Size-dependent Molecular-level Characterization of Secondary Organic Aerosol from NO3 Initiated Δ-carene Oxidation Using Nanospray Desorption Electrospray Ionization High-resolution Mass Spectrometry PDF Download

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Category :
Languages : en
Pages : 55

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Author: Rachel Elizabeth Sellon
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ISBN:
Category :
Languages : en
Pages : 274

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Atmospheric aerosols can affect visibility and the Earth's climate by scattering and absorbing light and they also can have adverse effects on human health. The organic portion of atmospheric aerosols is very complex and is a major fraction of fine particulate matter. High molecular weight (high-MW)/oligomeric organic compounds can make up a large part of this organic fraction and the composition, sources, and formation mechanisms for these compounds are not well understood. This knowledge and understanding is necessary to decrease the uncertainty in the climate affects of aerosols and to improve climate models. This dissertation investigates the composition and formation mechanisms for the high-MW/oligomeric fraction of secondary organic aerosols (SOA) collected in Bakersfield, CA and presents a comparative analysis of chamber and ambient SOA, from both Los Angeles (LA) and Bakersfield, to investigate sources at both locations. A novel sampling technique, nanospray-Desorption Electrospray Ionization (nano-DESI), was used with high resolution mass spectrometry (HR-MS) to determine the molecular formulas of the high molecular weight (HMW)/oligomeric fraction of SOA. Nano-DESI involves direct desorption from the sample surface and was used to limit reactions that can take place with extraction and storage in solvent. The samples were collected in Bakersfield and LA during CalNex 2010. Both Bakersfield and LA are out of compliance with EPA standards of ozone and particulate matter and provide opportunities to examine air masses affected by both anthropogenic and biogenic sources. This dissertation has provided the first evidence of observable changes in the composition of high-MW/oligomeric compounds throughout the day. Using positive mode nano-DESI, afternoon increases in the number of compounds that contain carbon, hydrogen and oxygen (CHO) were observed consistent with photochemistry/ozonolysis as a major source for these compounds. Compounds containing reduced nitrogen groups were dominant at night and had precursors consistent with imine formation products from the reaction of carbonyls and ammonia. In the negative mode, organonitrates (CHON) and nitroxy organosulfates (CHONS) had larger numbers of compounds in the night/morning samples consistent with nitrate radical formation reactions. A subset of the CHONS compounds and compounds containing sulfur (CHOS) had the same composition as known biogenic organosulfates and nitroxy organosulfates indicating contributions from both biogenic and anthropogenic sources to the SOA. This dissertation also provides the first analysis of the high-MW/oligomeric fraction in size resolved samples; the majority of the compounds were found in aerosol diameters between 0.18-1.0 micrometers and the CHON were bimodal with size. Finally, this dissertation presents the first comparative analysis of the overlap in the composition of this fraction of SOA between ambient and chamber samples. Samples collected in Pasadena, LA and Bakersfield were compared with samples collected in a smog chamber using diesel and isoprene sources. The results indicate that diesel had the highest overlap at both sites, Bakersfield samples were more oxidized, and LA showed evidence of a SOA plume arriving from downtown LA. The addition of ammonia to the diesel chamber experiment was necessary to form many of the 2N compounds found in Bakersfield. These results increase our understanding of the types of compounds found in urban environments and give evidence for the timescales of formation reactions in an ambient environment. They show that the majority of the high-MW oligomeric compounds are found in submicron size particles and that the composition of this fraction of SOA varies with aerosol size. Results from the chamber comparisons show that both diesel and isoprene are important sources for these compounds and also that there other sources are present. Future work that combines this type of analysis, in other ambient environments, with studies of the optical properties of aerosols could be used to help improve climate models and to start to close the gap in our understanding of the climate effects of atmospheric aerosols.

Author: Sandra Louise Blair
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ISBN: 9781339820262
Category :
Languages : en
Pages : 228

