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Atmospheric Aerosol Aging Involving Organic Compounds And Impacts On Particle Properties
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Book Synopsis Atmospheric Aerosol Aging Involving Organic Compounds and Impacts on Particle Properties by : Chong Qiu
Download or read book Atmospheric Aerosol Aging Involving Organic Compounds and Impacts on Particle Properties written by Chong Qiu and published by . This book was released on 2013 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: In the first part of this dissertation, we study the aging of soot, a representative type of primary aerosols, in the presence of OH-initiated oxidation products of toluene. Monodisperse soot particles are introduced into an environmental chamber where toluene is oxidized by OH radicals. The variations in soot particle properties are simultaneously monitored, including particle size, mass, organic mass faction, hygroscopicity, and optical properties. The changes in particle properties are found to be largely governed by the thickness of the organic coating that is closely related to reaction time and initial reactant concentrations. Derived from particle size and mass, the effective density increases while dynamic shape factor decreases as the organic coating grows, suggesting a compaction of the soot morphology. As the organic coating grows, the particles become more hygroscopic and have enhanced light scattering and absorption. The second part discusses the potential reactions between amines and some aerosol constituents and alteration of aerosol properties. The reactions between alkylamines and ammonium sulfate/bisulfate have been studied using a low-pressure fast flow reactor coupled to a mass spectrometer at 293 K. Alkylamines react with ammonium sulfate/bisulfate to form alkylaminium sulfates, suggesting the existence of alkylaminium salts in particle phase. We have extended our study to characterize the physicochemical properties of alkylaminium sulfates. The hygroscopicity, thermostability, and density of five representative alkylaminium sulfates have been measured by an integrated aerosol analytical system. All alkylaminium sulfate aerosols show monotonic size growth when exposed to increasing relative humidity. Mixing ammonium sulfate with alkylaminium sulfates lowers the deliquescence point corresponding to ammonium sulfate. Alkylaminium sulfates are thermally comparable to or more stable than ammonium sulfate. The densities of alkylaminium sulfate particles are lower than that of ammonium sulfate. Our results suggest that the organic compounds can effectively alter the composition and properties of atmospheric aerosols, considerably influencing the impacts of aerosols on air quality, climate forcing, and human health. The electronic version of this dissertation is accessible from http://hdl.handle.net/1969.1/149291
Book Synopsis Aerosols in Atmospheric Chemistry by : Yue Zhang
Download or read book Aerosols in Atmospheric Chemistry written by Yue Zhang and published by American Chemical Society. This book was released on 2022-04-01 with total page 176 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.
Book Synopsis The Aging of Organic Aerosol in the Atmosphere by : Sean Herbert Kessler
Download or read book The Aging of Organic Aerosol in the Atmosphere written by Sean Herbert Kessler and published by . This book was released on 2013 with total page 134 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.
Book Synopsis Chemical Aging of Single and Multicomponent Biomass Burning Aerosol Surrogate-particles by OH by :
Download or read book Chemical Aging of Single and Multicomponent Biomass Burning Aerosol Surrogate-particles by OH written by and published by . This book was released on 2015 with total page 49 pages. Available in PDF, EPUB and Kindle. Book excerpt: Multiphase OH and O3 oxidation reactions with atmospheric organic aerosol (OA) can influence particle physicochemical properties including composition, morphology, and lifetime. Chemical aging of initially insoluble or low soluble single-component OA by OH and O3 can increase their water-solubility and hygroscopicity, making them more active as cloud condensation nuclei (CCN) and susceptible to wet deposition. However, an outstanding problem is whether the effects of chemical aging on their CCN activity are preserved when mixed with other organic or inorganic compounds exhibiting greater water-solubility. In this work, the CCN activity of laboratory-generated biomass burning aerosol (BBA) surrogate-particles exposed to OH and O3 is evaluated by determining the hygroscopicity parameter, [kappa], as a function of particle type, mixing state, and OH/O3 exposure applying a CCN counter (CCNc) coupled to an aerosol flow reactor (AFR). Levoglucosan (LEV), 4-methyl-5-nitrocatechol (MNC), and potassium sulfate (KS) serve as representative BBA compounds that exhibit different hygroscopicity, water solubility, chemical functionalities, and reactivity with OH radicals, and thus exemplify the complexity of mixed inorganic/organic aerosol in the atmosphere. The CCN activities of all of the particles were unaffected by O3 exposure. Following exposure to OH, [kappa] of MNC was enhanced by an order of magnitude, from 0.009 to ~0.1, indicating that