SPECIATION STUDIES FOR BIOGENIC VOLATILE ORGANIC COMPOUNDS AND SECONDARY ORGANIC AEROSOL GENERATED BY OZONOLYSIS OF VOLATILE ORGANIC COMPOUND MIXTURES

摘要

Aerosols are either emitted directly into the atmosphere or are generated in the atmosphere; the latter process forms secondary organic aerosol (SOA). One of the important sources for SOA is the oxidation of volatile organic compounds (VOCs) by OH radicals, NOx, and O3. Aerosol can be visualized as suspended solid or liquid particle which is in equilibrium with surrounding gases. The products of SOA formation is a mixture of semi volatile organic compounds and a fraction of the products are condensable under atmospheric conditions. The condensable portion of aerosol is called particulate matter (PM) and these suspended particles can range in diameter from a few nanometers to microns. PM can impact climate through direct and indirect radiative forcing and can degrade air quality by reducing visibility and causing detrimental health effects. SOA can also form indoors, which also contributes to the health risk of PM. The severe impact of PM on human health and climate drives the scientific community to investigate the volatile organic compounds (VOCs) and their potential to form SOA, as well as the factors that alter the efficiency of SOA generation and the type of products. In a similar pursuit, the focus of this dissertation is the investigation of the SOA precursors that are emitted from trees and how they vary as a function of insect infestation. Also, the role of mixtures of VOCs as SOA precursors are investigated; commercial and lab made VOC mixtures are studied for SOA generation, product analysis, and absorption characteristics of aged SOA. Chapter 1 introduces PM, VOCs present in atmosphere, SOA generation, and speciation of products generated from the ozonolysis of VOCs. The impact of PM on human health and climate are summarized. A literature survey on the VOCs that are precursors to SOA and present in the outdoor and indoor environment is presented along with factors that may lead to variability in amount of VOCs. SOA generation from direct plant emissions and consumer products is surveyed. These studies show that VOC oxidation generate SOA which is important in the atmosphere due to climate and health effects and indoors due to health effects. A summary of SOA phase partitioning theories, the reaction mechanism for the formation of products from ozonolysis of the dominant biogenic SOA precursors (monoterpenes), and the factors that affect SOA generation is presented. Chapter 2 summarizes the results obtained from a field study assessing the impact of bark beetle infestation on SOA precursor emissions from forests in the Western United States. Samples of VOCs were collected by our collaborators from healthy and bark beetle infested trees using scent traps. We solvent extracted and analyzed by gas chromatography/mass spectrometry (GC/MS) nearly four hundred scent traps. An increase in the total and the individual VOCs emitted by infested trees was measured. A statistical analysis shows significant differences between the emissions from infested and healthy trees. A perspective is provided on potential impact of bark beetle infestation on regional SOA. The majority of the laboratory experiments for SOA generation have focused on individual VOCs as the single SOA precursor. However, as demonstrated in Chapter 2 for example, in a real environment multiple VOCs co-exist. Multiple SOA precursors undergo concurrent oxidation reactions, and it is not known if the products from concurrent oxidation of multiple precursors are the same as the sum of the products from individual SOA precursors. Mass closure analysis of field samples show that a significant fraction of the chemical identity of organic PM is unknown, but the chemistry impacts the toxicity of PM. Hence, it is important to understand SOA formation from realistic SOA mixtures. Chapter 3 describes the results of the SOA generation by ozonolysis of limonene and VOC mixtures containing limonene. We use an additive approach for building a surrogate VOC mixture close in composition to a commercially-available mixture. The yield of PM as a function of VOC precursor mixture was measured with respect to VOC composition using smog chamber SOA generation and scanning mobility particle sizing. PM in the chamber was collected onto filters and extracted, and the individual products of SOA were identified and quantified by GC/MS. The condensed-phase SOA products generated during these experiments for different VOC mixtures are compared. In Chapter 4, condensed-phase products sampled from SOA generated by the ozonolysis of α pinene and VOC mixtures containing α pinene, including two fir needle essential oils, are studied by extracting filter samples and analyzing the extracts by GC/MS. The products generated from VOC mixtures are characteristic of the most dominant VOC present in the mixture i.e. either limonene or α pinene. Some mixtures show the generation of new products which are not observed for corresponding individual VOC ozonolysis and hence can be used as marker for the corresponding VOC mixture. The distribution of α-pinene SOA products changes as the composition of the SOA precursor mixture changes. In Chapter 5, the UV visible absorption characteristics of ammonium ion aged SOA are discussed. Ammonium ion aging of aerosol leads impacts the radiative properties of aerosol and has the potential to impact aerosolu27s role in climate change. Filter samples containing SOA generated from two mixtures with different dominant monoterpenes (α-pinene-based Siberian fir needle oil and a limonene-based air freshener) were extracted. The absorption coefficients of the extracts were measured as a function of ammonium ion aging time using UV-visible absorption spectrometry. The conclusions from all above chapters are summarized in Chapter 6.