Download or read book Insights Into the Molecular Level Composition Sources and Formation Mechanisms of Dissolved Organic Matter in Aerolsols and Precipitation written by Katye Elisabeth Altieri and published by . This book was released on 2009 with total page 163 pages. Available in PDF, EPUB and Kindle. Book excerpt: Atmospheric aerosols scatter and absorb light influencing the global radiation budget and climate, and are associated with adverse effects on human health. Precipitation is an important removal mechanism for atmospheric dissolved organic matter (DOM), and a potentially important input for receiving ecosystems. However, the sources, formation, and composition of atmospheric DOM in aerosols and precipitation are not well understood. This dissertation investigates the composition and formation mechanisms of secondary organic aerosol (SOA) formed through cloud processing reactions, elucidates the composition and sources of DOM in rainwater, and provides links connecting the two. Photochemical batch aqueous-phase reactions of organics with both biogenic and anthropogenic sources (i.e., methylglyoxal, pyruvic acid) and OH radical were performed to simulate cloud processing. The composition of products formed through cloud processing experiments and rainwater collected in New Jersey, USA was investigated using a combination of electrospray ionization mass spectrometry techniques, including ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometry. This dissertation has resulted in the first evidence that oligomers form through cloud processing reactions, the first detailed chemical mechanism of aqueous phase oligomerization, the first identification of oligomers, organosulfates, and nitrooxy organosulfates in precipitation, and the first molecular level chemical characterization of organic nitrogen in precipitation. The formation of oligomers in SOA helps to explain the presence of large multifunctional compounds and humic like substances (HULIS) that dominate particulate organic mass. Oligomers have low vapor pressures and remain in the particle phase after cloud evaporation, enhancing SOA. The chemical properties of the oligomers suggest that they are less hygroscopic than the monomeric reaction products (i.e., organic acids). Their elemental ratios are consistent with the hypothesis that oligomers are a large contributor to aged organic aerosol mass. The majority of the compounds identified in rainwater samples by advanced mass spectrometry appear to be products of atmospheric reactions, including known contributors to SOA formed from gas phase, aerosol phase, and in-cloud reactions in the atmosphere. The similarities between the complex organic matter in rainwater and SOA suggest that the large uncharacterized component of SOA is the main contributor to the large uncharacterized component of rainwater DOM.

Download or read book Formation and Chemical Evolution of Secondary Organic Aerosol from Aqueous phase Reactions of Atmospheric Phenols written by Lu Yu and published by . This book was released on 2016 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Secondary organic aerosol (SOA) is formed and transformed in atmospheric aqueous phases (e.g., cloud and fog droplets and deliquesced airborne particles containing small amounts of water) through a multitude of chemical and physical processes. Understanding the formation and transformation processes of SOA via aqueous-phase reactions is important for properly presenting its atmospheric evolution pathways in models and for elucidating its climate and health effects. Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the formation and evolution of phenol (C6H6O), guaiacol (C7H8O2; 2-methoxyphenol) and syringol (C8H10O3; 2,6-dimethoxyphenol) and with two major aqueous phase oxidants -- the triplet excited state of an aromatic carbonyl (3C*) and hydroxyl radical (·OH) - and interpret the reaction mechanisms. In addition, given that dissolved organic matter (DOM) is an important component of fog and cloud water and that it can undergo aqueous reactions to form more oxidized, less volatile species, we further investigate the photochemical processing of DOM in fog water to gain insights into the aqueous-phase processing of organic aerosol (OA) in the atmosphere. In Chapter 2, we thoroughly characterize the bulk chemical and molecular compositions of phenolic aqSOA formed