chemically-aged MNC particles are better CCN and more prone to wet deposition than pure MNC particles. No significant enhancement in [kappa] was observed for pure LEV particles following OH exposure. [kappa] of the internally-mixed particles was not affected by OH oxidation. Furthermore, the CCN activity of OH exposed MNC-coated KS particles is similar to the OH unexposed atomized 1:1 by mass MNC: KS binary-component particles. Our results strongly suggest that when OA is dominated by water-soluble organic carbon (WSOC) or inorganic ions, chemical aging has no significant impact on OA hygroscopicity. The organic compounds exhibiting low solubility behave as if they are infinitely soluble when mixed with a sufficient amount of water-soluble compounds. At and beyond this point, the particles' CCN activity is governed entirely by the water-soluble fraction and not influenced by the oxidized organic fraction. Our results have important implications for heterogeneous oxidation and its impact on cloud formation given that atmospheric aerosol is a complex mixture of organic and inorganic compounds exhibiting a wide-range of solubilities.
Book Synopsis Laboratory Studies of the Multiday Oxidative Aging of Atmospheric Organic Aerosol by : Christopher Yung-Ta Lim
Download or read book Laboratory Studies of the Multiday Oxidative Aging of Atmospheric Organic Aerosol written by Christopher Yung-Ta Lim and published by . This book was released on 2019 with total page 101 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.
Book Synopsis Oxidation of Atmospheric Organic Carbon by : James Freeman Hunter
Download or read book Oxidation of Atmospheric Organic Carbon written by James Freeman Hunter and published by . This book was released on 2015 with total page 110 pages. Available in PDF, EPUB and Kindle. Book excerpt: .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.
Book Synopsis Atmospheric Aerosol Properties and Climate Impacts by :
Download or read book Atmospheric Aerosol Properties and Climate Impacts written by and published by . This book was released on 2009 with total page 136 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis A Computational Approach to Understanding Aerosol Formation and Oxidant Chemistry in the Troposphere by :
Download or read book A Computational Approach to Understanding Aerosol Formation and Oxidant Chemistry in the Troposphere written by and published by . This book was released on 2006 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: An understanding of the mechanisms and kinetics of aerosol formation and ozone production in the troposphere is currently a high priority because these phenomena are recognized as two major effects of energy-related air pollution. Atmospheric aerosols are of concern because of their effect on visibility, climate, and human health. Equally important, aerosols can change the chemistry of the atmosphere, in dramatic fashion, by providing new chemical pathways (in the condensed phase) unavailable in the gas phase. The oxidation of volatile organic compounds (VOCs) and inorganic compounds (e.g., sulfuric acid, ammonia, nitric acid, ions, and mineral) can produce precursor molecules that act as nucleation seeds. The U.S. Department of Energy (DOE) Atmospheric Chemistry Program (ACP) has identified the need to evaluate the causes of variations in tropospheric aerosol chemical composition and concentrations, including determining the sources of aerosol particles and the fraction of such that are of primary and secondary origin. In particular, the ACP has called for a deeper understanding into aerosol formation because nucleation creates substantial concentrations of fresh particles that, via growth and coagulation, influence the Earth's radiation budget. Tropospheric ozone is also of concern primarily because of its impact on human health. Ozone levels are controlled by NOx and by VOCs in the lower troposphere. The VOCs can be either from natural emissions from such sources as vegetation and phytoplankton or from anthropogenic sources such as automobiles and oil-fueled power production plants. The major oxidant for VOCs in the atmosphere is the OH radical. With the increase in VOC emissions, there is rising concern regarding the available abundance of HOx species needed to initiate oxidation. Over the last five years, there have been four field studies aimed at initial measurements of HOx species (OH and HO? radicals). These measurements revealed HOx levels that are two to four times higher than expected from the commonly assumed primary sources. Such elevated abundances of HOx imply a more photochemically active troposphere than previously thought. This implies that rates of ozone formation in the lower region of the atmosphere and the oxidation of SO? can be enhanced, thus promoting the formation of new aerosol properties. Central to unraveling this chemistry is the ability to assess the photochemical product distributions resulting from the photodissociation of by-products of VOC oxidation. We propose to use state-of-the-art theoretical techniques to develop a detailed understanding of the mechanisms of aerosol formation in multicomponent (mixed chemical) systems and the photochemistry of atmospheric organic species. The aerosol studies involve an approach that determines homogeneous gas-particle nucleation rates from knowledge of the molecular interactions that are used to define properties of molecular clusters. Over the past several years we developed Dynamical Nucleation Theory (DNT), a novel advance in the theoretical description of homogeneous gas-liquid nucleation, and applied it to gas-liquid nucleation of a single component system (e.g., water). The goal of the present research is to build upon these advances by extending the theory to multicomponent systems important in the atmosphere (such as clusters containing sulfuric acid, water, ions, ammonia, and organics). In addition, high-level ab initio electronic structure calculations will be used to unravel the chemical reactivity of the OH radical and water clusters.