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Aerosols can substantially impact human health, atmospheric chemistry, and climate. The composition and photochemistry of a variety of anthropogenic and biogenic primary and secondary organic aerosols (POA and SOA) have yet to be fully characterized. The composition of organic aerosols is extremely complex - they contain a variety of highly oxidized, multifunctional, low vapor pressure organic compounds. The primary focus of this thesis is on the molecular characterization of organic aerosols that are not well understood or have not been studied before, such as primary emissions from electronic cigarettes, iron (III) mediated SOA, and photooxidized biodiesel and diesel fuel SOA. Another focus of this dissertation is the effect of direct photochemical aging on the composition of organic aerosol. Direct photolysis experiments were first applied to a system that is known to have a photolabile composition, alpha-pinene ozonolysis SOA, such that characterization of a photochemical effect would be possible to quantify. Photolysis of more complex SOA that have not been studied before, photooxidized biodiesel and diesel fuel SOA, were also investigated in this thesis. Advanced high resolution mass spectrometry techniques were used in the molecular characterization of organic aerosols, including nano-Desorption Electrospray Ionization Mass Spectrometry (nano-DESI) and Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FTICR). An additional suite of online instrumentation was used to measure gas-phase composition, particle-phase composition, particle size and concentration, and absorption properties: Proton Transfer Reaction Time-of-Flight Mass Spectrometry (PTR-ToF-MS), Aerosol Mass Spectrometry (ToF-AMS), Scanning Mobility Particle Sizing (SMPS), and UV-vis spectroscopy. The molecular analysis of these aerosols provides valuable insight to the formation and photochemical behavior of unexpected, polymeric, light absorbing, and unique organosulfur species.

Author: Yadian Gómez González
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ISBN:
Category :
Languages : en
Pages :

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Author: Peijun Tu
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ISBN: 9780355733846
Category :
Languages : en
Pages : 154

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Secondary organic aerosol (SOA), which is produced by the oxidation of volatile organic compounds (VOCs) emitted from biogenic and anthropogenic sources, has great impact on the environment and human health. In this dissertation, SOA particles derived from biogenic precursors were characterized with various mass spectrometry techniques for molecular level analysis. Differences in the chemical compositions of these particles at different formation stages were used to gain insight into the formation and fate of SOA in the atmosphere. While not pursued in this dissertation, the changes studied here may also provide significant information about SOA toxicity and harm to human health. ☐ SOA derived from ozonolysis of biogenic precursors was generated in a flow tube reactor and then sent into a photo chamber where the OH radicals could be produced to simulate further aging (fresh SOA oxidation with OH radicals to produce aged SOA). The molecular compositions of both fresh and aged SOA were studied with high resolution ESI-MS, and thousands of unique molecular formulas were characterized. Among these, a class of highly oxidized multifunctional (HOM) components, which are believed to contribute significantly to the formation of SOA, were identified and compared with previously reported Extremely Low-Volatility Organic Compounds (ELVOC) detected in the gas phase and Low Volatility Organic Oxygenated Aerosol (LV-OOA) measurements of the particle phase. HOMs in fresh SOA consisted mostly of monomers and dimers, which are consistent with condensation of ELVOCs reported from a separate study. Aging caused an increase in the average number of carbon atoms per molecule of the HOMs, which is consistent with particle phase oxidation of (less oxidized) oligomers already existing in fresh SOA. For the biogenic precursors and experimental conditions studied, HOMs in fresh biogenic SOA have molecular formulas more closely resembling LVOOA than HOMs in aged SOA, suggesting that aging of biogenic SOA is not a good surrogate for ambient LVOOA. ☐ In a separate set of experiments, SOA particles were size-selected in the 30-100 nm range with a Differential Mobility Analyzer (DMA) and analyzed by both on- and off-line mass spectrometry techniques. The chemical composition was found to change significantly with particle size. Both the average oxygen-to-carbon (O/C) ratio and carbon oxidation state (OSc) were found to decrease with increasing particle size, while the change of relative abundance of oligomers was opposite as the particle size increases. These changes allowed the relative contributions of condensation, partitioning, and particle phase oligomerization to be determined at various stages of particle formation and growth. Condensation of non-/low- volatility, highly oxidized species dominates the formation/growth of smaller SOA particles, while the partitioning of semi-volatile, less oxidized species tends to play an important role in the growth of larger SOA particles. The formation of oligomers that primarily takes place in the particle phase (accretion reactions) becomes more favored as the volume to surface area ratio of the particle increases. ☐ Additionally, due to the complex molecular components of atmospheric nanoparticles, Reverse Phase Liquid Chromatography (RPLC) and Ion-Mobility Separation (IMS)- Mass Spectrometry were employed for molecular separation. Compositions partially separated based on their size, shape and polarity were subjected to tandem mass spectrometry for structure elucidation. In some cases, isomers/ isobars were identified and separated with the help of HPLC using gradient elution method.

