Laboratory Studies of the Multiday Oxidative Aging of Atmospheric Organic Aerosol PDF Download

Author: Christopher Yung-Ta Lim
Publisher:
ISBN:
Category :
Languages : en
Pages : 101

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Book Description
Fine particulate matter (PM, or "aerosol") in the atmosphere affects the Earth's radiative balance and is one of the most important risk factors leading to premature mortality worldwide. Thus, understanding the processes that control the loading and chemical composition of PM in the atmosphere is key to understanding air quality and climate. However, the chemistry of organic aerosol (OA), which comprises a significant fraction of submicron atmospheric PM, is immensely complex due to the vast number of organic compounds in the atmosphere and their numerous reaction pathways. Laboratory experiments have generally focused on the initial formation of OA from volatile organic compounds (VOCs), but have neglected processes that can change the composition and loading of OA over longer timescales ("aging"). This thesis describes several laboratory studies that better constrain the effect of two important aging processes over timescales of several days, the oxidation of gas phase species to form secondary OA (condensation) and the reaction of gas phase radicals with organic molecules in the particle phase (heterogeneous oxidation). First, the oxidation of biomass burning emissions is studied by exposing particles and gases present in smoke to hydroxyl radicals (OH). Increases in organic aerosol mass are observed for all fuels burned, and the amount of OA formed is explained well by the extent of aging and the total concentration of measured organic gases. Second, the effect of particle morphology on the rate of heterogeneous oxidation is examined by comparing the oxidation of particles with thin organic coatings to the oxidation of pure organic particles. Results show that morphology can have a strong impact on oxidation kinetics and that particles with high organic surface area to volume ratios can be rapidly oxidized. Third, the molecular products from the heterogeneous OH oxidation of a single model compound (squalane) are measured. Formation of a range of gas-phase oxygenated VOCs is observed, indicating the importance of fragmentation reactions that decrease OA mass, and providing insight into heterogeneous reaction mechanisms. The results from this work emphasize that the concentration and composition of OA can change dramatically over multiple days of atmospheric oxidation.

Author: Kenneth Stephen Docherty
Publisher:
ISBN:
Category : Aerosols
Languages : en
Pages : 626

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Author: James Freeman Hunter
Publisher:
ISBN:
Category :
Languages : en
Pages : 110

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.Organic molecules have many important roles in the atmosphere, acting as climate and biogeochemical forcers, and in some cases as toxic pollutants. The lifecycle of atmospheric organic carbon is extremely complex, with reaction in multiple phases (gas, particle, aqueous) and at multiple timescales. The details of the lifecycle chemistry (especially the amount and properties of particles) have important implications for air quality, climate, and human and ecosystem health, and need to be understood better. Much of the chemical complexity and uncertainty lies in the reactions and properties of low-volatility oxidized intermediates that result from the oxidation of volatile organic precursors, and which have received comparatively little study thus far. This thesis describes three projects that link together the entire chain of oxidation (volatile to intermediate to condensed) in an effort to improve our understanding of carbon lifecycle and aerosol production. Laboratory studies of atmospherically relevant aerosol precursors show that the slow oxidation of intermediates is critical to explaining the yield and properties of aerosol under highly oxidized ("aged") conditions, and that the production of organic particles is significantly increased when intermediates are fully oxidized. This aging process is a strong function of molecular structure, and depends on aerosol concentration through the phenomenon of condensational trapping. Further laboratory studies of a series of (poly)cyclic 10 carbon alkanes show that structural effects are largely explained through fragmentation reactions, and that more generally, carbon-carbon bond scission is a ubiquitous and important reaction channel for oxidized intermediates. Finally, direct measurement of oxidized intermediate compounds in field studies shows that these compounds are abundant and important in the ambient atmosphere, with concentrations and properties in between those of volatile and particulate organic compounds. Together with other co-located measurements and complementary techniques, this enables estimates of emission, oxidation, and deposition to be constructed. The results from this thesis can be used to inform more sophisticated models of atmospheric organic carbon cycling, and to improve prediction of organic particulate matter concentrations.

Author: Sean Herbert Kessler
Publisher:
ISBN:
Category :
Languages : en
Pages : 134