Book Synopsis Atmospheric Aerosols by : Rekha Kale
Download or read book Atmospheric Aerosols written by Rekha Kale and published by Scitus Academics LLC. This book was released on 2015-03 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: Atmospheric Aerosols is a vital problem in current environmental research due to its importance in atmospheric optics, energetics, radiative transfer studies, chemistry, climate, biology and public health. Aerosols can influence the energy balance of the terrestrial atmosphere, the hydrological cycle, atmospheric dynamics and monsoon circulations. Because of the heterogeneous aerosol field with large spatial and temporal variability and reduction in uncertainties in aerosol quantification is a challenging task in atmospheric sciences. Keeping this in view the present study aims to assess the impact of aerosols on coastal Indian station Visakhapatnam and the adjoining Bay of Bengal. An aerosol is a colloid of fine solid particles or liquid droplets, in air or another gas. Aerosols can be natural or not. Examples of natural aerosols are fog, forest exudates and geyser steam.
Book Synopsis Development of Novel Instrumentation and Methods to Investigate the Composition and Phase Partitioning of Semivolatile and Intermediately Volatile Organic Compounds in Atmospheric Organic Aerosol by : Claire Francis Fortenberry
Download or read book Development of Novel Instrumentation and Methods to Investigate the Composition and Phase Partitioning of Semivolatile and Intermediately Volatile Organic Compounds in Atmospheric Organic Aerosol written by Claire Francis Fortenberry and published by . This book was released on 2020 with total page 327 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.
Book Synopsis Observations of Secondary Organic Aerosol Production and Soot Aging Under Atmospheric Conditions Using a Novel Environmental Aerosol Chamber by : Crystal Glen
Download or read book Observations of Secondary Organic Aerosol Production and Soot Aging Under Atmospheric Conditions Using a Novel Environmental Aerosol Chamber written by Crystal Glen and published by . This book was released on 2012 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Secondary organic aerosols (SOA) comprise a substantial fraction of the total global aerosol budget. While laboratory studies involving smog chambers have advanced our understanding of the formation mechanisms responsible for SOA, our knowledge of the processes leading to SOA production under ambient gaseous and particulate concentrations as well as the impact these aerosol types have on climate is poorly understood. Although the majority of atmospheric aerosols scatter radiation either directly or indirectly by serving as cloud condensation nuclei, soot is thought to have a significant warming effect through absorption. Like inorganic salts, soot may undergo atmospheric transformation through the vapor condensation of non-volatile gaseous species which will alter both its chemical and physical properties. Typical smog chamber studies investigating the formation and growth of SOA as well as the soot aging process are temporally limited by the initial gaseous concentrations injected into the chamber environment. Furthermore, data interpretation from such experiments is generally restricted to the singular gaseous species under investigation. This dissertation discusses the use of a new aerosol chamber designed to study the formation and growth of SOA and soot aging under atmospherically relevant conditions. The Ambient Aerosol Chamber for Evolution Studies (AACES) was deployed at three field sites where size and hygroscopic growth factor (HGF) of ammonium sulfate seed particles was monitored over time to examine the formation and growth of SOA. Similar studies investigating the soot aging process were also conducted in Houston, TX. It is shown that during the ambient growth of ammonium sulfate seed particles, as particle size increases, hygroscopic growth factors decrease considerably resulting in a significant organic mass fraction in the particle phase concluding an experiment. Observations of soot aging show an increase in measured size, HGF, mass and single scattering albedo. Ambient growth rate comparisons with chamber growth yielded similar trends verifying the use of AACES to study aerosol aging. Based on the results from this study, it is recommended that AACES be employed in future studies involving the production and growth of SOA and soot aging under ambient conditions in order to bridge the gaps in our current scientific knowledge.
