Download or read book Characterization of Secondary Organic Aerosols in the Atmosphere by Using Mass Spectrometric Approaches written by Farhat Yasmeen and published by . This book was released on 2011 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Characterization of the Molecular Composition of Secondary Organic Aerosols Using High Resolution Mass Spectrometry written by Rachel Elizabeth Sellon and published by . This book was released on 2012 with total page 274 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.

Download or read book Molecular Characterization of Organic Aerosol by Mass Spectrometry written by Yuqian Gao and published by . This book was released on 2011 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Organic aerosol is a major constituent of atmospheric fine particles, especially over continental regions. These particles adversely affect human health and global climate. A significant fraction of organic aerosol is considered to be from the oxidation products of ozone and volatile organic compounds, which are called secondary organic aerosol (SOA). To study the formation mechanisms of secondary organic aerosol, it is important to characterize their molecular composition. The composition of secondary organic aerosol is very complex including thousands of species with molecular weight up to over a thousand Dalton. Methods utilized for the identification of these oxidation products involve advanced mass spectrometry techniques. In this dissertation, three mass spectrometry techniques were developed to study the molecular composition of organic aerosol. Firstly, online nano-aerosol sample deposition methods for matrix-assisted laser desorption/ionization (MALDI) mass spectrometry was developed to incorporate matrix particles directly with analyte particles onto a conventional MALDI plate. Secondly, a microsampling and analysis technique was developed in order to collect microgram samples and analyze them with high performance mass spectrometry. With this technique, the molecular composition of particle phase SOA at a low mass loading can be elucidated, which provides information about SOA formation at the early stages. A species with the (neutral molecule) formula C 17 H 26 O 8 (MW 358) increased substantially in intensity relative to other products as the mass loading decreased. Tandem mass spectrometry (MS n) of this species showed it to be a dimer of C 9 H 14 O 4 and C 8 H 12 O 4, most likely pinic acid and terpenylic acid, respectively. This species is likely to be critical at the early stages of SOA formation. Thirdly, ambient secondary electrospray ionization (ESI) source was designed to characterize the molecular composition of both gas and particle phases SOA online. This ion source was demonstrated to be applicable to a wide range of mass spectrometers having an ambient inlet. This technique provides a tool to acquire detailed information about possible SOA nucleation agents. A species with the (neutral molecule) formula C 20 H 36 O 6 (MW 372) was found in the gas-phase products of SOA, which could be critical for the new particle formation of SOA. Tandem mass spectrometry (MS n) of this species showed it to be a dimer of an organic hydroperoxide C 10 H 18 O 3, which is likely formed via OH-initiated oxidation pathway.

Download or read book Characterization of Secondary Organic Aerosol Precursors Using Two Dimensional Gas Chromatography with Time of Flight Mass Spectrometry GC GC TOFMS written by and published by . This book was released on 2013 with total page 64 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.

Download or read book Characterization of Biogenic Secondary Organic Aerosol Using Mass Spectrometry written by Katherine J. Heaton and published by . This book was released on 2010 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Secondary Organic Aerosol (SOA) forms in the atmosphere from the oxidation of biogenic emissions. Even though SOA has been linked to health and climate effects, the chemical mechanism of SOA formation is not well understood. Through the use of mass spectrometry, this work characterizes SOA during the early stages of growth from the reaction of ozone with monoterpenes, a major biogenic emission. In this thesis, three types of studies are described for analyzing SOA formation: (1) the molecular composition of SOA is studied using the photoionization aerosol mass spectrometer, (2) the atomic composition is studied with the nanometer aerosol mass spectrometer and (3) high resolution mass spectrometry is used to help reconcile atomic and molecular composition data. The monoterpene ozonolysis reactions were performed in a flow tube reactor, where the reaction period could vary from 3s to 22s. The Photoionization Aerosol Mass Spectrometer (PIAMS) detected the formation of oligomers within seconds of the onset of the reaction. Ions that were detected were mapped to dimers that could form via the stabilized Criegee intermediate channel or the hydroperoxy channel. The Nanometer Aerosol Mass Spectrometer (NAMS) analyzed the elemental composition of the SOA which showed the formation of highly polar compounds during the early stages of SOA growth. NAMS also analyzed the changes in the composition of SOA when it formed in the presence of atmospheric species (water vapor, nitric acid vapor and sodium chloride seed particles). The data collected indicated that there is not as much change for endocyclic compounds as there is for exocyclic compounds. Finally, a new off-line analysis technique was created to micro-extract SOA deposited on a plate from the flow tube reactor. The samples were analyzed with the Fourier Transform Ion Cyclotron Resonance Mass Spectrometer (FTICR-MS). The FTICR-MS was used to collect molecular and elemental data simultaneously. The FTICR-MS produced accurate mass data that could be used to calculate molecular formulas. This provided a direct comparison of the data acquired with PIAMS and NAMS.

