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.


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.


Air Quality

Air Quality

Author: Ashok Kumar

Publisher: IntechOpen

Published: 2010-08-18

Total Pages: 392

ISBN-13: 9789533071312

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Air pollution is about five decades or so old field and continues to be a global concern. Therefore, the governments around the world are involved in managing air quality in their countries for the welfare of their citizens. The management of air pollution involves understanding air pollution sources, monitoring of contaminants, modeling air quality, performing laboratory experiments, the use of satellite images for quantifying air quality levels, indoor air pollution, and elimination of contaminants through control. Research activities are being performed on every aspect of air pollution throughout the world, in order to respond to public concerns. The book is grouped in five different sections. Some topics are more detailed than others. The readers should be aware that multi-authored books have difficulty maintaining consistency. A reader will find, however, that each chapter is intellectually stimulating. Our goal was to provide current information and present a reasonable analysis of air quality data compiled by knowledgeable professionals in the field of air pollution.


Toward a Comprehensive and Efficient Thermodynamic Model of Organic Aerosols Indoors

Toward a Comprehensive and Efficient Thermodynamic Model of Organic Aerosols Indoors

Author: Bryan Edward Cummings

Publisher:

Published: 2021

Total Pages: 310

ISBN-13:

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Within residential buildings, organic aerosols (OA) often constitute the majority of particulate matter (PM) pollution, which is known to cause adverse cardiovascular and respiratory conditions. OA is composed of thousands of unique organic compounds, many of which are susceptible to partitioning between the aerosol and the gas phase. Until relatively recently, indoor air pollution models have largely neglected OA thermodynamic considerations, although certain organic thermodynamics modeling tools have been used with narrow applications to indoor PM studies over the past decade. Most of these cases have investigated particular processes, such as secondary organic aerosol (SOA) formation indoors or the repartitioning of outdoor OA. The need for the development of a comprehensive indoor OA thermodynamic model motivated the work done for this dissertation. Organic aerosol thermodynamics was modeled by the Indoor Model of Aerosols, Gases, Emissions, and Surfaces (IMAGES) using the volatility basis set (VBS). Explicitly representing indoor OA volatility allowed for errors associated with baseline, traditional particle models to be quantified across various model types and domains. For instance, traditional estimates of indoor particle emission rates for activities such as cooking may yield erroneous concentration predictions when used in other models. In such cases, error is driven by differences between model and experimental building conditions. Such errors were found to reach up to ~80% for typical stir-fry activities, associated with a magnitude of ~15-20 (microgram)/m3 depending on the particular emission strength. Epidemiological models that seek to predict indoor exposure to ambient pollution also have traditionally neglected volatility considerations. Such models fail to account for repartitioning driven by temperature and mass-loading gradients between the indoors and outdoors, leading to errors up to ~60% for total ambient PM, or about 3 (microgram)/m3 in the urban U.S. simulation domain that was considered. The two-dimensional volatility basis set (2D-VBS) was also incorporated into the underlying IMAGES model framework, representing its first known application to indoor air studies. Using the 2D-VBS to account for oxidation state in addition to volatility allowed OA aging transformations and water uptake to be modeled in addition to gas-to-particle partitioning. Simulation results showed that aging reactions are not likely to affect indoor OA composition and character from a day-averaged perspective, but may enhance peak OA concentrations under certain SOA-forming conditions on the order of ~10 (microgram)/m3. Also predicting the indoor humidity and aerosol water content in typical U.S. residences demonstrated that OA likely exists in a semisolid phase state indoors. Slow molecular diffusion within such particles challenges the implicit assumption often held by tradition indoor OA studies: that equilibrium thermodynamics holds, and that particles are typically liquid and well-mixed. A kinetic partitioning model of indoor organics was developed to more accurately represent the partitioning of material into and out of semisolid or glassy aerosols. This model was applied to a simulation of ambient aerosols that are transported into buildings and experience a temperature gradient that affects its effective volatility. Simulation results suggested that low diffusion inhibits repartitioning to at least some extent in the majority of simulated cases, representing residences in each of the 16 U.S. climate zones. Condensation may occur at equilibrium mostly in the southeastern U.S. in the summertime, where a hot and humid climate leads to a high indoor RH and therefore an indoor OA population in a liquid phase state. More northern locations along the east coast are typically associated with a drier indoor environment as the outdoor climate cools. In these cases, evaporation is often partially prohibited or fully prohibited. Dry climate zones from Arizona to Montana are more likely to experience limited or prohibited partitioning on hot outdoor days. And west coast marine climate zones are more likely to experience partial or equilibrium partitioning even in cooler regions.