Terpene and Terpenoid Emissions and Secondary Organic Aerosol Production

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Terpene and Terpenoid Emissions and Secondary Organic Aerosol Production Michigan Technological University Digital Commons @ Michigan Tech Dissertations, Master's Theses and Master's Dissertations, Master's Theses and Master's Reports - Open Reports 2013 TERPENE AND TERPENOID EMISSIONS AND SECONDARY ORGANIC AEROSOL PRODUCTION Rosa M. Flores Michigan Technological University Follow this and additional works at: https://digitalcommons.mtu.edu/etds Part of the Atmospheric Sciences Commons, and the Environmental Engineering Commons Copyright 2013 Rosa M. Flores Recommended Citation Flores, Rosa M., "TERPENE AND TERPENOID EMISSIONS AND SECONDARY ORGANIC AEROSOL PRODUCTION", Dissertation, Michigan Technological University, 2013. https://doi.org/10.37099/mtu.dc.etds/818 Follow this and additional works at: https://digitalcommons.mtu.edu/etds Part of the Atmospheric Sciences Commons, and the Environmental Engineering Commons TERPENE AND TERPENOID EMISSIONS AND SECONDARY ORGANIC AEROSOL PRODUCTION By Rosa M. Flores A DISSERTATION Submitted in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY In Environmental Engineering MICHIGAN TECHNOLOGICAL UNIVERSITY 2013 © Rosa M. Flores This dissertation has been approved in partial fulfillment of the requirements for the Degree of DOCTOR OF PHILOSOPHY in Environmental Engineering. Department of Civil and Environmental Engineering Dissertation Advisor: Paul V. Doskey Committee Member : Chandrashekhar P. Joshi Committee Member : Claudio Mazzoleni Committee Member : Lynn Mazzoleni Committee Member : Judith Perlinger Department Chair: David Hand To dad and mom Table of Contents Preface ..................................................................................................................................... 7 Abstract .................................................................................................................................... 9 Chapter 1. Introduction ........................................................................................................... 11 Chapter 2. Terpenoid Signatures of Conifer Essential Oils: New Measurements and a Review 14 2.1. Introduction ................................................................................................................. 17 2.2. Materials and Methods ................................................................................................. 20 2.2.1. Biological and chemical materials ......................................................................... 20 2.2.2. Gas chromatographic-mass spectrometric methods ................................................ 20 2.3. Results and discussion ................................................................................................. 22 2.3.1. Essential oil composition of Pinus sylvestris, Picea mariana, and Thuja occidentalis ....................................................................................................................................... 22 2.3.2. Variations related to taxonomy .............................................................................. 24 2.3.3. Variations related to season and age ...................................................................... 33 2.3.4. Variations related to geographical location and stresses ......................................... 39 2.3.5. Variations related to isolation and analytic methods ............................................... 44 2.4. Conclusions ................................................................................................................. 46 2.5. Acknowledgements ...................................................................................................... 48 2.6. References ................................................................................................................... 49 Chapter 3. Estimating Terpene and Terpenoid Emission Signatures from Conifer Oleoresin Composition ........................................................................................................................... 95 3.1. Introduction ................................................................................................................. 97 3.2. Methods ...................................................................................................................... 99 3.2.1. Modeling Approach ............................................................................................ 100 3.3. Results and discussion .............................................................................................. 103 3.4. Conclusions .............................................................................................................. 105 3.5. Acknowledgements .................................................................................................... 107 3.6. References ................................................................................................................. 108 Chapter 4. Comparison of Multistep Derivatization Methods for Identification and Quantification of Oxygenated Species in Organic Aerosol .................................................... 118 4.1. Introduction ............................................................................................................... 120 4 4.2. Experimental Method ................................................................................................. 122 4.3. Results and Discussion ............................................................................................... 125 4.4. Conclusions ............................................................................................................... 130 4.5. Acknowledgements .................................................................................................... 130 4.6. References ................................................................................................................. 132 Chapter 5. Using Multidimensional Gas Chromatography to Define a Carbon Number- Functionality Grid for Characterizing Oxidation of Organic Aerosol ..................................... 149 5.1. Introduction .............................................................................................................. 151 5.2. Methods .................................................................................................................... 154 5.2.1. Estimation of theoretical retention indices ........................................................... 155 5.2.2. Measurement of gas chromatographic retention times for assessment of non-additive effects ........................................................................................................................... 158 5.2.3. Error Analysis ..................................................................................................... 158 5.3. Results and discussion .............................................................................................. 159 5.3.1. Estimated retention indices vs. experimental retention times of multifunctional species .......................................................................................................................... 161 5.3.2. GC u GC and GC u 2GC retention index diagrams. ............................................. 163 5.3.3. Error analysis. ..................................................................................................... 164 5.4. Conclusions .............................................................................................................. 165 5.5. Acknowledgments ..................................................................................................... 167 5.6. References ................................................................................................................. 168 5.7. Supplementary Material ............................................................................................. 183 Chapter 6. Vapor- and Aerosol-Phase Atmospheric Organic Matter in the Midwestern United States: Methods and Measurements ...................................................................................... 197 6.1. Introduction ............................................................................................................... 200 6.2. Experimental Methods ............................................................................................... 203 6.2.1. Chemicals and solvents. ...................................................................................... 203 6.2.2. Sample Collection. .............................................................................................. 203 6.2.3. Glassware Preparation. ........................................................................................ 204 6.2.4. Sample processing. .............................................................................................. 204 6.2.5. GC-MS analysis. ................................................................................................. 205 6.2.6. Method Detection Limits and Quantification. ...................................................... 206 5 6.3. Results and Discussion ............................................................................................... 207 6.3.1. Extraction Efficiencies and Method Detection Limits for n-Alkanes and PAH. .... 207 6.3.2. Temporal Trends in HSVOCs, Monoterpenes, and Monoterpenoids..................... 209 6.3.3. Temporal Trends in Functionalized OA Species .................................................. 212 6.3.4. GC × GC-ToF-MS Capabilities.
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