Download or read book Methods of Collecting and Separating Atmospheric Organic Aerosols for Analysis Using Two Dimensional Gas and Liquid Chromatography with Mass Spectrometry written by and published by . This book was released on 2015 with total page 30 pages. Available in PDF, EPUB and Kindle. Book excerpt: In the atmosphere, biogenic and anthropogenic emissions are oxidized to form secondary organic aerosols (SOA); however, the identities and concentrations of the compounds formed are inadequately known. In this work an aerosol (gas+particle) collection system was designed and tested in order to more fully characterize atmospheric volatile organic compounds (VOCs) and semi-volatile organic compounds (SVOCs) that contribute to SOA. Target compounds to be collected were C6 to C20 compounds with oxygenated functional groups such as aldehydes and alcohols. The collection system was designed to allow characterization of atmospheric aerosols using multiple analytical methods: two-dimensional gas chromatography with time of flight-mass spectrometry (GCxGC-TOFMS), with and without derivatization, and two- dimensional liquid chromatography with mass spectrometry (LCxLC-MS). The first stage of collection in the system uses a polytetrafluoroethelyne (PTFE) filter to capture the low volatility compounds in the particle phase. The flow is then split for two different collection mechanisms: adsorption thermal desorption (ATD) cartridges for gas phase VOCs, and solid phase extraction (SPE) filters for SVOCs. In order to test the viability of aerosol collection on PTFE filters and subsequent analysis using derivatization, four aerosol samples were collected on PTFE filters at Reed College. The average mass collected over 4 trials was 10.15 [microgram]. The U.S. Department of Energy Environmental and Molecular Science Lab (EMSL) performed extraction and derivatization on the Reed College samples, followed by GC-MS. Results show identifiable peaks that are significantly different than the filter blanks, suggesting that derivatization methods can be used to facilitate identification of relatively polar organic compounds sampled onto PTFE filters. Additional aerosol collection trials were conducted at Portland State University (PSU) using two SPE filters in series to collect gases and particles from tobacco smoke. A literature review was conducted to determine the type of SPE filter, time, and necessary flow rates to collect an optimum amount of sample for analysis. The tobacco smoke PM mass collected was 6mg/2mg and 2mg/0.9mg for trials one and two, respectively (front/back filter). PSU tobacco smoke samples were analyzed at EMSL using GC-MS with derivatization. Results showed successful collection of polar compounds in the semi-volatile range of interest, including alcohols, aldehydes, and phenols. Next steps of this research include collecting aerosol samples with the whole system (PTFE + ATD + SPE) and subsequent analysis of samples using GCxGC-TOFMS, with and without derivatization, and LCxLC-MS. Results to date suggest a more complete characterization of atmospheric organic aerosols can be attained using multiple offline analyses. Further characterization of atmospheric organic aerosols is necessary to improve air quality and climate modeling and develop efficient air quality and climate change mitigation technologies.