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The immense chemical complexity of atmospheric organic particulate matter ("aerosol") has left the general field of condensed-phase atmospheric organic chemistry relatively under-developed when compared with either gas-phase chemistry or the formation of inorganic compounds. In this work, we endeavor to improve the general understanding of the narrow class of oxidation reactions that occur at the interface between the particle surface and the gas-phase. The heterogeneous oxidation of pure erythritol (C4H1 00 4 ) and levoglucosan (C6H1 00 5) particles by hydroxyl radical (OH) was studied first in order to evaluate the effects of atmospheric aging on the mass and chemical composition of atmospheric organic aerosol, particularly that resembling fresh secondary organic aerosol (SOA) and biomass-burning organic aerosol (BBOA). In contrast to what is generally observed for the heterogeneous oxidation of reduced organics, substantial volatilization is observed in both systems. As a continuation of the heterogeneous oxidation experiments, we also measure the kinetics and products of the aging of highly oxidized organic aerosol, in which submicron particles composed of model oxidized organics -- 1,2,3,4-butanetetracarboxylic acid (C8H100 8), citric acid (C6 H8 0 7), tartaric acid (C4H6 0 6 ), and Suwannee River fulvic acid -- were oxidized by gas-phase OH in the same flow reactor, and the masses and elemental composition of the particles were monitored as a function of OH exposure. In contrast to studies of the less-oxidized model systems, particle mass did not decrease significantly with heterogeneous oxidation, although substantial chemical transformations were observed and characterized. Lastly, the immense complexity inherent in the formation of SOA -- due primarily to the large number of oxidation steps and reaction pathways involved -- has limited the detailed understanding of its underlying chemistry. In order to simplify this inherent complexity, we give over the last portion of this thesis to a novel technique for the formation of SOA through the photolysis of gas-phase alkyl iodides, which generates organic peroxy radicals of known structure. In contrast to standard OH-initiated oxidation experiments, photolytically initiated oxidation forms a limited number of products via a single reactive step. The system in which the photolytic SOA is formed is also repurposed as a generator of organic aerosol for input into a secondary reaction chamber, where the organic particles undergo additional aging by the heterogeneous oxidation mechanism already discussed. Particles exiting this reactor are observed to have become more dramatically oxidized than comparable systems containing SOA formed by gas-phase alkanes undergoing "normal" photo-oxidation by OH, suggesting simultaneously the utility of gas-phase precursor photolysis as an effective experimental platform for studying directly the chemistry involved in atmospheric aerosol formation and also the possibility that heterogeneous processes may play a more significant role in the atmosphere than what is predicted from chamber experiments. Consideration is given for the application of these results to larger-scale experiments, models, and conceptual frameworks.

Author:
Publisher:
ISBN:
Category :
Languages : en
Pages :

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The oxidative evolution (?aging?) of organic species in the atmosphere is thought to have a major influence on the composition and properties of organic particulate matter, but remains poorly understood, particularly for the most oxidized fraction of the aerosol. Here we measure the kinetics and products of the heterogeneous oxidation of highly oxidized organic aerosol, with an aim of better constraining such atmospheric aging processes. Submicron particles composed of model oxidized organics--1,2,3,4-butanetetracarboxylic acid (CH10O8), citric acid (C6H8O-- ), tartaric acid (C4H6O6), and Suwannee River fulvic acid--were oxidized by gas-phase OH in a flow reactor, and the masses and elemental composition of the particles were monitored as a function of OH exposure. In contrast to our previous studies of less-oxidized model systems (squalane, erythritol, and levoglucosan), particle mass did not decrease significantly with heterogeneous oxidation. Carbon content of the aerosol always decreased somewhat, but this mass loss was approximately balanced by an increase in oxygen content. The estimated reactive uptake coefficients of the reactions range from 0.37 to 0.51 and indicate that such transformations occur at rates corresponding to 1-2 weeks in the atmosphere, suggesting their importance in the atmospheric lifecycle of organic particulate matter.

Author: Claire Francis Fortenberry
Publisher:
ISBN:
Category : Electronic dissertations
Languages : en
Pages : 327

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Book Description
Atmospheric particulate matter (PM) is ubiquitous in both indoor and outdoor air and is generally detrimental to human health. PM composed of particles with aerodynamic diameters less than 2.5 um (PM2.5) are related to adverse health outcomes including heart disease and respiratory disease. Fundamentally, particle physical properties such as size and hygroscopicity are dictated by chemical composition, which can be highly complex, particularly for organic aerosol (OA). In both outdoor and indoor air, OA is composed substantially of intermediately volatile and semivolatile organic compounds (I/SVOCs), which exist in both gas and particle phases under typical atmospheric conditions. The distribution of these compounds between the two phases can change rapidly depending on conditions like temperature, relative humidity, and concentrations of surrounding particles and gases. The chemical complexity and rapidly-changing dynamics of I/SVOCs in OA necessitates improved instrumentation to speciate complex mixtures of I/SVOCs in both gas and particle phases at fast time scales relative to phase partitioning dynamics.The Thermal desorption Aerosol Gas Chromatograph (TAG), which performs in-situ ambient collection and molecular-level speciation of organics at hourly time resolution, is uniquely suited to meet these challenges. The TAG system has been modified in various ways to collect and analyze different targeted molecules in both the gas and particle phases. In addition to speciated organics, the impactor-based collection and thermal desorption (ICTD) system developed for the original TAG features unique thermal decomposition data, which provides information on thermally labile organic and inorganic fragments. These data have been used in laboratory and field studies to evaluate different species not normally analyzable by gas chromatography. However, the ICTD cell is not suitable for gas-phase quantification.This dissertation addresses two major research themes: laboratory and field measurements to improve understanding of I/SVOCs in indoor and outdoor air, and development of improved I/SVOC measurement techniques. Within the first theme, atmospheric aging of I/SVOCs from biomass burning plumes was characterized in controlled laboratory studies with an oxidation flow reactor using molecular speciation and thermal decomposition data from the ICTD-TAG. I/SVOCs in indoor air were investigated under different natural ventilation (window opening) conditions using the ICTD-TAG in two field studies, and phase partitioning dynamics of indoor-measured I/SVOCs were examined in targeted experiments conducted in the field. Within the second theme, a denuder-based gas trap (GT) was developed and incorporated in parallel into the ICTD-TAG. Following initial GT testing in field studies, the design was modified and characterized through standard calibrations. Simple laboratory studies demonstrate that the GT-ICTD-TAG effectively measures changes in particle-phase fractions.