at half-life (t[subscript 1/2]), and interpret the formation mechanisms. We find that phenolic aqSOA formed at t[subscript 1/2] is highly oxygenated with atomic oxygen-to-carbon ratio (O/C) in the range of 0.85-1.23. Dimers, higher oligomers (up to hexamers), functionalized monomers and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acids are detected. Compared with ·OH-mediated reactions, reactions mediated by 3C* are faster and produce more oligomers and hydroxylated species at t[subscript1/2]. We also find that aqSOA shows enhanced light absorption in the UV-vis region, suggesting that aqueous-phase reactions of phenols are an important source of secondary brown carbon in the atmosphere, especially in regions impacted by biomass burning. In Chapter 3, we investigate the chemical evolution of phenolic aqSOA via aqueous-phase reactions on the molecular level and interpret the aging mechanisms. Our results indicate that oligomerization is an important aqueous reaction pathway for phenols, especially during the initial stage of photooxidation. Functionalization and fragmentation become dominant at later stages, forming a variety of functionalized aromatic and ring-opening products with higher carbon oxidation states. Fragmentation reactions eventually dominate the photochemical evolution of phenolic aqSOA, forming a large number of highly oxygenated ring-opening molecules. In addition, phenolic aqSOA has a wide range of saturation vapor pressures (C*), varying from 10−20 [mu]g m−3 for functionalized phenolic oligomers to 10 [mu]g m−3 for ring-opening species with number of carbon less than 6. The detection of abundant extremely low volatile organic compounds (ELVOC) indicates that aqueous reactions of phenolic compounds are likely an important source of ELVOC in the atmosphere. Chapter 3 investigates the molecular transformation with aging based on the characterization of three aqSOA filter samples collected at the defined time intervals of the photoreaction. However, the chemical evolution of aqSOA products with hours of illumination at a higher time resolution is largely unknown. In Chapter 4, we investigate the chemical evolution of aqSOA at a 1-min time resolution based on high-resolution aerosol mass spectrometer (AMS) analysis. This is important for understanding the continuous evolution of phenolic aqSOA with aging as well as for elucidating the formation and transformation of different generations of products. Our results suggest that dimer and higher-order oligomers (trimers, tetramers, etc.) are formed continuously during the first 1-2 hours of photoreaction but show a gradual decrease afterwards. Functionalized derivatives grow at a later time and then gradually decrease. Highly oxidized ring-opening species continuously increase over the course of reactions. Positive matrix factorization (PMF) analysis of the AMS spectra of phenolic aqSOA identifies multiple factors, representing different generations of products. The 1st-generation products include dimers, higher-order oligomers and their oxygenated derivatives. The 2nd-generation products include oxygenated monomeric derivatives. The 3rd-generation products include highly oxidized ring-opening species. In Chapter 5, we investigate the evolution of dissolved organic matter (DOM) in fog water. Our results show that the mass concentration of DOM[subscript OA] (i.e., low-volatility DOM in fog water) is enhanced over the course of illumination, with continuous increase of O/C and atomic nitrogen-to-carbon ratio (N/C). The increase of DOM[subscript OA] is due to the incorporation of oxygen- and nitrogen-containing functional groups into the molecules. The aqueous aging of DOM[subscript OA] can be modeled as a linear combination of the dynamic variations of 3 factors using PMF analysis. Factor 1 is chemically similar to the DOM[subscript OA] before illumination, which is quickly reacted away. Factor 2 is representative of an intermediate component, which is first formed and then transformed, and O/C of Factor 2 is intermediate between that of Factor 1 and Factor 3. Factor 3 represents highly oxidized final products, which is continuously formed during illumination. Fog DOM absorbs significantly in the tropospheric sunlight wavelengths, but this absorption behavior stays almost constant over the course of illumination, despite the significant change in chemical composition.

