University of Vermont ScholarWorks @ UVM Graduate College Dissertations and Theses Dissertations and Theses 2015 Organic Chemical Characterization Of Primary And Secondary Biodiesel Exhaust Particulate Matter John Kasumba University of Vermont Follow this and additional works at: https://scholarworks.uvm.edu/graddis Part of the Environmental Engineering Commons, and the Place and Environment Commons Recommended Citation Kasumba, John, "Organic Chemical Characterization Of Primary And Secondary Biodiesel Exhaust Particulate Matter" (2015). Graduate College Dissertations and Theses. 358. https://scholarworks.uvm.edu/graddis/358 This Dissertation is brought to you for free and open access by the Dissertations and Theses at ScholarWorks @ UVM. It has been accepted for inclusion in Graduate College Dissertations and Theses by an authorized administrator of ScholarWorks @ UVM. For more information, please contact [email protected]. ORGANIC CHEMICAL CHARACTERIZATION OF PRIMARY AND SECONDARY BIODIESEL EXHAUST PARTICULATE MATTER A Dissertation Presented by John Kasumba to The Faculty of the Graduate College of The University of Vermont In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy Specializing in Civil and Environmental Engineering May, 2015 Defense Date: October 29, 2014 Dissertation Examination Committee: Britt A. Holmén, Ph.D, Advisor Giuseppe A. Petrucci, Ph.D, Chairperson Donna M. Rizzo, Ph.D Robert G. Jenkins, Ph.D Cynthia J. Forehand, Ph.D., Dean of the Graduate College ABSTRACT Biodiesel use and production has significantly increased in the United States and in other parts of the world in the past decade. This change is driven by energy security and global climate legislation mandating reductions in the use of petroleum-based diesel. Recent air quality research has shown that emission of some pollutants such as CO, particulate matter (PM), SO2, hydrocarbons, and carcinogenic polycyclic aromatic hydrocarbons (PAHs) is greatly reduced with biodiesel. However, studies have also shown that some unregulated emissions, such as gas-phase carbonyls, are increased with biodiesel combustion. Very limited research has been done to investigate the particle- phase carbonyl and quinone emissions from biodiesel combustion. Also, very limited studies have investigated the ozone oxidation of biodiesel exhaust PM. Fatty acid methyl esters (FAMEs) are found in high abundance in biodiesel exhaust PM. The presence of these FAMEs in biodiesel exhaust PM can potentially alter the kinetics of the reactions between ozone and particle-phase PAHs. In this study, an Armfield CM-12 automotive light-duty diesel engine operated on a transient drive cycle was used to generate PM from various waste vegetable oil (WVO) and soybean biodiesel blends (containing 0%, (B00), 10% (B10), 20% (B20), 50% (B50), and 100% (B100) biodiesel by volume). The primary PM emissions were sampled using Teflon-coated fiberfilm filters. Laboratory PAHs, FAMEs, and B20 exhaust PM were exposed to ~0.4 ppm ozone for time periods ranging from 0-24 hours in order to study the effect of FAMEs and biodiesel exhaust PM on the ozonolysis of PAHs. Organic chemical analysis of samples was performed using gas chromatography/mass spectrometry (GC/MS). PAHs, carbonyls, FAMEs, and n-alkanes were quantified in the exhaust PM of petrodiesel, WVO and soybean fuel blends. The emission rates of the total PAHs in B10, B20, B50, and B100 exhaust PM decreased by 0.006-0.071 ng/µg (5-51%) compared to B00, while the emission rates for the FAMEs increased with increasing biodiesel content in the fuel. The emission rates of the total n-alkanes in B10, B20, B50, and B100 exhaust PM decreased by 0.5-21.3 ng/µg (4-86%) compared to B00 exhaust PM. The total emission rates of the aliphatic aldehydes in biodiesel exhaust PM (B10, B20, B50, and B100) increased by 0.019-2.485 ng/µg (36-4800%) compared to petrodiesel. The emission rates of the total aromatic aldehydes, total aromatic ketones, and total quinones all generally decreased with increasing biodiesel content in the fuel. With the exception of benzo[a]pyrene, the pseudo-first order ozone reaction rate constants of all the PAHs decreased by 1.2-8 times in the presence of the FAMEs. Phenanthrene, fluoranthene, and pyrene were the only PAHs detected in the B20 exhaust PM, and their ozone reaction rate constants were about 4 times lower than those obtained when the PAHs alone were exposed to ozone. The findings of this study indicate that there are both positive and negative effects to emissions associated with biodiesel use in light-duty diesel engines operating on transient drive cycle. CITATIONS Material in Appendix D of this dissertation was published in the journal of Atmospheric Environment in the form: Kasumba, J., Holmén, B.A., Hiscox, A., Wang, J., Miller, D.. (2011). Agricultural