Investigation of Fundamental Processes Governing Secondary Organic Aerosol Formation in Laboratory Chambers

Investigation of Fundamental Processes Governing Secondary Organic Aerosol Formation in Laboratory Chambers

Author: Xuan Zhang

Publisher:

Published: 2015

Total Pages: 562

ISBN-13:

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Our understanding of the processes and mechanisms by which secondary organic aerosol (SOA) is formed is derived from laboratory chamber studies. In the atmosphere, SOA formation is primarily driven by progressive photooxidation of SOA precursors, coupled with their gas-particle partitioning. In the chamber environment, SOA-forming vapors undergo multiple chemical and physical processes that involve production and removal via gas-phase reactions; partitioning onto suspended particles vs. particles deposited on the chamber wall; and direct deposition on the chamber wall. The main focus of this dissertation is to characterize the interactions of organic vapors with suspended particles and the chamber wall and explore how these intertwined processes in laboratory chambers govern SOA formation and evolution. A Functional Group Oxidation Model (FGOM) that represents SOA formation and evolution in terms of the competition between functionalization and fragmentation, the extent of oxygen atom addition, and the change of volatility, is developed. The FGOM contains a set of parameters that are to be determined by fitting of the model to laboratory chamber data. The sensitivity of the model prediction to variation of the adjustable parameters allows one to assess the relative importance of various pathways involved in SOA formation. A critical aspect of the environmental chamber is the presence of the wall, which can induce deposition of SOA-forming vapors and promote heterogeneous reactions. An experimental protocol and model framework are first developed to constrain the vapor-wall interactions. By optimal fitting the model predictions to the observed wall-induced decay profiles of 25 oxidized organic compounds, the dominant parameter governing the extent of wall deposition of a compound is identified, i.e., wall accommodation coefficient. By correlating this parameter with the molecular properties of a compound via its volatility, the wall-induced deposition rate of an organic compound can be predicted based on its carbon and oxygen numbers in the molecule. Heterogeneous transformation of delta-hydroxycarbonyl, a major first-generation product from long-chain alkane photochemistry, is observed on the surface of particles and walls. The uniqueness of this reaction scheme is the production of substituted dihydrofuran, which is highly reactive towards ozone, OH, and NO3, thereby opening a reaction pathway that is not usually accessible to alkanes. A spectrum of highly-oxygenated products with carboxylic acid, ester, and ether functional groups is produced from the substituted dihydrofuran chemistry, thereby affecting the average oxidation state of the alkane-derived SOA. The vapor wall loss correction is applied to several chamber-derived SOA systems generated from both anthropogenic and biogenic sources. Experimental and modeling approaches are employed to constrain the partitioning behavior of SOA-forming vapors onto suspended particles vs. chamber walls. It is demonstrated that deposition of SOA-forming vapors to the chamber wall during photooxidation experiments can lead to substantial and systematic underestimation of SOA. Therefore, it is likely that a lack of proper accounting for vapor wall losses that suppress chamber-derived SOA yields contribute substantially to the underprediction of ambient SOA concentrations in atmospheric models.


Chemistry of Secondary Organic Aerosol

Chemistry of Secondary Organic Aerosol

Author: Lindsay Diana Yee

Publisher:

Published: 2013

Total Pages: 466

ISBN-13:

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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.


Secondary Organic Aerosol Formation from Radical-initiated Reactions of Alkenes

Secondary Organic Aerosol Formation from Radical-initiated Reactions of Alkenes

Author: Aiko Matsunaga

Publisher:

Published: 2009

Total Pages: 289

ISBN-13:

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The products and mechanisms of secondary organic aerosol (SOA) formation from reactions of 1-alkenes, internal alkenes, and 2-methyl-1-alkenes with OH radicals in the presence of NO[subscript x] were investigated in an environmental chamber and the results used to develop quantitative models for SOA formation. Aerosol chemical composition was analyzed using a thermal desorption particle beam mass spectrometer (TDPBMS), and multifunctional organic nitrate products were quantified using a high-performance liquid chromatograph with UV-vis detector and identified using the TDPBMS and 1H NMR. The major products observed in reactions of linear alkenes were [beta]-hydroxynitrates, dihydroxynitrates, cyclic hemiacetals, dihydrofurans, and dimers formed from dihydroxycarbonyls. Trihydroxynitrates and trihydroxycarbonyls were observed in reactions of 2-methyl-1-alkenes, in addition to the products listed above. Dimers were not observed, apparently because electron donation by the additional methyl group (compared to linear 1-alkenes) reduces the driving force for hemiacetal formation. The measured yields of [beta]-hydroxynitrates, dihydroxynitrates, and trihydroxynitrates were used to calculate relative ratios of 1.0:1.9:4.3 for forming primary, secondary, and tertiary [beta]-hydroxyalkyl radicals by OH radical addition to the C=C double bond, and branching ratios of 0.12, 0.15, and 0.25 for forming [beta]-hydroxynitrates from reactions of primary, secondary, and tertiary â-hydroxyperoxy radicals with NO. The trends are consistent with expected relative stabilities of [beta]-hydroxyalkyl radicals and ß-hydroxyperoxy radical-NO complexes. It should be possible to use these values to estimate product yields from similar reactions of other alkenes. Comparison of measured and model-calculated SOA yields showed that in some cases the models provide accurate predictions of SOA yields, but that uncertainties in gas- and particle-phase chemistry and gas-particle partitioning can lead to significant discrepancies. More limited environmental chamber studies were also carried out on SOA formation from reactions of linear alkenes with NO3 radicals. The major products were [beta]-hydroxynitrates, [beta]-carbonylnitrates, dihydroxynitrates, and hydroxy- and oxo- dinitrooxytetrahydrofurans, which had not been observed previously. It was observed that isomerization of [delta]-hydroxycarbonyls to cyclic hemiacetals, followed by dehydration to highly reactive dihydrofurans that can be further oxidized, can be important sources of SOA from reactions of alkenes with OH and NO3 radicals.


Secondary Organic Aerosol Formation Indoors

Secondary Organic Aerosol Formation Indoors

Author: Chunyi Wang

Publisher:

Published: 2019

Total Pages: 372

ISBN-13:

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People in developed countries spend about 90% of their time indoors, so controlling in-door air quality (IAQ) is of primary importance for not harming public health. Airborne particu-late matter (PM) is one of the most problematic pollutants indoors, since exposure to particles with aerodynamic diameters smaller than 2.5 Îơm (i.e, PM2.5) is associated with respiratory dis-eases, as well as morbidity and mortality outcomes. Organic aerosol components, so called organic aerosol (OA), generally comprise the ma-jor portion of indoor PM, owing to its large indoor emission. One important component of OA indoors is secondary organic aerosol (SOA), which are condensed phase particles composed of semi- and low-volatility compounds. Most research has focused on SOA generated by terpene ozonolysis occurring in the gas phase. This work, however, explores a lesser researched for-mation mechanism, which is the possibility of airborne SOA generated by ozone surface reac-tions with sorbed squalene (C30H50), which is a nonvolatile constituent of skin oil. As such, thirteen steady state chamber experiments were performed to measure the SOA formation en-tirely initiated by ozone reactions with squalene sorbed to glass at two RH conditions of 21% and 51%, in the absence of seed particles. SOA was initiated from these surface reactions, and all experiments but one exhibited nucleation and mass formation. Mass formation increased with ozone concentration at RH = 51% while nucleation was more obvious at RH = 21%. Additionally, most indoor OA, either emitted or generated (i.e., not only SOA), is at composed of semivolatile compounds (SVOCs) in a state of dynamic equilibrium between gas and particle phases. Filters might have a reduced efficiency on removing these kinds of particles since they coexist in gas and condensed aerosol phases. The preferential filtration of particle phase material of the OA system could disrupt the equilibrium, and the removed aerosols might be enhanced by desorption from surfaces and repartitioning from gas phase. To explore this phenomenon, three types of particles, including non-volatile ammonium sulfate ((NH4)2SO4) aerosol, incense aerosol (which might be partly semi-volatile), and SOA derived from ozone + d-limonene reactions (the majority of which are SVOCs), were characterized and compared in terms of their effective removal by a portable air cleaner. For this comparison, the metric of the Clean Air Delivery Rate, CADR (m3/h), was used, which is the volumetric flow of pollutant-free air produced by an air cleaner. Results demonstrated that the lowest effective CADR was for SOA, followed by the incense, and then the ammonium sulfate particles, indicating a repar-titioning processes reduced the filter efficiency. Then a model based on the principles of desorp-tion and repartition process was developed, to quantify the reduced CADR as a function of par-ticle concentration and distribution, in terms of parameter ATSP, which is the ratio of particle surface area to mass. Finally, the influence of the above two parameters on amount of CADR reduction was discussed. Using some details gleaned from the above two experimental studies, a thermodynamic equilibrium model was developed using the volatile basis set (VBS), to predict indoor organic aerosol concentrations and behavior. The model outcomes are the total organic mass indoors (gas + condensed phase), and the fraction of it that partitions to the aerosol phase, including that existing as SOA formed by ozone + d-limonene reactions. With this model, the total OA concentration was simulated at key locations in an indoor environment, such as in the occupied space and different positions in a building mechanical system. The impacts of different condi-tions were compared, including commercial against residential buildings, surface against gas reactions, and winter against summer, within a Monte Carlo framework. Indoor OA concentra-tion indoors were higher when reactions were involved, and gas phase reactions had much more influence on SOA than surface reactions. Finally, the result dataset was used to evaluate the influence of key factors on the indoor OA concentrations, using multiple linear regression sen-sitivity methods. The most important factor that enhanced indoor particles was d-limonene emission rate with average SRC of 0.73, while the negative related factors were filtration effi-ciency with SRC of -0.33 for commercial and surface deposition rate with SRC of -0.22 for resi-dential buildings. Beyond the three SOA studies discussed above, humidifiers used indoors might be strong PM emitters. So, as a supplementary piece, this work also investigated the influence of three humidifier types (ultrasonic, evaporative, and steam humidifiers), and water type used (tap water, de-ionized (DI) water or distilled water), on indoor aerosol number/mass concentra-tions by performing 16 experiments. Particle size distribution during emission periods and size-resolved emission rates were explored to compare the emission ability of humidifiers. Two lung deposition models were also applied to simulate the deposition percentage of particles breathed in on three lung regions (HA, TB, and AL), and total percentage on varying age groups. Results showed that two year-old group was most vulnerable, with number deposition fractions of 0.36, compared with 0.25 for adults. Furthermore, roughly 70% of the total emitted particles pene-trates into the AL region of the lung.


Impacts of Controlling Reactivity and Temperature on Advanced Study of Secondary Organic Aerosol Formation

Impacts of Controlling Reactivity and Temperature on Advanced Study of Secondary Organic Aerosol Formation

Author: Mary Elizabeth Kacarab

Publisher:

Published: 2016

Total Pages: 131

ISBN-13: 9781369088045

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Secondary organic aerosol (SOA) is formed via the oxidation of volatile organic compounds emitted to the atmosphere from both biogenic and anthropogenic sources. Due to the complexity of atmospheric composition and range of ambient conditions, aerosol models, which are mostly based off observed yields from controlled laboratory chamber experiments, greatly underestimate global SOA formation. To increase the understanding of the formation and properties of ambient SOA, it is imperative to explore ways to improve the complexity of chamber studies while still maintaining a level of control not found outside of the laboratory.