Download or read book Dissolved Organic Matter in Atmospheric Deposition written by Lidiia Iavorivska and published by . This book was released on 2016 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Dissolved organic matter (DOM) in the atmosphere affects air quality and climate. Unlike inorganic constituents that typically consist of single compounds, DOM is a mixture of multiple organic compounds having varying molecular weights, reactivity and solubility. Dissolved organic carbon (DOC) is typically used as a measure of the total DOM present in solution. In the atmosphere, DOC originates from emissions of various biogenic and anthropogenic sources, such as vegetation, incomplete combustion of fossil fuels, biomass burning, and sea-spray. The ultimate fate of atmospheric DOC is to be oxidized to inorganic forms of carbon dioxide and carbon monoxide, or to be removed from the atmosphere and transferred to the landscape through deposition. Deposition can occur as wet deposition via precipitation and as dry deposition via surface settling of particles and gases. The concentration, or quantity, of DOC in precipitation plays an important role in the carbon cycle and in other elemental cycles; while the chemical composition, or quality, of DOC in precipitation largely determines its fate in the environment. Rain and snow deposited to the landscape are a source of nutrient enrichment to ecosystems and water bodies, and are especially important as an input of carbon in coastal regions. Since DOC in precipitation is highly chemically reactive and bioavailable it influences rates of productivity in aquatic ecosystems. Despite the significance of DOC to many ecosystem processes, knowledge about its contributions to landscapes in precipitation remains limited. With anthropogenic influences on the carbon cycle now widely recognized, the need for synthesis of existing datasets on atmospheric deposition of DOC and further determining its rates and drivers is great. My dissertation is focused on wet deposition of DOC and assesses the magnitude and patterns of variation of organic matter in precipitation over space and time. The dissertation is organized into four manuscripts. Chapter 1 is a literature review where I provide a new data synthesis from 83 contemporary, peer-reviewed studies where organic carbon (OC) in precipitation was measured at sites around the world. Data regarding the concentrations of OC in precipitation and rates of atmospheric deposition were compiled in a common set of units and presented along with the summary statistics. These data give insights into the magnitude and regional variability of OC in precipitation. Organic carbon was ubiquitous in precipitation in rural and urban locations; with DOC in precipitation spanning several orders of magnitude between locations. This synthesis brings attention to atmospheric deposition as an under-sampled piece of the global carbon cycle; highlights gaps in data availability and challenges for data inter-comparison; and provides a unique data set that can be used for toward exploring future changes in the carbon cycle. Chapter 2 aims to understand how DOC concentration and composition in precipitation change temporally from storm to storm. Precipitation samples were collected at the Susquehanna Shale Hills Critical Zone Observatory watershed (Pennsylvania, USA) during 90 storm events. Observational data revealed temporal variability associated with seasonality and meteorological conditions. Using a mixed modeling statistical approach, I showed that there are multiple processes that work in synergy to influence the quantity and quality of DOC in precipitation. Factors related to storm properties, emission sources, and to the chemical composition of the atmosphere could explain more than 60% of the storm to storm variability in DOC concentrations. This study provided observations on changes in DOC that can be useful in modeling of atmospheric chemistry and in considering temporal changes in ecosystem nutrient balances and microbial activity.Chapter 3 explores how DOC concentration and composition vary throughout the course of storm events. I measured DOC in sequential samples during 13 storms at the Shale Hills watershed. The observational data generated hypotheses about potential factors that influence variability of DOC within storms. While previous studies have observed that concentrations of other elements in precipitation typically decrease over the course of individual storms, results from this study showed that DOC concentrations are highly variable. During most storms concentrations decreased towards the end of the event; however increasing concentrations in the later stages of some storms highlight that DOC removal with precipitation is not merely an exponential decay process. The variability of DOC during events is related to the balance between the cloud microphysics, atmospheric chemical transformations, and synoptic scale gradients in the abundance of organic compounds in the boundary layer. This work advances understanding of physicochemical processes occurring during storms that are relevant to studies of atmospheric chemistry, carbon cycling, and ecosystem responses.Chapter 4 quantifies spatial gradients in wet atmospheric DOC deposition across the state of Pennsylvania (USA). DOC concentrations were measured in selected precipitation samples collected for six years at a network of atmospheric deposition monitoring sites. A simple modeling approach was used to estimate the first statewide, annual estimates of wet atmospheric DOC deposition. Results showed that DOC inputs with wet deposition in Pennsylvania represented about one-third as much as literature reported values for DOC exported by rivers from watersheds in the region. The rates of DOC wet deposition showed a pronounced seasonality and spatial distribution, with highest deposition rates observed in the summer, especially at the sites located in western Pennsylvania.

