Secondary Organic Aerosol Formation and Gas/aerosol Partitioning PDF Download
Are you looking for read ebook online? Search for your book and save it on your Kindle device, PC, phones or tablets. Download Secondary Organic Aerosol Formation and Gas/aerosol Partitioning PDF full book. Access full book title Secondary Organic Aerosol Formation and Gas/aerosol Partitioning by Jay Russell Odum. Download full books in PDF and EPUB format.
Author: Jay Russell Odum
Publisher:
ISBN:
Category : Electronic dissertations
Languages : en
Pages : 246
Get Book Here
Book Description
Author: Jay Russell Odum
Publisher:
ISBN:
Category : Electronic dissertations
Languages : en
Pages : 246
Get Book Here
Book Description
Author: Chen Wang
Publisher:
ISBN:
Category :
Languages : en
Pages :
Get Book Here
Book Description
A sound parameterization of the gas-particle partitioning process is essential for understanding and quantifying secondary organic aerosol (SOA) formation. This thesis aimed to improve the understanding and description of phase partitioning during SOA formation through a combination of both laboratory and modeling studies. Partitioning of organic compounds between gas and particle phase is influenced by the presence of a large quantity of inorganic salts in aerosol, which is known as the salt effect. The salt effects of atmospherically relevant inorganic salts for a large number of organic compounds with various functional groups were measured in this study. The results revealed the importance of both salt species and organic compound identities on the salt effect, with the former as the dominant determinant. Models in predicting salt effect were calibrated and evaluated using the experimental data. Salt effect in mixtures was also investigated, which assists the understanding of salt effect in mixture salt solutions, including aerosols. A new approach for predicting gas-particle partitioning during SOA formation based on quantum chemical calculations was presented, which considers the partitioning species explicitly and captures the dynamic aspects of the aerosol formation processes. The role of different atmospheric parameters and chemical properties (organic loading, liquid water content, salinity, chemical ageing, etc.) was investigated and compared. Performance of the model was found to be comparable to the best currently used group contribution methods. SOA formation from constant emission and oxidation of precursor compounds was simulated to resemble the realistic scenario in the ambient atmosphere. The differential yield that describes the amount of SOA formed from a certain amount of added oxidation products was introduced, which is more relevant for SOA formation in the ambient atmosphere. The necessity of considering kinetic processes in addition to the thermodynamic equilibrium process was also discussed.
Author: Xuan Zhang
Publisher:
ISBN:
Category : Electronic dissertations
Languages : en
Pages : 562
Get Book Here
Book Description
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.
Author: Wayne Li-wen Chang
Publisher:
ISBN: 9781124791869
Category :
Languages : en
Pages : 89
Get Book Here
Book Description
The detrimental impact on both human health and global climate of atmospheric particular matter (PM) is now well-established. Among the various classifications of PM, a significant portion is comprised of secondary organic aerosol (SOA). Despite its importance, there are still much uncertainty regarding the formation and evolution of SOA in the atmosphere, beginning with the oxidation of organic gases that leads to semi-volatile and low volatility products. The need to further improve the current knowledge SOA is made apparent by the observed large discrepancy between model predictions and field measurements of SOA. Proposed explanations behind the orders of magnitude underprediction of ambient SOA levels by state-of-the-art airshed models include: missing particle-forming oxidized organic products, unidentified SOA precursor emissions, and issues related to the fundamentals of current SOA partition theory, all of which are considered in this study to develop corresponding improvements to the latest airshed models. The model used in this study is the UCI-CIT airshed model, and the improvement scenario tests are set in the urban region of South Coast Air Basin of California. Recent chamber results have shown that the original implementation of alkane-derived SOA provided an underestimate for what was likely to be occurring in urban atmospheres. Thus, the original chemical mechanism is revised to include higher generation products of medium- and long-chain alkanes that can contribute to SOA in this study. Primary organic aerosol (POA) has been identified to be able to evaporate with dilution; therefore, test cases are developed that treat fractions of POA as semi-volatile, a source of SOA, rather than nonvolatile. While current atmospheric models assume that SOA are liquids into which semi-VOCs undergo equilibrium partitioning and grow the particles, recent laboratory and field experiments have shown otherwise. Hence, a new kinetics-driven partition theory is developed and analyzed against the original formulations. The results from the expanded chemical mechanism to include higher-generation products of alkane in the atmosphere shows that only the tetrahydrofurans will contribute to SOA and those contributions are only a small fraction compared to other SOA sources in the model, contrary to the prediction made based on chamber experiments and box models. In the tests for redistribution of POA as gas-phase parent VOCs sources, POA decreased with no commensurate increase in SOA. This is essentially due to the fact that the amount of mass that the POA can contribute is a small fraction of that already in the gas-phase parent VOC pool. Finally, using the newly developed kinetically determined SOA growth mechanism, to achieve the same level of predicted SOA levels as the original equilibrium approach requires 40-50% of SOA parent species to be allocated to the particle phase. The new formulation of SOA partition behavior based on kinetics will require the measurement of new input data and the corresponding parameterization for models in the future. The implication of this new approach should demand wider attention from the community.
Author: Chunyi Wang
Publisher:
ISBN:
Category : Aerosols
Languages : en
Pages : 372
Get Book Here
Book Description
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.