Download or read book Using Mass Spectrometry and Ftir to Characterize Atmospherically relevant Particles Generated in Laboratory Systems written by Emily Anne Bruns and published by . This book was released on 2011 with total page 166 pages. Available in PDF, EPUB and Kindle. Book excerpt: Atmospheric aerosols are known to have multifaceted effects on human health, visibility and climate. To understand these effects, characterization of aerosol properties is necessary. This dissertation focuses on several specific topics with the overall goal of improving our understanding of aerosols in the atmosphere. One area of importance is particulate organic nitrates, which are known to be ubiquitous in the atmosphere; however, there is a lack of proven analytical techniques for their measurement. The qualitative and quantitative response of a high resolution time of flight aerosol mass spectrometer to particulate organic nitrates was studied by analyzing secondary organic aerosol (SOA) from NO3 radical reactions with [Alpha]- and [Beta]-pinene, 3-carene, limonene, and isoprene. Extensive fragmentation of the organic nitrate products was observed in the mass spectra, which precluded molecular speciation. Another area of interest is the recent development of a number of ambient ionization techniques, which are promising for aerosol characterization. One such technique, atmospheric solids analysis probe mass spectrometry (ASAP-MS), was applied for the first time to the identification of organics in SOA, which was generated in the laboratory from the ozonolysis of & alpha;-pinene and isoprene, and from the NO3 oxidation of & alpha;-pinene. Also, ambient samples were collected from a forested and a suburban location. ASAP-MS data for the laboratory-generated samples showed peaks corresponding to well-known products of these reactions, and higher molecular weight oligomers were present in all samples. This is consistent with previously published studies of similar systems and shows that ASAP-MS should have wide applicability in both laboratory and field studies. Vapor pressures of low volatility compounds are important parameters in several atmospheric processes, including the formation of new particles and the partitioning of compounds between the gas-phase and particles. However, vapor pressures of low volatility compounds are challenging to measure and reported values vary significantly, illustrating the need for new approaches. ASAP-MS was applied for the first time to the measurement of vapor pressures and heats of sublimation. The measured heats of sublimation were in good agreement with published values. The vapor pressures were typically within a factor of three of published values made at similar temperatures. This study establishes that ASAP-MS is a promising new technique for vapor pressure and heat of sublimation measurements of low volatility compounds. To further understand new particle formation, laboratory and field measurements were made to identify gas-phase amines, which could play a role in new particle formation, from previously unknown sources using proton transfer reaction mass spectrometry. The work presented in this dissertation advances our understanding of aerosols and explores novel methods for their characterization.

Download or read book Chemical and Physical Characterization of Secondary Organic Aerosol Formation from Select Agricultural Emissions written by Quentin Gerald James Malloy and published by . This book was released on 2009 with total page 414 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Measurement Analysis and Remediation of Environmental Pollutants written by Tarun Gupta and published by Springer Nature. This book was released on 2019-10-08 with total page 474 pages. Available in PDF, EPUB and Kindle. Book excerpt: This book discusses contamination of water, air, and soil media. The book covers health effects of such contamination and discusses remedial measures to improve the situation. Contributions by experts provide a comprehensive discussion on the latest developments in the detection and analysis of contaminants, enabling researchers to understand the evolution of these pollutants in real time and develop more accurate source apportionment of these pollutants. The contents of this book will be of interest to researchers, professionals, and policy makers alike.

Download or read book A Molecular Characterization of Biogenic Secondary Organic Aerosol by High resolution Time of flight Mass Spectrometry written by Felipe Daniel Lopez-Hilfiker and published by . This book was released on 2015 with total page 178 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.

Download or read book Characterization of Products in Secondary Organic Aerosol Formation Using Mass Spectrometric Techniques written by Yongjie Li and published by . This book was released on 2010 with total page 121 pages. Available in PDF, EPUB and Kindle. Book excerpt:

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.

Download or read book Molecular Characterization of Atmospheric Organic Matter in Biogenic Secondary Organic Aerosol Ambient Aerosol and Clouds written by Yunzhu Zhao and published by . This book was released on 2014 with total page 256 pages. Available in PDF, EPUB and Kindle. Book excerpt: Atmospheric aerosol affects the Earth's energy budget, reduces visibility and influences human health. The organic composition of aerosol is quite complex and continuously evolves through various atmospheric processes. To gain a deeper understanding of the molecular composition of atmospheric organic matter (AOM), chamber-generated biogenic secondary organic aerosol (SOA), ambient aerosol and cloud water samples were studied. Ultrahigh resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry was used to provide detailed molecular characterization of the atmospheric samples. Due to the extremely high mass resolution and mass accuracy, thousands of individual molecular formulas were identified in all of the samples studied. Multivariate statistical analysis methods were evaluated to compare the similarities and differences of the sample compositions. The biogenic SOA from three individual monoterpene precursors and a sesquiterpene precursor have clusters of peaks in their mass spectra, indicating that high molecular weight oligomers are a major component of the SOA. The monoterpene SOA have similar molecular compositions, which are different from the sesquiterpene SOA composition. The indicator species of SOA were identified using multivariate statistical analysis. Daily 24-hour water-soluble organic carbon samples from ambient aerosol collected at the Storm Peak Laboratory (SPL) show similar bulk chemical properties regarding their average elemental ratios and double bond equivalents. Using multivariate statistical analysis, the site meteorological conditions were found to affect the aerosol molecular composition. Days with strong UV radiation and high temperature were found to contain large numbers of biogenic SOA molecular formulas. Days with high relative humidity and high sulfate ion concentrations were found to contain many sulfur-containing compounds, suggesting their aqueous phase formation. The collection of cloud samples at the SPL provided an opportunity to study aqueous processing of AOM. The cloud composition was affected by biomass burning and SOA. Comparisons of the sample compositions indicate biogenic SOA components are commonly observed in ambient aerosol and cloud samples collected at the SPL. Thus, the ambient samples were used to confirm the biogenic SOA indicator species identified in chamber-generated SOA. This study of the three types of atmospheric samples helps to understand the composition of AOM with respect to atmospheric processes.