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 Spectroscopic Characterization of Dissolved Organic Matter written by Xiaoyan Cao and published by . This book was released on 2014 with total page 406 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Molecular and Optical Characterization of Dissolved Organic Matter in the Central Arctic Ocean written by Xianyu Kong and published by . This book was released on 2022 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: Dissolved organic matter (DOM) in the ocean is a complex mixture of molecules derived from autochthonous (marine) or allochthonous (terrestrial) origins. DOM plays an important role in marine biogeochemical cycles by attenuating light available for primary production, serving as an energy and nutrient source for heterotrophic communities, regulating the ultraviolet and visible light absorption, undergoing photochemical processing, and acting as a trace metal ligand. DOM in the Central Arctic Ocean (CAO) is influenced by increased freshwater input and associated terrestrial materials in recent decades due to rapid climate change. The quantification of DOM sources (terrestrial versus marine) in the water column of the CAO is not well constrained. Few studies have systematically investigated the seasonality and spatial variability of DOM by combining optical and molecular-level analytical techniques in the CAO, especially during winter. State of the art chemical characterization of DOM is subject to major challenges: Solid phase extraction (SPE) that is often used to desalt and pre-concentrate marine DOM introduces chemical fractionation effects, which limits the comparability between analytical results for original samples and those carried out for SPE-DOM. There is no specific method to quantify fractionation effects, nor specific guidelines to avoid fractionation. Using mass spectrometry, quantitative DOM analyses is challenged by selective ionization of molecules and the large number of unresolved structural isomers that prevent classical external calibration. In the first part of this thesis, a method was developed to quantitatively track optical or chemical fractionation during SPE and investigate the potential mechanisms. We found a decrease in extraction efficiency of dissolved organic carbon (DOC), fluorescence and absorbance, and polar organic substances with increasing carbon loading on the SPE column. As the surface loading of the solid-phase increased, the dominant extraction mechanism shifted from PPL physisorption to increased DOM self-assembly, resulting in optical and chemical fractionation. The relative DOC loading (DOCload) was used to assess the carbon loading during SPE, and a double sigmoid model was applied to our online permeate fluorescence data as a function of DOCload, which allowed us to assess the degree of variability induced by DOCload. This finding has ample implications for the future processing and previous interpretation of chemical characteristics in SPE-DOM of aquatic organic matter. For the second part of the thesis, original water samples were acquired from the “Multidisciplinary Drifting Observatory for the Study of Arctic Climate” (MOSAiC) expedition. The water column samples covered a full year (2019 / 2020) and included the regions Amundsen Basin, western Nansen Basin and Yermak Plateau and Fram Strait. Samples were analyzed using optical spectroscopy to determine chromophoric DOM (CDOM) and fluorescent DOM (FDOM). In addition, a new method was applied that used Fourier transform ion cyclotron resonance mass spectrometry hyphenated to high performance liquid chromatography (LC-FTMS). The method allowed DOM analysis in original filtered water and thus avoided the chemical fractionation introduced by SPE. During the MOSAiC expedition, DOC concentrations and CDOM characteristics in the water column were primarily influenced by regional differences. These differences were largely dependent on terrestrially-derived DOM (tDOM) input by the transpolar drift (TPD) as indicative of average 136% and 45% higher aCDOM(350) and DOC concentration, respectively, in the Amundsen compared to the western Nansen Basin and Yermak Plateau, and slightly modified by seasonal changes. Despite the convenient identification of tDOM, optical spectroscopy was not suitable to quantify the contribution of tDOM to bulk DOC or to track sea ice derived DOM in the water column. In contrast, using LC-FTMS, we found quantitative linear correlation between the summed mass peak magnitudes for each sample (intsum) and DOC concentration. By combing LC-FTMS and source identification with optical parameters, we were able to quantify DOM sources (terrestrial versus marine) in the water column: 83% of the summed peak magnitude of all samples could be related to marine or terrestrial sources. tDOM contributed ∼17% (or 8 μmol kg-1) to deep DOC (~2000 m) in the CAO and was more refractory and had a higher state of unsaturation compared to marine DOM. The quantitative characterization of DOM in original seawater from different origin is a major step in the field of research. It provides a unique and new insight into the molecular changes in marine DOM composition and an improved understanding of the terrestrial DOM distribution in the CAO.

