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Organic aerosol is a central topic in environmental science due to its role in climate forcing and negative health effects. The transformation of organic species from primary gas phase emissions to secondary organic aerosol (SOA) is highly complex and poorly understood, proving difficult for even stateof- the-art computational models to predict. This thesis describes the in-depth characterization and redesign of a previously developed technique for the quantification of intermediate volatility organic compounds (IVOCs), which are compounds with saturation vapor pressures of 103-107 [mu]g/m3. This analytical technique, the thermal-desorption electron ionization mass spectrometer (TD-EIMS) provides a volatility separated, bulk measurement of IVOCs and will be used to investigate the primary emissions as well as production and evolution of IVOCs in a series of experiments described in this thesis. Primary emissions of IVOCs have been previously measured in vehicle exhaust and have been theorized as a significant precursor to secondary organic aerosol (SOA) in urban atmospheres. IVOCs are predominately emitted during cold start periods, but maintain a similar chemical composition across all engine states. As emissions controls have tightened, emissions of non-methane hydrocarbons and primary particulate matter have decreased, however emissions of IVOCs have only decreased significantly (as much as 80%) between the newest ULEV and SULEV emissions control tiers. Laboratory studies examining the atmospheric oxidation of common biogenic and anthropogenic SOA precursors in environmental "smog" chambers show different production and evolution profiles of IVOCs. The comparison of IVOCs measured by the TD-EIMS with other analytical techniques sampling in parallel show the TD-EIMS may detect a previously characterized fraction of carbon. Production of secondary low volatility organic compounds can also occur in low oxygen systems, such as in planetary atmospheres or in the process of soot formation. Ultraviolet light or heat can form radical hydrocarbon species, which, in low oxygen environments, will react with other hydrocarbon or radical species, undergoing oxidation by molecular growth. Particles made from ethane and ethylene are composed of very saturated compounds. The particles produced from the photolysis of acetylene are fundamentally different showing significantly larger molecule sizes and substantially higher degrees of unsaturation. The results from this thesis demonstrate measurements of the production and evolution of primary and secondary low volatility organic gases by new analytical techniques and provide a new insight to the complex chemical processes in the atmosphere leading to the production of secondary organic aerosol.
Every day, large quantities of volatile organic compounds (VOCs) are emitted into the atmosphere from both anthropogenic and natural sources. The formation of gaseous and particulate secondary products caused by oxidation of VOCs is one of the largest unknowns in the quantitative prediction of the earth’s climate on a regional and global scale, and on the understanding of local air quality. To be able to model and control their impact, it is essential to understand the sources of VOCs, their distribution in the atmosphere and the chemical transformations which remove these compounds from the atmosphere. In recent years techniques for the analysis of organic compounds in the atmosphere have been developed to increase the spectrum of detectable compounds and their detection limits. New methods have been introduced to increase the time resolution of those measurements and to resolve more complex mixtures of organic compounds. Volatile Organic Compounds in the Atmosphere describes the current state of knowledge of the chemistry of VOCs as well as the methods and techniques to analyse gaseous and particulate organic compounds in the atmosphere. The aim is to provide an authoritative review to address the needs of both graduate students and active researchers in the field of atmospheric chemistry research.
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.
.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.
Papers delivered at the symposium of the same name, April 1994, by speakers from seven nations. Twenty presentations are arranged under six topics: regulation and assessment, air quality, environmental fate, environmental measurement, environmental monitoring, and control and remediation. A sampling
"Coming to a conclusion, this wonderful, informative and very interesting book presents an excellent overview of small volatile organic compounds and their role in our life and environment. Really fascinating is the entirety of scientific disciplines which were addressed by this book." –Flavour and Fragrance Journal, 2011 "... this book deserves to be a well-used reference in the library of any laboratory specialising in VOC". –Chemistry World, 2011 Volatile compounds are molecules with a relatively low molecular weight allowing for an efficient evaporation into the air. They are found in many areas of our everyday-life: they are responsible for the communication between species such as plants, insects or mammals; they serve as flavours or fragrances in many food products or perfumed consumer articles; and they play an important role in atmospheric chemistry. This book takes an interdisciplinary approach to volatile molecules. Review-style introductions to the main topics in volatile chemistry and biology are provided by international experts, building into a broad overview of this fascinating field. Topics covered include: The structural variety of volatile compounds Biogeneration of volatiles Synthesis of natural and non-natural volatiles Analysis of volatiles Volatile compounds as semiochemicals in plant-plant or plant-insect interactions Volatiles in pest control Pheromones and the influence of volatiles on mammals Olfaction and human perception Volatiles as fragrances The generation of flavours and food aroma compounds Stabilisation and controlled release of volatiles The impact of volatiles on the environment and the atmosphere
Developed from a symposium at the 199th National Meeting of the ACS, Boston, April 1990, this volume describes state-of-the-art techniques for collecting, separating, and analyzing aerosols and gases, and discusses current problems that must be solved for progress in the understanding of the atmosphere to continue. A reference for atmospheric scientists and researchers of gas-phase and aerosol interactions, and a tutorial for analytic chemists interested in undertaking atmospheric studies. Annotation copyright by Book News, Inc., Portland, OR
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.
Organic chemicals constitute minor gaseous components of the earth's atmosphere. Despite low concentrations they play an important role in the global processes influencing the composition of our atmosphere. The author summarizes the multidisciplinary data on sources and thermo- and photochemical transformations of organic components in the atmosphere. Modern methods of atmospheric microimpurity analysis are explained. Models for their time-dimensional distribution both in the urban atmosphere and in unpolluted air are developed. The book provides a unique source of contemporary information for scientists involved in atmospheric chemistry, meteorology, ecology and geophysics.