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Development of an Aerosol Mass Spectrometry System for the Analysis of the Composition of Aerosol Particles in Real Time

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Development of an Aerosol Mass Spectrometry System for the Analysis of the Composition of Aerosol Particles in Real Time DEVELOPMENT OF AN AEROSOL MASS SPECTROMETRY SYSTEM FOR THE ANALYSIS OF THE COMPOSITION OF AEROSOL PARTICLES IN REAL TIME Sandra Elizabeth Spencer A dissertation submitted to the faculty at the University of North Carolina at Chapel Hill in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Department of Chemistry (Analytical) in the School of Arts and Sciences Chapel Hill 2015 Approved by: Gary L. Glish Mark H. Schoenfisch Leslie M. Hicks Jeffrey S. Johnson Jason D. Surratt © 2015 Sandra Elizabeth Spencer ALL RIGHTS RESERVED ii ABSTRACT Sandra Elizabeth Spencer: Development of an Aerosol Mass Spectrometry System for the Analysis of the Composition of Aerosol Particles in Real Time (Under the direction of Gary L. Glish) Commercially available aerosol mass spectrometers are capable of sampling compounds from size selected aerosol particles without the requirement for collection of aerosol particles onto a surface. However, one primary disadvantage of the systems available commercially is the inability to gain structural information from analytes in complex samples. Fragmentation of analytes during ionization results in convolution of the observed mass spectrum and prevents identification of analytes. Separation of compounds by gas chromatography prior to ionization allows analytes to be identified but limits the utility of the mass spectrometer for analysis of the composition of aerosol particles in real time. Though one commercial design employs an ion source that does not induce significant fragmentation during ionization, the mass analyzer cannot be used to perform tandem mass spectrometry and thus the instrument is not useful for structural analysis of compounds from aerosol particles. The goal of the research presented in this dissertation is to develop an aerosol mass spectrometer for the evaluation of the structure of compounds in size-selected aerosol particles from components that are either commercially available or inexpensive and simple to custom build. Aerosol particle separations and analyte ionization are performed at atmospheric pressure to prevent preferential evaporation of the more volatile compounds from the particles in the high vacuum region of the mass spectrometer. To separate isomeric and isobaric analytes prior to mass analysis, ion mobility separations are used. Though the front end of this mass spectrometer can be retrofitted to couple with any mass analyzer, ion trap mass analyzers are used for these experiments to allow for a variety of unique capabilities including selective ion-molecule reactions and tandem mass spectrometry. iii ACKNOWLEDGEMENTS First and foremost, I would like to thank my advisor, Gary Glish. Gary, thank you for always pushing me to improve, especially when it was the most difficult. Thank you for your advice, your guidance, and all the opportunities you have made available to me in graduate school and beyond. Really and truly, no matter how unlikely this seems, thank you for every comment you have made on abstracts, papers, posters, talks, and this document. Your guidance has had a profound impact on my ability as a scientist and I count myself very lucky to have had the opportunity to learn from you. I also would like to thank the entire Glish group, past and present members, for their friendship and support. Thank you all for having the time to brainstorm and work through problems, to help each other with experiments, and to have a laugh when it’s needed. The group has been a safe place to have ideas, be they good or bad. I will remember and cherish all of our failures and triumphs, all the intellectual corners we have backed ourselves into, and all the times it felt like we were arguing when we weren’t. I don’t think anyone could ask for a better community in which to learn and grow. I am so appreciative to my parents: for everything they have done for me, for all the support and encouragement they have given me, and for teaching me to work hard and reach for the stars. To my siblings, thank you for teaching me that no matter how big the problem seems you can always get past it if you work hard. To the NC Waters family: Phil, Colleen, Sean, and Matthew, thank you for welcoming me with open arms, for all the holiday dinners and weekend visits, and for making NC feel more like home. Finally, I would like to thank the friends I have made in this phase of my life. Specifically I would like to thank Kady, Michelle, Vivien, and Casey. I would not be where I am without you. Thank you to each and every one of you for being who you are and for being here for me when I have needed you most. iv TABLE OF CONTENTS LIST OF TABLES .......................................................................................................................................... x LIST OF FIGURES ....................................................................................................................................... xi LIST OF ABBREVIATIONS........................................................................................................................ xvii CHAPTER 1: INTRODUCTION TO AEROSOL ANALYSIS BY MASS SPECTROMETRY ....................... 21 1.1 Importance of compositional analysis of aerosol particles ................................................................ 21 1.2 Analysis of the composition of aerosol particles ............................................................................... 21 1.2.1 Challenges associated with compositional analysis of aerosols................................................ 21 1.2.2 Collection of aerosol particles .................................................................................................... 22 1.2.3 Analysis of collected aerosol particles by mass spectrometry ................................................... 23 1.2.4 Drawbacks associated with particle collection ........................................................................... 24 1.3 Ambient sampling aerosol mass spectrometry ................................................................................. 24 1.3.1 Commercially available instrumentation .................................................................................... 24 1.3.2 Importance of the mass analyzer for structural analysis ............................................................ 26 1.3.3 Motivation for the work presented in this dissertation ................................................................ 27 1.4 Summary ........................................................................................................................................... 27 REFERENCES ........................................................................................................................................ 29 CHAPTER 2: EXPERIMENTAL .................................................................................................................. 34 2.1 Materials and reagents...................................................................................................................... 34 2.2 Aerosol generation and off-line characterization .............................................................................. 34 2.2.1 Aerosol particle generation ........................................................................................................ 34 2.2.2 Determination of aerosol particle size distribution ..................................................................... 35 2.2.3 Filter collection and extraction ................................................................................................... 36 2.3 Ionization ........................................................................................................................................... 37 2.3.1 Secondary electrospray ionization ............................................................................................. 37 v 2.3.2 Desorption electrospray ionization ............................................................................................. 37 2.3.3 Paper spray ionization ................................................................................................................ 38 2.3.4 Extractive electrospray ionization .............................................................................................. 38 2.3.5 Nano-extractive electrospray ionization ..................................................................................... 38 2.3.6 Low temperature plasma ionization ........................................................................................... 39 2.4 Mass spectrometry ............................................................................................................................ 42 2.4.1 Gas chromatography-mass spectrometry .................................................................................. 42 2.4.2 Ion trap mass spectrometry........................................................................................................ 43 2.5 Differential ion mobility spectrometry ................................................................................................ 45 2.6 Data analysis ..................................................................................................................................... 47 REFERENCES ........................................................................................................................................ 49 CHAPTER 3: IONIZATION OF COMPOUNDS FROM AEROSOL PARTICLES COLLECTED ON FILTERS.....................................................................................................................................................
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