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 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 Modeling of Atmospheric Aerosols written by Wei Lin and published by . This book was released on 2014 with total page 202 pages. Available in PDF, EPUB and Kindle. Book excerpt: Aerosols are tiny particles suspended in the atmosphere, which can directly be generated by biogenic and anthropogenic processes or be formed through nucleation of gas-phase species. Aerosols influence the chemical composition of the atmosphere, and have both direct and indirect effects on the Earth's radiative balance. These processes have major implications for climate, ecosystems, and public health. In this dissertation, we first discuss computational studies aimed at providing fundamental insights into the molecular mechanisms of aerosol nucleation through the characterization of structural, thermodynamic, and spectroscopic properties of important nucleation species, with a particular focus on HCl(H2O)n and HSO4−(HO2C(CH2)2CO2H)n binary systems. We then describe the development and application of molecular models for characterizing proton transfer and transport in water and ice. In particular, we use computer simulations with our improved multistate empirical valence bond models to characterize the mechanisms responsible for proton mobility in ice Ih as well as on the surface of both ice Ih and amorphous ice. Based on our simulation results, we thus develop a unified picture of proton transfer and transport in and on ice. The last part of this dissertation focuses on the properties of sea spray particles, which represent one of the most important components of biogenic aerosols. Field measurements have demonstrated that sea-spray particles contain a large fraction of organic material, which correlates with the extent of biological activity at the surface microlayer of the ocean. In this context, we perform molecular dynamics simulations to characterize the properties of model sea-spray aerosol surfaces. Specifically, we study the phase behavior and structural properties of three Langmuir monolayers (palmitic acid, dipalmitoyl phosphatidic acid, and Lipid-A) at the air/water interface. Through a detailed analysis of the molecular dynamics trajectories, direct connections between order/disorder transitions of the Langmuir monolayers and water structure/dynamics are determined as a function of surface pressure and structural complexity of the monolayers. Our results provide key molecular-level insights into the physical behavior of organic material at aqueous interfaces which can help understand the reactivity and nucleation properties of sea-spray aerosols.

Download or read book Chemistry of Secondary Organic Aerosol written by Lindsay Diana Yee and published by . This book was released on 2013 with total page 466 pages. Available in PDF, EPUB and Kindle. Book excerpt: The photooxidation of volatile organic compounds (VOCs) in the atmosphere can lead to the formation of secondary organic aerosol (SOA), a major component of fine particulate matter. Improvements to air quality require insight into the many reactive intermediates that lead to SOA formation, of which only a small fraction have been measured at the molecular level. This thesis describes the chemistry of secondary organic aerosol (SOA) formation from several atmospherically relevant hydrocarbon precursors. Photooxidation experiments of methoxyphenol and phenolic compounds and C12 alkanes were conducted in the Caltech Environmental Chamber. These experiments include the first photooxidation studies of these precursors run under sufficiently low NOx levels, such that RO2 + HO2 chemistry dominates, an important chemical regime in the atmosphere. Using online Chemical Ionization Mass Spectrometery (CIMS), key gas-phase intermediates that lead to SOA formation in these systems were identified. With complementary particle-phase analyses, chemical mechanisms elucidating the SOA formation from these compounds are proposed. Three methoxyphenol species (phenol, guaiacol, and syringol) were studied to model potential photooxidation schemes of biomass burning intermediates. SOA yields (ratio of mass of SOA formed to mass of primary organic reacted) exceeding 25% are observed. Aerosol growth is rapid and linear with the organic conversion, consistent with the formation of essentially non-volatile products. Gas and aerosol-phase oxidation products from the guaiacol system show that the chemical mechanism consists of highly oxidized aromatic species in the particle phase. Syringol SOA yields are lower than that of phenol and guaiacol, likely due to unique chemistry dependent on methoxy group position. The photooxidation of several C12 alkanes of varying structure n-dodecane, 2-methylundecane, cyclododecane, and hexylcyclohexane) were run under extended OH exposure to investigate the effect of molecular structure on SOA yields and photochemical aging. Peroxyhemiacetal formation from the reactions of several multifunctional hydroperoxides and aldehyde intermediates was found to be central to organic growth in all systems, and SOA yields increased with cyclic character of the starting hydrocarbon. All of these studies provide direction for future experiments and modeling in order to lessen outstanding discrepancies between predicted and measured SOA.

