Secondary Organic Aerosol Formation from Select Volatile Organic Compounds
Secondary Organic Aerosol Formation from Select Volatile Organic Compounds

Author: Chia-Li Chen

Publisher:

Published: 2015

Total Pages: 150

ISBN-13: 9781339182704

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This thesis enhances our understanding of secondary organic aerosol (SOA) formation from select anthropogenic sources including polycyclic aromatic hydrocarbons (PAHs), PAHs mixed with m -xylene and an atmospheric surrogate, and unburned whole gasoline vapors. Major SOA chemical characteristics and physical properties were explored along with SOA formation within the UCR CE-CERT environmental chamber.

Chemical Characterization of Biogenic Secondary Organic Aerosol Generated from the Oxidation of Plant and Leaf Litter Emissions
Chemical Characterization of Biogenic Secondary Organic Aerosol Generated from the Oxidation of Plant and Leaf Litter Emissions

Author: Celia L. Faiola

Publisher:

Published: 2014

Total Pages:

ISBN-13:

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Atmospheric aerosol impact climate by scattering and absorbing radiation and contributing to cloud formation processes. One of the largest uncertainties in climate change predictions is due to limitations in our understanding of the formation of secondary organic aerosol (SOA). This dissertation investigated SOA formation from the oxidation of plant and leaf litter emissions in a laboratory chamber. To accurately measure the biogenic volatile organic compound (BVOC) emissions, a dynamic dilution system was developed and is described in the first study. This system was used to calibrate the GC-MS-FID and improve quantitation with a maximum instrumental error of +/-10%. In the second study, two separate sets of soil and leaf litter samples were transported from the University of Idaho experimental forest and brought back to the lab. The BVOC emissions from these samples were pumped to an aerosol growth chamber where they were oxidized to generate SOA. The resulting SOA composition was similar to SOA formed from the oxidation of other biogenic SOA precursors. Soil/leaf litter BVOC missions were compared to a canopy emission model and contributed from 12-136% of canopy emissions during spring and fall. Results suggest this could be a significiant emission source during those times of the year. In the third and fourth study, coniferous plants were treated with a plant hormone, methyl jasmonate, to simulate herbivory stress. The third study focused on the plant responses to the stress treatment by investigating changes to the BVOC emission profile. There was a high degree of inter- and intra-plant species variability. Some of the compounds most affected by the stress treatment were alpha-pinene, beta-pinene, limonene, 1,8-cineol, beta-myrcene, terpinolene, and the aromatic cymene isomers. The fourth study investigated changes to SOA composition due to changes in the BVOC emission profiles. Most pre-treatment SOA was very similar in composition with Pearson correlation coefficients between the AMS spectra greater than 0.88. The SOA generated after MeJA treatment produced aerosol mass spectra with similar m/z enhancements. This could indicate an herbivory stress mass spectral fingerprint that could be used to identify plant stress at an ecosystem scale.

Aerosols in Atmospheric Chemistry
Aerosols in Atmospheric Chemistry

Author: Yue Zhang

Publisher: American Chemical Society

Published: 2022-04-01

Total Pages: 176

ISBN-13: 0841299293

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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.

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

Author: Felipe Daniel Lopez-Hilfiker

Publisher:

Published: 2015

Total Pages: 178

ISBN-13:

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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.

Characterization of Secondary Organic Aerosols in the Atmosphere by Using Mass Spectrometric Approaches
Characterization of Secondary Organic Aerosols in the Atmosphere by Using Mass Spectrometric Approaches

Author: Farhat Yasmeen

Publisher:

Published: 2010

Total Pages: 103

ISBN-13:

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Secondary organic aerosol (SOA) accounts for a significant fraction of ambient tropospheric aerosol. The chemical composition of SOA is highly uncertain as it depends on different ongoing chemical and physical processes of biogenic volatile organic compounds (BVOC) and anthropogenic volatile organic compounds in the atmosphere. The research performed within the frame of this doctoral thesis is focused on the characterization of SOA produced from BVOC under a variety of atmospheric reactions resorting to mass spectrometric approaches. In a first study, the aqueous-phase oligomer formation of a major atmospheric photooxidation product, i.e., methylglyoxal, has been investigated to explore an additional pathway producing SOA through cloud processes during night-time. A second study deals with the chemical characterization (sulfate and organic matter) of marine aerosols. methanesulfonic acid was the dominating organic compound in in the fine size fraction of aerosol. A third study concerns the structural characterization of a dimeric [alpha]- and [beta]-pinene SOA product. It is proposed that diaterpenylic acid is a key monomeric unit for dimers of the ester type. A fourth study deals with the chemical characterization by fragmentation of major terpenoic acids in ambient fine aerosols from a rural site. Emphasis is given to the mass spectrometric differentiation of isobaric terpenoic acids that occur in fine forest aerosol. This thesis presents results on aerosol characterization from a wide range of parent organic compounds under a variety of atmospheric conditions.

Characterization of Biogenic Secondary Organic Aerosol Using Mass Spectrometry
Characterization of Biogenic Secondary Organic Aerosol Using Mass Spectrometry

Author: Katherine J. Heaton

Publisher:

Published: 2010

Total Pages:

ISBN-13: 9781124086231

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Secondary Organic Aerosol (SOA) forms in the atmosphere from the oxidation of biogenic emissions. Even though SOA has been linked to health and climate effects, the chemical mechanism of SOA formation is not well understood. Through the use of mass spectrometry, this work characterizes SOA during the early stages of growth from the reaction of ozone with monoterpenes, a major biogenic emission. In this thesis, three types of studies are described for analyzing SOA formation: (1) the molecular composition of SOA is studied using the photoionization aerosol mass spectrometer, (2) the atomic composition is studied with the nanometer aerosol mass spectrometer and (3) high resolution mass spectrometry is used to help reconcile atomic and molecular composition data. The monoterpene ozonolysis reactions were performed in a flow tube reactor, where the reaction period could vary from 3s to 22s. The Photoionization Aerosol Mass Spectrometer (PIAMS) detected the formation of oligomers within seconds of the onset of the reaction. Ions that were detected were mapped to dimers that could form via the stabilized Criegee intermediate channel or the hydroperoxy channel. The Nanometer Aerosol Mass Spectrometer (NAMS) analyzed the elemental composition of the SOA which showed the formation of highly polar compounds during the early stages of SOA growth. NAMS also analyzed the changes in the composition of SOA when it formed in the presence of atmospheric species (water vapor, nitric acid vapor and sodium chloride seed particles). The data collected indicated that there is not as much change for endocyclic compounds as there is for exocyclic compounds. Finally, a new off-line analysis technique was created to micro-extract SOA deposited on a plate from the flow tube reactor. The samples were analyzed with the Fourier Transform Ion Cyclotron Resonance Mass Spectrometer (FTICR-MS). The FTICR-MS was used to collect molecular and elemental data simultaneously. The FTICR-MS produced accurate mass data that could be used to calculate molecular formulas. This provided a direct comparison of the data acquired with PIAMS and NAMS.