PM10 Emissions from Cotton Field Disking in Las Cruces, NM. Atmospheric Environment, 45, 1668-1674. DOI: 10.1016/j.atmosenv.2011.01.004. Material in Appendix E of this dissertation was published in the Journal of Agricultural and Food Chemistry in the form: Holmén, B.A., Kasumba, J., Hiscox, A., Wang, J., Miller, D.. (2013). Mechanized and Natural Soil-to-Air Transfer of Trifluralin and Prometryn from a Cotton Field in Las Cruces, New Mexico. Journal of Agricultural and Food Chemistry, 61, 9776-9783. DOI: 10.1021/jf4020697. My contribution towards this publication was about 60%. I was responsible for developing the extraction and analysis procedures for all the field samples. I also wrote the initial draft of this publication. ii ACKNOWLEDGMENTS I would like to start by thanking Professor Britt Holmén, my advisor, for mentoring me during my graduate studies at UVM. Her continuous support and push for excellence helped me succeed through my Ph.D. program. I also thank her for reading through all the manuscripts in this dissertation. I would also like to thank Professor Giuseppe Petrucci for chairing my dissertation committee. I also thank Professors Donna Rizzo and Robert Jenkins for serving on my dissertation committee. I thank them for all the helpful suggestions they gave me when I was writing this dissertation. I also acknowledge the present members of the Holmén Research Group (Karen Sentoff, Tyler Feralio, Jim Dunshee, Matt Conger, and Ben Rukavina) and the past members (Dan Nielsen, Tucker Stevens, Mitchell Robinson, Terry Barrett, Phil Cannata, Chris Gavitt, Dan Cooney, Timothy Kelly, and Wesley Miller) for their help in the lab, advice, and contributions in group meetings. I also wish to thank Bruce O’Rourke for helping troubleshoot the GC/MS systems in our laboratory. Lastly, I thank my family and friends for supporting me throughout my Ph.D. journey. Special thanks to my friends John Hanley, Mr. Joseph Rogers, Mrs. Laurene Rogers, and Laura Obregon for the great love they showed me while I was in this cold part of the world. iii TABLE OF CONTENTS CITATIONS ....................................................................................................................... ii ACKNOWLEDGMENTS ................................................................................................. iii LIST OF TABLES ............................................................................................................. vi LIST OF FIGURES .......................................................................................................... vii TABLE OF ABBREVIATIONS ....................................................................................... ix Chapter 1 INTRODUCTION ........................................................................................ 1 1.1 Organization of Dissertation .................................................................................... 1 1.2 Background .............................................................................................................. 4 1.3 Overall Research Objectives .................................................................................... 7 1.4 Research Questions .................................................................................................. 8 1.5 Literature Review ..................................................................................................... 9 1.5.1 Chemical Composition of Biodiesel and Biodiesel Exhaust PM ...................... 9 1.5.2 Chemical Composition of Diesel and Diesel Exhaust PM .............................. 17 1.5.3 Effects of Biodiesel on the Organic Compounds in PM from Diesel Engines 19 1.5.4 Reaction of Ozone with Biodiesel Exhaust PM .............................................. 22 Chapter 2 METHODS .................................................................................................. 26 2.1 Methods for Organic Chemical Analysis of Diesel and Biodiesel Exhaust PM .... 26 2.1.1 Fuels used in Emission Tests ........................................................................... 26 2.1.2 Emissions Test Procedure and Sampling ......................................................... 29 2.1.3 Chemicals ........................................................................................................ 32 2.1.4 Extraction and Analysis of Target Organic Chemical Compounds ................ 35 2.1.5 Quality Control /Quality Assurance ................................................................ 38 2.1.6 Data Analysis ................................................................................................... 41 2.2 Methods for Analysis of Fuel Samples .................................................................