Author: Adam Patrick Bateman
Publisher:
ISBN: 9781124668659
Category :
Languages : en
Pages : 189

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Organic aerosols comprise hundreds, if not thousands, of distinct chemical compounds. Traditional analytical techniques for analysis of chemical composition lack the ability to completely characterize complex mixtures such as organic aerosol. Until recently, the best available methods could only provide information on selected aerosol compounds, on selected groups of compounds, or on sample-averaged elemental ratios. Such experimental limitations posed significant barriers to understanding the detailed chemical composition of organic aerosols and its atmospheric evolution. The unique HR ESI-MS methods developed in this research are able to not only characterize the organic aerosols average elemental ratios, but also simultaneously obtain information about hundreds or even thousands of individual compounds in organic aerosols. One of the key achievements of this work was the development of new methods for classification of individual compounds in organic aerosols by their functional groups using reactive HR ESI-MS. This contribution made it possible to track organic aerosols throughout their atmospheric evolution via functional group composition and average elemental ratios while still retaining the chemical composition of each individual compound. Other important scientific advances described in this thesis include: complete characterization of the chemical composition of limonene SOA as a function of particle size and reaction time; adaptation of PILS (particle-into-liquid sampler) to the HR ESI-MS platform; chemical characterization of the water soluble component of several types of organic aerosols; the effects of photochemical aging on the water soluble component of limonene SOA through characterization of the optical properties coupled with chemical composition; and investigation of photochemistry of carbonyls in model SOA matrices. The research included in this dissertation reviews the development of unique aerosol characterization tools utilizing the facilities at UCI and the Environmental Molecular Sciences Laboratory at the Pacific Northwest National Laboratory. The research project answered important questions regarding organic aerosol formation, evolution, and chemical composition that impact the direct and indirect influences of aerosols on Earth's climate.

Author: Alan J.. Kwan
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ISBN:
Category : Aerosols
Languages : en
Pages : 370

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Secondary organic aerosol (SOA) are important components in atmospheric processes and significantly impact human health. The complexity of SOA composition and formation processes has hampered efforts to fully characterize their impacts, and to predict how those impacts will be affected by changes in climate and human activity. Here, we explore SOA formation in the laboratory by coupling an environmental chamber with a suite of analytical tools, including a gas-phase mass spectrometry technique that is well suited for tracking the hydrocarbon oxidation processes that drive SOA formation. Focusing on the oxidation of isoprene by the nitrate radical, NO3, we find that reactions of peroxy radicals (RO2) to form ROOR dimers is an important process in SOA formation. The other gas-phase products of these RO2 reactions differ from what is expected from studies of simpler radicals, indicating that more studies are necessary to fully constrain RO2 chemistry. Finally, we examine the role of heterogeneous oxidation as a sink of organic aerosol and a source of oxygenated volatile organic compounds in the free troposphere.

Author: Huiming Gong
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ISBN:
Category : Aerosols
Languages : en
Pages : 162

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Author: Anna Victoria Fee
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ISBN:
Category :
Languages : en
Pages :

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Author: Dian Elizabeth Romonosky
Publisher:
ISBN: 9781369227819
Category :
Languages : en
Pages : 199

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A large fraction of organic aerosol particles are formed as secondary organic aerosol (SOA) resulting from the condensation of partially oxidized biogenic and anthropogenic volatile organic compounds (VOCs) with gas phase oxidants such as O3, OH, NOx, and NO3. An additional pathway for SOA formation is by the photochemical aqueous processing of VOC occurring inside cloud and fog droplets, followed by droplet evaporation. Once formed, SOA can age through heterogeneous oxidation and fog photochemical processes involving the hydroxyl radical (OH) as well as various other oxidants in the atmosphere. In addition to condensed phase oxidation, SOA can also age in the atmosphere upon exposure to radiation, for many of these organic compounds are photolabile and can degrade through direct photolysis, wherein the compounds absorb radiation and break into products, and indirect photolysis, wherein absorption of solar radiation initiates chemistry through the production of non-selective oxidants such as OH. These photochemical aging processes have the potential to be on time scales that are comparable to the typical lifetimes of droplets (hours) and particles (days), making them relevant to study further for both climate and health reasons. This dissertation presents a systematic investigation of the optical properties, molecular composition, and the extent of photochemical processing in different types of SOA from various biogenic and anthropogenic VOC precursors. Chamber- or flowtube-generated SOA is made and then analyzed using high-resolution mass spectrometry (HR-MS) to observe the extent of change in the molecular level composition of the material before and after aqueous photolysis. Significant differences in the molecular composition between biogenic and anthropogenic SOA were observed, while the composition further evolved during photolysis. To study the optical properties and lifetimes of organic aerosol, spectroscopy tools such as UV-Vis is utilized. Results of this study suggest that the condensed phase photolysis of SOA can occur with effective lifetimes ranging from minutes to hours, and therefore represents a potentially important aging mechanism for SOA. The outcome of this dissertation will be improved understanding of the role of condensed-phase photochemistry in chemical aging of aerosol particles and cloud droplets.