Book Synopsis Complex Mixtures by : Emma Quinn Walhout
Download or read book Complex Mixtures written by Emma Quinn Walhout and published by . This book was released on 2019 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.
Book Synopsis Atmospheric Aerosol Properties and Climate Impacts by :
Download or read book Atmospheric Aerosol Properties and Climate Impacts written by and published by . This book was released on 2009 with total page 128 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Enabling the Identification, Quantification, and Characterization of Organics in Complex Mixtures to Understand Atmospheric Aerosols by : Gabriel Avram Isaacman
Download or read book Enabling the Identification, Quantification, and Characterization of Organics in Complex Mixtures to Understand Atmospheric Aerosols written by Gabriel Avram Isaacman and published by . This book was released on 2014 with total page 167 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.
Book Synopsis Aerosol Pollution Impact on Precipitation by : Zev Levin
Download or read book Aerosol Pollution Impact on Precipitation written by Zev Levin and published by Springer Science & Business Media. This book was released on 2008-09-30 with total page 399 pages. Available in PDF, EPUB and Kindle. Book excerpt: Life on Earth is critically dependent upon the continuous cycling of water between oceans, continents and the atmosphere. Precipitation (including rain, snow, and hail) is the primary mechanism for transporting water from the atmosphere back to the Earth’s surface. It is also the key physical process that links aspects of climate, weather, and the global hydrological cycle. Changes in precipitation regimes and the frequency of extreme weather events, such as floods, droughts, severe ice/snow storms, monsoon fluctuations and hurricanes are of great potential importance to life on the planet. One of the factors that could contribute to precipitation modification is aerosol pollution from various sources such as urban air pollution and biomass burning. Natural and anthropogenic changes in atmospheric aerosols might have important implications for precipitation by influencing the hydrological cycle, which in turn could feed back to climate changes. From an Earth Science perspective, a key question is how changes expected in climate will translate into changes in the hydrological cycle, and what trends may be expected in the future. We require a much better understanding and hence predictive capability of the moisture and energy storages and exchanges among the Earth’s atmosphere, oceans, continents and biological systems. This book is a review of our knowledge of the relationship between aerosols and precipitation reaching the Earth's surface and it includes a list of recommendations that could help to advance our knowledge in this area.