Secondary Organic Aerosol Formation Initiated by Îł-Terpineol Ozonolysis and Exposure Quantified by the Secondary Intake Fraction

Secondary Organic Aerosol Formation Initiated by Îł-Terpineol Ozonolysis and Exposure Quantified by the Secondary Intake Fraction

Author: Yanan Yang

Publisher:

Published: 2017

Total Pages: 338

ISBN-13:

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Indoor air quality (IAQ) is associated with human health due to people spending most of their time indoors. Secondary organic aerosol (SOA) formation is an important source of fine airborne particles, which can cause acute airway effects and decreased lung function. SOA is a product of reactive organic gas (ROG) ozonolysis, which can be parameterized by the aerosol mass fraction (AMF). The AMF is the ratio of SOA formation mass to the reacted ROG mass, and it is positively correlated with the total organic aerosol mass concentration. Îł-Terpineol is a terpenoid that can have a strong emission rate indoors owing to consumer product usage. It reacts strongly with oxidants such as ozone, hydroxyl radical (OH), and nitrate radical (NO3), where those radicals are produced indoors due to ozone reaction with alkenes or nitrogen dioxide (NO2), respectively. Due to the fast reaction rates of Îł-terpineol with these oxidants, SOA formation has the potential to increase in-door fine particle concentrations. However, SOA formation from Îł-terpineol has not been systematically quantified. Therefore, the purpose of this work was to quantify SOA formation owing to Îł-terpineol ozonolysis, for two sets of experiments, one without and one with NO2 present. In the first set of 21 experiments, the SOA formation initiated by reacting 6.39 to 226 ppb Îł-terpineol with high ozone (~25 ppm) to ensure rapid and complete ozonolysis for high (0.84 h8́21), moderate (0.61 h8́21) and low (0.36 h8́21) air exchange rates (AER) was studied in a stainless steel chamber system. The resulting SOA mass formation was parameterized with the AMF for all experiments. The impact of reacted Îł-terpineol and AERs on AMFs as well as the SOA size distribution was investigated, and different AMF models (one-product, two-product, and volatility basis set) were fit to the AMF data. Predictive modeling investigated the impact of the SOA formation from Îł-terpineol ozonolysis in residential indoor air. Furthermore, a second set of 21 experiments in a Teflon bag operated as semi-batch reactor explored the impact of NO2 at 0 to 2000 ppb on SOA formation from Îł-terpineol ranging from 20 ppb to 200 ppb with excess ozone (~25ppm). In this system, ozone can either initiate reactions with Îł-terpineol to produce organic peroxy radicals (RO28́9) or react with NO2 to produce NO3, which can react with Îł-terpineol. For analysis of results, we classified experiments by logarithmic spacing into four groups according to the initial ratio of VOC/NO2 values. SOA mass was again parameterized by the AMF as a function of the organic aerosol concentration. The impact of VOC/NO2 on SOA mass as well as the SOA size distribution was investigated, and the SOA composition for each grouping of experiments was elucidated by the kinetic modeling. Finally, this SOA formation was put into context using the 'secondary intake fraction' (siF), which is a developed metric that evaluates SOA exposure during various human activities. The siF is defined as the up-taken mass of a secondary product for an exposed individual per unit mass of primary product emitted during human residential activities, over a given exposure time. The siF for individual intake was evaluated for SOA formation from d-limonene, Îł-terpineol, or Îł-pinene ozonolysis in five residential scenarios, including: I. Constant emission, II. Pulse emission, III. Surface cleaning, IV. Solution cleaning, and V. Skin cleaning. For a given input set, a transient model was used to predict SOA concentrations and the siF, using inputs cast as probability distributions within a Monte Carlo approach. Multiple linear regression techniques were applied to fit siF values for the five scenarios, for use in sensitivity analyses. Also, the multiple linear regression results can be used to predict the siF and the potential for human intake of SOA within exposure models.