition onto the aerosol surface depending on their chemical and physical properties. I developed an insitu gas and aerosol sampling system, the FIGAERO (Filter Inlet for Gases and AEROsol) to speciate gas and particle phase organics derived from photochemical reactions with biogenic volatile organic compounds under both field and laboratory conditions. By coupling the FIGAERO to a High-Resolution Time-of-Flight Chemical Ionization Mass Spectrometer (HR-TOF-CIMS) I am able to elucidate chemical pathways by identifying elemental compositions and in some cases functional groups present in the detected molecular ions. The coupling of the FIGAERO to the HR-TOF-CIMS also allows the estimation of effective vapor pressures of the aerosol components and this information can be used to improve vapor pressure models and test associated partitioning theories and parameterizations. The approach also provides hundreds of speciated chemical tracers that can be correlated with traditional environmental and chemical measurements (e.g AMS, NOx, SO2, SMPS, VOC) to help derive sources and sinks and to constrain the mechanisms responsible for the formation and growth of organic aerosol. Measurements obtained across a wide range of conditions and locations allowing connections and contrasts between different chemical systems, providing insights into generally controlling factors of secondary organic aerosol (SOA) and its properties.