Download or read book Linking Optical and Chemical Properties of Dissolved Organic Matter in Natural Waters written by Christopher L. Osburn and published by Frontiers Media SA. This book was released on 2017-01-17 with total page 244 pages. Available in PDF, EPUB and Kindle. Book excerpt: A substantial increase in the number of studies using the optical properties (absorbance and fluorescence) of dissolved organic matter (DOM) as a proxy for its chemical properties in estuaries and the coastal and open ocean has occurred during the last decade. We are making progress on finding the actual chemical compounds or phenomena responsible for DOM’s optical properties. Ultrahigh resolution mass spectrometry, in particular, has made important progress in making the key connections between optics and chemistry. But serious questions remain and the last major special issue on DOM optics and chemistry occurred nearly 10 years ago. Controversies remain from the non-specific optical properties of DOM that are not linked to discrete sources, and sometimes provide conflicting information. The use of optics, which is relatively easier to employ in synoptic and high resolution sampling to determine chemistry, is a critical connection to make and can lead to major advances in our understanding of organic matter cycling in all aquatic ecosystems. The contentions and controversies raised by our poor understanding of the linkages between optics and chemistry of DOM are bottlenecks that need to be addressed and overcome.

Download or read book Insights Into Predicting Secondary Organic Aerosol Formation from Anthropogenic Volatile Organic Compounds written by Lijie Li and published by . This book was released on 2016 with total page 274 pages. Available in PDF, EPUB and Kindle. Book excerpt: Understanding secondary organic aerosol (SOA) formation is of critical importance to public health and global climate. SOA formation from anthropogenic volatile organic compounds (VOCs) is influenced by NO, precursor molecular structure, oxidation conditions and other factors. This dissertation explores the impact of NO effect and molecular structure for two categories of VOCs at urban atmosphere relevant conditions by utilizing the state of art 90 m3 UCR/CE-CERT chamber facilities.

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.

Download or read book From Freshly Produced Compounds to Refractory Molecules written by and published by . This book was released on 2014 with total page 153 pages. Available in PDF, EPUB and Kindle. Book excerpt: This thesis includes the results of two field studies and one laboratory incubation experiment focusing on the production and turnover of freshly produced dissolved organic matter (DOM) by microorganisms. High resolution methods were applied to elucidate the DOM molecular composition and the microbial community structure, and the data was analyzed via multivariate statistics to provide novel insights into the relationship between the two key players. Main findings include 1. DOM in high latitude environments is rapidly transformed due to microbial activity, 2. the North Sea is highly impacted by the input of terrigenous DOM and the molecular DOM composition can be connected with the composition of the total and the active microbial community, and 3. refractory deep ocean-like DOM may be biologically produced by microorganisms in the laboratory within several weeks. engl.

Download or read book High Molecular Weight HMW Dissolved Organic Matter DOM in Seawater written by Lihini I. Aluwihare and published by . This book was released on 1999 with total page 436 pages. Available in PDF, EPUB and Kindle. Book excerpt: The goal of this thesis was to use high resolution analytical techniques coupled with molecular level analyses to chemically characterize high molecular weight (> 1 k Da (HMW)) dissolved organic matter (DOM) isolated from seawater in an attempt to provide new insights in to the cycling of DOM in the ocean. While a variety of sites spanning different environments (fluvial, coastal and oceanic) and ocean basins were examined, the chemical structure of the isolated HMW DOM varied little at both the polymer and monomer levels. All samples show similar ratios of carbohydrate:acetate:lipid carbon (80±4:10±2:9±4) indicating that these biochemicals are present within a family of related polymers. The carbohydrate fraction shows a characteristic distribution of seven major neutral monosaccharides: rhamnose, fucose, arabinose, xylose, mannose, glucose and galactose; and additionally contains Nacetylated amino sugars as seen by Nuclear Magnetic Resonance Spectroscopy (NMR). This family of compounds, consisting of a specifically linked polysaccharide backbone that is acylated at several positions, has been termed acylated polysaccharides (APS) by our laboratory. APS accounts for 50% of the carbon in HMW DOM isolated from the surface ocean and 20% of the carbon in HMW DOM isolated from the deep ocean. In order to identify a possible source for APS three species of phytoplankton, Thalassiossira weissflogii, Emiliania huxleyi and Phaeocystis, were cultured in seawater and their HMW DOM exudates examined by variety of analytical techniques. Both the T. weissflogii and E. huxleyi exudates contain compounds that resemble APS indicating that phytoplankton are indeed a source of APS to the marine environment. Furthermore, the degradation of the T. weissflogii exudate by a natural assemblage of microorganisms indicates that the component resembling APS is more resistant to microbial degradation compared to other polysaccharides present in the culture. Molecular level analyses show the distribution of monosaccharides to be conservative in surface and deep waters suggesting that APS is present throughout the water column. In order to determine the mechanism by which APS is delivered to the deep ocean the [delta]14C value of APS in the deep ocean was compared to the A14C value of the dissolved inorganic carbon (DIC) at the same depth. If the formation of deep water is the dominant mode of transport then both the DIC and APS will have similar [delta]14C values. However, if APS is injected into the deep ocean from particles or marine snow then the [delta]14C value of APS will be higher than the DIC at the same depth. Our results indicate that APS in the deep Pacific Ocean carries a modem [delta]14C value and is substantially enriched in 14C relative to the total HMW DOM and the DIC at that depth. Thus, particle dissolution appears to be the most important pathway for the delivery of APS to the deep ocean.

