Characterizing the Formation of Secondary Organic Aerosols

Characterizing the Formation of Secondary Organic Aerosols

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Published: 2004

Total Pages: 34

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Organic aerosol is an important fraction of the fine particulate matter present in the atmosphere. This organic aerosol comes from a variety of sources; primary organic aerosol emitted directly from combustion process, and secondary aerosol formed in the atmosphere from condensable vapors. This secondary organic aerosol (SOA) can result from both anthropogenic and biogenic sources. In rural areas of the United States, organic aerosols can be a significant part of the aerosol load in the atmosphere. However, the extent to which gas-phase biogenic emissions contribute to this organic load is poorly understood. Such an understanding is crucial to properly apportion the effect of anthropogenic emissions in these rural areas that are sometimes dominated by biogenic sources. To help gain insight on the effect of biogenic emissions on particle concentrations in rural areas, we have been conducting a field measurement program at the University of California Blodgett Forest Research Facility. The field location includes has been used to acquire an extensive suite of measurements resulting in a rich data set, containing a combination of aerosol, organic, and nitrogenous species concentration and meteorological data with a long time record. The field location was established in 1997 by Allen Goldstein, a professor in the Department of Environmental Science, Policy and Management at the University of California at Berkeley to study interactions between the biosphere and the atmosphere. The Goldstein group focuses on measurements of concentrations and whole ecosystem biosphere-atmosphere fluxes for volatile organic compounds (VOC's), oxygenated volatile organic compounds (OVOC's), ozone, carbon dioxide, water vapor, and energy. Another important collaborator at the Blodgett field location is Ronald Cohen, a professor in the Chemistry Department at the University of California at Berkeley. At the Blodgett field location, his group his group performs measurements of the concentrations of important gas phase nitrogen compounds. Experiments have been ongoing at the Blodgett field site since the fall of 2000, and have included portions of the summer and fall of 2001, 2002, and 2003. Analysis of both the gas and particle phase data from the year 2000 show that the particle loading at the site correlates with both biogenic precursors emitted in the forest and anthropogenic precursors advected to the site from Sacramento and the Central Valley of California. Thus the particles at the site are affected by biogenic processing of anthropogenic emissions. Size distribution measurements show that the aerosol at the site has a geometric median diameter of approximately 100 nm. On many days, in the early afternoon, growth of nuclei mode particles (


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:

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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.


Characterization of Secondary Organic Aerosol Precursors Using Two-Dimensional Gas Chromatography with Time of Flight Mass Spectrometry (GC×GC/TOFMS)

Characterization of Secondary Organic Aerosol Precursors Using Two-Dimensional Gas Chromatography with Time of Flight Mass Spectrometry (GC×GC/TOFMS)

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Published: 2013

Total Pages: 64

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The oxidation of volatile organic compounds (VOCs) plays a role in both regional and global air quality through the formation of secondary organic aerosols (SOA). More than 1000TgC/yr of non-methane VOCs are emitted from biogenic sources (significantly greater than from anthropogenic sources). Despite this magnitude and potential importance for air quality, the body of knowledge around the identities, quantities and oxidation processes of these compounds is still incomplete (e.g., Goldstein & Galbally, 2007; Robinson et al., 2009). Two-dimensional gas chromatography paired with time-of-flight mass spectrometry (GC×GC/TOFMS) is a powerful analytical technique which is explored here for its role in better characterizing biogenic VOCs (BVOCs) and thus SOA precursors.


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 the Molecular Composition of Secondary Organic Aerosols Using High Resolution Mass Spectrometry

Characterization of the Molecular Composition of Secondary Organic Aerosols Using High Resolution Mass Spectrometry

Author: Rachel Elizabeth Sellon

Publisher:

Published: 2012

Total 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.


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.


Complex Mixtures

Complex Mixtures

Author: Emma Quinn Walhout

Publisher:

Published: 2019

Total Pages:

ISBN-13:

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Complex organic mixtures in the environment can contain hundreds to thousands of different organic molecules, and their composition and reactivity can have important environmental implications. In addition to gases, the atmosphere is made of a variety of small liquids and solids called aerosols. These aerosols have large impacts on human health, climate, and atmospheric chemical reactions. Here, secondary organic aerosol (SOA) from the ozonolysis of [alpha]-pinene is characterized. The atmospheric lifetime of SOA is very uncertain, but recent laboratory and modeling studies have demonstrated that photolysis is potentially an important process for organic mass loss from aerosol particles.1-5 Photolysis modifies the molecular composition and properties of aerosols through photolytic cleaving and repartitioning of volatile products. Characterization of dry, irradiated SOA can provide insights into photolysis driven changes in absorption properties and chemical composition. These results illuminate aging mechanisms and chemical and physical properties of organic aerosols in order to improve atmospheric modeling and the understanding of atmospheric chemical reactions. However, the high chemical complexity and low atmospheric abundance presents a difficult analytical challenge. Milligrams, or more, of material may be needed for speciated spectroscopic analysis.6 This study used a suite of advanced analytical techniques, including a novel combination of action spectroscopy and mass spectrometry that provides more structural information on organic mixtures than mass spectrometry alone. This study also used tunable light from a free electron laser, infrared and UV/Vis absorption, and computational chemistry to characterize molecules in [alpha]-pinene SOA. In addition, complex organic mixtures are also found in particulate matter that has deposited onto Earth’s surface. The preliminary results of dew analysis, including a foundation method of analysis for future study, gives the first look at organic material deposited into dew water on natural surfaces. This offers insight into atmospheric organic deposition to better understand chemical transport, air quality, and carbon cycling in the atmosphere.