Book Synopsis Elucidation of Mechanisms and Impacts of Oxidation on Organic Particulate Matter by : Katheryn Ruth Kolesar
Download or read book Elucidation of Mechanisms and Impacts of Oxidation on Organic Particulate Matter written by Katheryn Ruth Kolesar and published by . This book was released on 2015 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Atmospheric particulate matter (PM) is a component of air pollution that negatively impacts human health and welfare and has strong impacts on global climate. The organic fraction of PM, organic aerosol (OA), is often a dominant fraction of PM mass. Organic aerosol can be emitted directly into the atmosphere as primary OA (POA) or can be produced in the atmosphere from processes such as gas phase reactions of volatile organic compounds (VOCs) with oxidants or aqueous phase reactions of dissolved organics both of which form secondary OA (SOA). The formation and evolution of SOA, as well as the interaction between SOA and POA, are poorly characterized, which leads to uncertainties in the prediction of their concentrations and impacts in the atmosphere. This dissertation addresses processes associated with gas phase SOA formation as well as chemical and physical processing of SOA and POA through experimental studies investigating: 1) the volatility of SOA, 2) the influence of SOA on the heterogeneous oxidation of POA, and 3) the chemical mechanisms of POA oxidation. In the first set of studies (Chapters 2-3), it is experimentally demonstrated that there has been a fundamental disconnect between the properties of SOA as derived from SOA formation and growth experiments and those derived from evaporation experiments, which has implications for the representation of SOA within air quality and climate models. Specifically, SOA is experimentally determined to be less volatile than predicted based on formation studies through the measurement of the extent of evaporation with temperature change along with concurrent measurement of the particle composition. Volatility measurements were made as a function of mass concentration for [alpha]pinene+O3 SOA and with accompanying particle composition measurements for different SOA types. It was found that SOA volatility was independent of mass concentration and that nine types of SOA had similar volatilities. Furthermore, SOA composition remained constant as particles evaporated. When compared to results from a detailed, physically based model of evaporation, these observations suggest that there are condensed-phase chemical reactions that rapidly produce oligomers and that oligomers are likely the majority of the SOA mass. In a second study (Chapter 4), a detailed experimental and model assessment of the chemical pathways associated with OH-driven heterogeneous chemistry of two model POA compounds is discussed. The chemical pathways for oxidation of POA are often assumed to be the same as gas phase reactions, yet the higher density of molecules in the condensed phase may increase the dominance of alternate mechanisms. The heterogeneous oxidation of squalane and BES are used as model POA compounds to investigate structure-dependent chemical mechanisms of oxidation. The oxidation of squalane is dominated by the formation of products with added ketone or alcohol functionality whereas the oxidation of BES is dominated by the addition of ketone moieties with minor contributions from pathways forming alcohol substituted products. These differences are shown to be linked directly to differences in the dominant chemical pathways available to the different precursor molecules that result from structural differences in the molecules. In Chapter 5, the influence of an SOA "coating" on the OH initiated heterogeneous oxidation of model POA particles, comprised of squalane, is considered. Previous studies have shown that SOA can protect buried compounds from reaction with O3 but the extent to which such protection extends to other oxidants had not been established. Here, it is shown that when OH is the oxidant SOA does not block squalane from oxidation and, in fact, the rate of oxidation with OH exposure is enhanced. Although it is clear that an enhancement occurs, the exact extent of enhancement is dependent on the assumed particle morphology, i.e. whether the particle is well mixed, partially engulfed or there is an SOA coating on the squalane core.
Book Synopsis Atmospheric Aerosols by : Claudio Tomasi
Download or read book Atmospheric Aerosols written by Claudio Tomasi and published by John Wiley & Sons. This book was released on 2017-03-20 with total page 706 pages. Available in PDF, EPUB and Kindle. Book excerpt: Ein Blick auf die morphologischen, physikalischen und chemischen Eigenschaften von Aerosolen aus den unterschiedlichsten natürlichen und anthropogenen Quellen trägt zum besseren Verständnis der Rolle bei, die Aerosolpartikel bei der Streuung und Absorption kurz- und langwelliger Strahlung spielen. Dieses Fachbuch bietet Informationen, die sonst schwer zu finden sind, und vermittelt ausführlich die Kenntnisse, die erforderlich sind, um die mikrophysikalischen, chemischen und Strahlungsparameter zu charakterisieren, die bei der Wechselwirkung von Sonnen- und Erdstrahlen so überaus wichtig sind. Besonderes Augenmerk liegt auf den indirekten Auswirkungen von Aerosolen auf das Klima im Rahmen des komplexen Systems aus Aerosolen, Wolken und der Atmosphäre. Auch geht es vorrangig um die Wirkungen natürlicher und anthropogener Aerosole auf die Luftqualität und die Umwelt, auf die menschliche Gesundheit und unser kulturelles Erbe. Mit einem durchgängig lösungsorientierten Ansatz werden nicht nur die Probleme und Gefahren dieser Aerosole behandelt, sondern auch praktikable Lösungswege aufgezeigt.