Author: Georges Le Bras
Publisher: Springer Science & Business Media
ISBN:
Category : Science
Languages : en
Pages : 348

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Book Description
Oxidation and removal of atmospheric constituents involve complex sequences of reactions which can lead to the production of photo-oxidants such as ozone. In order to understand and model these complex reaction sequences, it is necessary to have a comprehensive understanding of reaction mechanisms and accurate estimates of kinetic parameters for relevant gas-phase atmospheric reactions. This book presents recent advances in the field and includes the following topics: e.g. the oxidation of simple organic compounds, NOx kinetics and mechanisms, OH radical production and rate constants for the OH attack on more complex organic compounds, peroxy and alkoxy radical reactions, photo-oxidation of aromatic and biogenic compounds, and the interaction between radical species.

Author: Kirsten Sue Johnson
Publisher:
ISBN:
Category :
Languages : en
Pages : 151

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Carbonaceous aerosols are among the most prevalent yet least understood constituents of the atmosphere, particularly in urban environments. We have performed analyses of field samples and laboratory studies to probe the physico-chemical properties of soot and organic aerosols in a complimentary approach to obtain information essential for understanding their atmospheric evolution and environmental effects. Samples of particulate matter

Author: Gabriel Avram Isaacman
Publisher:
ISBN:
Category :
Languages : en
Pages : 167