Author: Christopher James Hennigan
Publisher:
ISBN:
Category : Air
Languages : en
Pages :
Get Book Here
Book Description
This thesis characterizes properties of ambient secondary organic aerosol (SOA), an important and abundant component of particulate matter. The findings presented in this thesis are significant because they represent the results from ambient measurements, which are relatively scarce, and because they report on properties of SOA that, until now, were highly uncertain. The analyses utilized the fraction of particulate organic carbon that was soluble in water (WSOCp) to approximate SOA concentrations in two largely different urban environments, Mexico City and Atlanta. In Mexico City, measurements of atmospheric gases and fine particle chemistry were made at a site ~ 30 km down wind of the city center. Using box model analyses and a comparison to ammonium nitrate aerosol, a species whose thermodynamic properties are generally understood, the morning formation and mid-day evaporation of SOA are investigated. In Atlanta, simultaneous measurements of WSOCp and water-soluble organic carbon in the gas phase (WSOCg) were carried out for an entire summer to investigate the sources and partitioning of WSOC. The results suggest that both WSOCp and WSOCg were secondary and biogenic, except possibly in several strong biomass burning events. The gas/particle partitioning of WSOC in Atlanta was investigated through the parameter, Fp, which represented the fraction of WSOC in the particle phase. Factors that appear to influence WSOC partitioning in Atlanta include ambient relative humidity and the WSOCp mass concentration. There was also a relationship between the NOx concentration and Fp, though this was not likely related to the partitioning process. Temperature did not appear to impact Fp, though this may have been due to positive relationships WSOCp and WSOCg each exhibited with temperature. Neither the total Organic Carbon aerosol mass concentration nor the ozone concentration impacted WSOC partitioning.
Author: Chen Song
Publisher:
ISBN:
Category : Aerosols
Languages : en
Pages : 532
Get Book Here
Book Description
Author: Emma Louise D'Ambro
Publisher:
ISBN:
Category :
Languages : en
Pages : 129
Get Book Here
Book Description
Author: Bethany A. Warren
Publisher:
ISBN:
Category : Aerosols
Languages : en
Pages : 414
Get Book Here
Book Description
Author: Yunliang Zhao
Publisher:
ISBN:
Category :
Languages : en
Pages : 96
Get Book Here
Book Description
Understanding organic aerosol (OA) sources and secondary OA (SOA) formation is crucial to elucidate their human health and climate change effects, but has been limited by lack of instrumentation capable of in-situ measurements of organic speciation in the atmosphere across the vapor pressure range of semi-volatile organic compounds (SVOCs) and OA. This dissertation describes 1) the development of a novel instrument based on a thermal desorption aerosol gas chromatograph (TAG), called semi-volatile TAG (SV-TAG) which enables quantitative measurements of specific chemical tracers in SVOCs and OA and 2) application of this new instrument to investigate the various source contributions to OA and SOA formation. The development of the SV-TAG was initiated by employing a denuder difference method to improve the capability of the TAG for quantitative gas/particle separation. Using this technique, hourly time resolution in-situ measurements of organic species were made and then used to investigate the pathways of gas-to-particle partitioning for oxygenated compounds and particle-phase organics were used for source apportionment calculations. The measurements of gas/particle partitioning of phthalic acid, pinonaldehyde and 6, 10, 14-trimethyl-2-pentadecanone were explored to elucidate the pathways of gas-to-particle partitioning whereby SOA was formed. The observations show that multiple pathways of gas-to-particle partitioning contribute to formation of SOA in the atmosphere and the dominance of different pathways are compound-dependent. Absorption into particles is shown to be the dominant pathway for 6, 10, 14-trimethyl-2-pentadecanone to contribute to SOA in Bakersfield, CA. The major pathway to form particle-phase phthalic acid is likely attributed to formation of condensable salts through reactions between phthalic acid and gas-phase ammonia. The observations of pinonaldehyde in particles while inorganic acids in particles were fully neutralized suggest that the occurrence of reactive uptake of pinonaldehyde onto particles does not require the presence of inorganic acids. The relationship between particle-phase pinonaldehyde and RH suggests that aerosol water content plays a significant role in the formation of particle-phase pinonaldehyde. To investigate the contributions of various sources to OA in Bakersfield, CA, positive matrix factorization (PMF) analysis was performed on a subset of the measured particle-phase organic compounds. Six OA source factors were identified, including one representing primary organic aerosol (POA), four different types of secondary organic aerosol (SOA) representing local, regional, and nighttime production, and one representing a complex mixture of additional OA sources that were not further resolvable. POA accounted for 15% of OA on average with a significant contribution from local vehicles. SOA was the dominant contributor to OA, accounting for on average 72% of OA. The rest of OA was unresolved as a mixture of OA sources. Both local and regional SOA had a significant contribution to OA during the day but regional SOA was the largest contributor to OA during the afternoon. SOA formed from the oxidation of biogenic SOA precursors substantially contributed to OA at night. The absorption of organic compounds into particles is suggested to be the major pathway to form SOA, although other pathways also played significant roles. To achieve quantitative collection of SVOCs following improved gas/particle separation, a new collection and thermal desorption system was developed with the key component being a passivated metal fiber filter collector. This final configuration of the SV-TAG enabled in-situ quantitative measurements of speciated SVOCs with vapor pressures lower than n-tetradecane (C14). The capability for measurements of gas/particle partitioning was demonstrated by measurements of n-alkanes in both gas and particle phases. Organic tracers in both gas and particle phases can be quantified. Percentages of speciated organic compounds in total measured organics can be estimated. For example, ~7% and less than 1% of total measured organics in the same retention range of n-alkanes (C14-C20) in the atmosphere in Berkeley, CA were accounted for by the sum of measured n-alkanes (C14-C20) and the sum of n alkylcyclohexanes (C14-C20). The SV-TAG has been demonstrated to enable investigation of the pathways of gas-to-particle partitioning and source apportionment of OA with hourly time resolution. The SV-TAG is also capable of quantitative measurements of speciated SVOCs, defining their gas/particle partitioning in-situ for the first time, and providing observational constraints on the abundance of SVOCs with which to investigate their primary emissions, chemical transformation, and fate.