Download or read book Analytical Chemistry of Aerosols written by Kvetoslav R. Spurny and published by Routledge. This book was released on 2017-11-22 with total page 504 pages. Available in PDF, EPUB and Kindle. Book excerpt: Until the 1980s, researchers studied and measured only the physical properties of aerosols. Since the 80s, however, interest in the physicochemcal properties of aerosols has grown tremendously. Scientists in environmental hygiene, medicine, and toxicology have recognized the importance held by the chemical composition and properties of aerosols and the interactions of inhaled, "bad" aerosols. This book offers the first comprehensive treatment of modern aerosol analytical methods, sampling and separation procedures, and environmental applications, and offers critical reviews of the latest literature. This important field has developed rapidly in the last 15 years, but until now, no book effectively summarized or analyzed the existing research. Analytical Chemistry of Aerosols reviews procedures, techniques, and trends in the measurement and analysis of atmospheric aerosols. With contributions from acknowledged, international experts, the book discusses various methods of bulk analysis, single particle analysis, and the analysis of special aerosol systems, including fibrous and bacterial aerosols.

Download or read book Secondary Organic Aerosol Composition Studies Using Mass Spectrometry written by Katherine Ann Schilling and published by . This book was released on 2015 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: Trace volatile organic compounds emitted by biogenic and anthropogenic sources into the atmosphere can undergo extensive photooxidation to form species with lower volatility. By equilibrium partitioning or reactive uptake, these compounds can nucleate into new aerosol particles or deposit onto already-existing particles to form secondary organic aerosol (SOA). SOA and other atmospheric particulate matter have measurable effects on global climate and public health, making understanding SOA formation a needed field of scientific inquiry. SOA formation can be done in a laboratory setting, using an environmental chamber; under these controlled conditions it is possible to generate SOA from a single parent compound and study the chemical composition of the gas and particle phases. By studying the SOA composition, it is possible to gain understanding of the chemical reactions that occur in the gas phase and particle phase, and identify potential heterogeneous processes that occur at the surface of SOA particles. In this thesis, mass spectrometric methods are used to identify qualitatively and qualitatively the chemical components of SOA derived from the photooxidation of important anthropogenic volatile organic compounds that are associated with gasoline and diesel fuels and industrial activity (C12 alkanes, toluene, and o-, m-, and p-cresols). The conditions under which SOA was generated in each system were varied to explore the effect of NOx and inorganic seed composition on SOA chemical composition. The structure of the parent alkane was varied to investigate the effect on the functionalization and fragmentation of the resulting oxidation products. Relative humidity was varied in the alkane system as well to measure the effect of increased particle-phase water on condensed-phase reactions. In all systems, oligomeric species, resulting potentially from particle-phase and heterogeneous processes, were identified. Imines produced by reactions between (NH4)2SO4 seed and carbonyl compounds were identified in all systems. Multigenerational photochemistry producing low- and extremely low-volatility organic compounds (LVOC and ELVOC) was reflected strongly in the particle-phase composition as well.

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.

Download or read book Chemical Composition and Photochemical Evolution of Limonene Secondary Organic Aerosol Studied Using High Resolution Electrospray Ionization Mass Spectrometry written by Adam Patrick Bateman and published by . This book was released on 2011 with total page 189 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.