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Particles in the atmosphere are known to have negative health effects and important but highly uncertain impacts on global and regional climate. A majority of this particulate matter is formed through atmospheric oxidation of naturally and anthropogenically emitted gases to yield highly oxygenated secondary organic aerosol (SOA), an amalgamation of thousands of individual chemical compounds. However, comprehensive analysis of SOA composition has been stymied by its complexity and lack of available measurement techniques. In this work, novel instrumentation, analysis methods, and conceptual frameworks are introduced for chemically characterizing atmospherically relevant mixtures and ambient aerosols, providing a fundamentally new level of detailed knowledge on their structures, chemical properties, and identification of their components. This chemical information is used to gain insights into the formation, transformation and oxidation of organic aerosols. Biogenic and anthropogenic mixtures are observed in this work to yield incredible complexity upon oxidation, producing over 100 separable compounds from a single precursor. As a first step toward unraveling this complexity, a method was developed for measuring the polarity and volatility of individual compounds in a complex mixture using two-dimensional gas chromatography, which is demonstrated in Chapter 2 for describing the oxidation of SOA formed from a biogenic compound (longifolene: C15H24). Several major products and tens of substantial minor products were produced, but none could be identified by traditional methods or have ever been isolated and studied in the laboratory. A major realization of this work was that soft ionization mass spectrometry could be used to identify the molecular mass and formula of these unidentified compounds, a major step toward a comprehensive description of complex mixtures. This was achieved by coupling gas chromatography to high resolution time-of-flight mass spectrometry with vacuum ultraviolet (VUV) photo-ionization. Chapters 3 and 4 describe this new analytical technique and its initial application to determine the structures of unknown compounds and formerly unresolvable mixtures, including a complete description of the chemical composition of two common petroleum products related to anthropogenic emissions: diesel fuel and motor oil. The distribution of hydrocarbon isomers in these mixtures - found to be mostly of branched, cyclic, and saturated - is described with unprecedented detail. Instead of measuring average bulk aerosol properties, the methods developed and applied in this work directly measure the polarity, volatility, and structure of individual components to allow a mechanistic understanding of oxidation processes. Novel characterizations of these complex mixtures are used to elucidate the role of structure and functionality in particle-phase oxidation, including in Chapter 4 the first measurements of relative reaction rates in a complex hydrocarbon particle. Molecular structure is observed to influence particle-phase oxidation in unexpected and important ways, with cyclization decreasing reaction rates by ~30% and branching increasing reaction rates by ~20-50%. The observed structural dependence is proposed to result in compositional changes in anthropogenic organic aerosol downwind of urban areas, which has been confirmed in subsequent work by applying the techniques described here. Measurement of organic aerosol components is extended to ambient environments through the development of instrumentation with the unprecedented capability to measure hourly concentrations and gas/particle partitioning of individual highly oxygenated organic compounds in the atmosphere. Chapters 5 and 6 describe development of new procedures and hardware for the calibration and analysis of oxygenates using the Semi-Volatile Thermal desorption Aerosol Gas chromatograph (SV-TAG), a custom instrument for in situ quantification of gas- and particle-phase organic compounds in the atmosphere. High time resolution measurement of oxygenated compounds is achieved through a reproducible and quantitative methodology for in situ "derivatization"--Replacing highly polar functional groups that cannot be analyzed by traditional gas chromatography with less polar groups. Implementation of a two-channel sampling system for the simultaneous collection of particle-phase and total gas-plus-particle phase samples allows for the first direct measurements of gas/particle partitioning in the atmosphere, significantly advancing the study of atmospheric composition and variability, as well as the processes governing condensation and re-volatilization. This work presents the first in situ measurements of a large suite of highly oxygenated biogenic oxidation products in both the gas- and particle-phase. Isoprene, the most ubiquitous biogenic emission, oxidizes to form 2-methyltetrols and C5 alkene triols, while [alpha]-pinene, the most common monoterpene, forms pinic, pinonic, hydroxyglutaric, and other acids. These compounds are reported in Chapter 7 with unprecedented time resolution and are shown for the first time to have a large gas-phase component, contrary to typical assumptions. Hourly comparisons of these products with anthropogenic aerosol components elucidate the interaction of human and natural emissions at two rural sites: the southeastern, U.S. and Amazonia, Brazil. Anthropogenic influence on SOA formation is proposed to occur through the increase in liquid water caused by anthropogenic sulfate. Furthermore, these unparalleled observations of gas/particle partitioning of biogenic oxidation products demonstrate that partitioning of oxygenates is unexpectedly independent of volatility: many volatile, highly oxygenated compounds have a large particle-phase component that is poorly described by traditional models. These novel conclusions are reached in part by applying the new frameworks developed in previous chapters to understand the properties of unidentified compounds, demonstrating the importance of detailed characterization of atmospheric organic mixtures. Comprehensive analysis of anthropogenic and biogenic emissions and oxidation product mixtures is coupled in this work with high time-resolution measurement of individual organic components to yield significant insights into the transformations of organic aerosols. Oxidation chemistry is observed in both laboratory and field settings to depend on molecular properties, volatility, and atmospheric composition. However, this work demonstrates that these complex processes can be understood through the quantification of individual known and unidentified compounds, combined with their classification into descriptive frameworks.

Author: Ingrid Jennifer George
Publisher:
ISBN: 9780494609651
Category :
Languages : en
Pages : 0

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The chemical aging of organic aerosols by OH-initiated heterogeneous oxidation was investigated using both model organic and ambient aerosol particles. Organic aerosol particles were exposed to OH radicals in an aerosol flow tube and the modification of their chemical composition and particle properties was studied. Overall, this work has shown that OH-initiated heterogeneous oxidation enhanced the degree of oxidation and the Cloud Condensation Nucleus (CCN) activity of organic aerosol particles for equivalent OH exposure timescales of a few days to a week. The modification of the hygroscopicity of model primary and secondary organic aerosols from chemical aging was investigated by measuring the CCN activity of organic aerosols exposed to OH radicals. Primary organic aerosols, initially CCN inactive, became as CCN active as secondary organic aerosols due to heterogeneous reaction, where surface tension reduction played a major role. The CCN activity for model secondary organic aerosols was also enhanced due to OH oxidation, but changes were less dramatic than for the model primary organic aerosols. Aerosol Mass Spectrometer (AMS) measurements showed that the heterogeneous uptake kinetics of OH radicals onto model primary organic aerosols was efficient. The heterogeneous reaction of organic aerosols with OH led to the production of high molecular weight particle-phase species with the addition of multiple oxygenated functional groups. These results were consistent with the observed increase in particle density with OH exposure. With the exception of solid organic aerosols, the particle volume and mass of organic particles were reduced by less than 20% from OH oxidation at high OH exposures due to volatilization of particle-phase reaction products. The degree of oxidation of the organic fraction of urban ambient aerosols was significantly enhanced for an equivalent atmospheric OH exposure time of 4 days for a daily average atmospheric OH concentration of 2x10 6 cm-3. Ambient aerosol particles sampled from a sparsely populated, forested region were initially more oxygenated than the urban aerosol particles and did not become more oxidized from reaction with OH radicals.