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 The Influence of Dissolved Organic Matter Composition on Its Reactivity in Natural and Engineered Systems written by Reid Milstead and published by . This book was released on 2023 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: Dissolved organic matter (DOM) is a complex heterogeneous mixture of organic compounds that is found in all water systems. DOM is derived from both terrestrial and microbial sources. The composition of DOM can vary greatly depending on a number of variables, including time of year, surrounding groundcover type, and water column depth. The characterization of DOM composition is increasingly performed using high-resolution mass spectrometry, although different instrumentation and techniques may yield different results. Importantly, DOM plays a key role in a number of chemical processes in both natural and engineered systems, such as the generation of carbon dioxide (CO2) from surface waters, the degradation of aquatic contaminants, and the formation of disinfection byproducts (DBPs) during drinking water treatment. The composition of DOM determines its reactivity in all of these processes. Using both bulk and high-resolution analytical techniques, the photooxidation of DOM can be explored. DOM compounds that are more oxidized and aromatic tend to be associated with the consumption of oxygen and the production of CO2. Bulk scale measurements show that DOM becomes less aromatic and lower in molecular weight as a result of partial photooxidation. High-resolution mass spectrometry also provides evidence of oxygen addition and the loss of CO2 from DOM during irradiation experiments. However, the chemical formulas that are most photolabile vary depending on the initial composition of DOM. Using light exposure experiments the kinetics of degradation of four contaminants were quantified for a large set of diverse waters. Using this information, we evaluated the relationships between indirect photolysis rate constants and the formation of photochemically produced reactive intermediates (PPRI) using linear regression analysis. Additionally, quencher experiments were performed to identify the PPRI associated with the degradation of each contaminant in all waters. Triplet state DOM (3DOM) and singlet oxygen (1O2) were identified as critical for atorvastatin, carbamazepine, and sulfadiazine, while hydroxyl radical (•OH) is important for benzotriazole. Our results suggest that quenching experiments should be used with caution due to the non-targeted nature of quenching compounds and the interconnection of PPRI. All of these factors result in probe compounds possibly overstating the importance of PPRI in the indirect photolysis of common contaminants. The characterization of DOM in drinking waters reveals a high degree of variability in DOM composition and reactivity with chlorine, particularly in groundwater samples. Despite the variability in DOM composition, novel DBPs with up to three halogen substituents are compositionally similar among all waters. These novel DBPs are positively correlated with trihalomethane and, to a lesser extent, the formation of haloacetonitriles. This suggests that some low molecular weight DBPs and novel DBPs detected via high-resolution mass spectrometry share similar aromatic precursors, providing evidence that low molecular weight DBPs are useful proxies for the formation of unknown, unidentified high molecular weight DBPs. Compared to Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS), Orbitrap MS yields significantly fewer formula matches and appears to have a bias towards sulfur-containing formulas and against nitrogen-containing formulas. Additionally, the choice of calibration method is particularly important for the less powerful Orbitrap MS. The matched formulas yielded from Orbitrap MS tend to be more oxidized and less highly saturated than those yielded by FT-ICR MS. Despite these differences, the formulas produced by both instruments tend to yield similar relative differences between samples, suggesting that Orbitrap MS is an acceptable replacement for FT-ICR MS in some cases.