AN ABSTRACT OF THE THESIS OF Scott Lafontaine for the degree of Master of Science in Chemistry presented on December 12, 2014. Title: Relative Influence of Trans-Pacific and Regional Atmospheric Transport of Polycyclic Aromatic Hydrocarbons (PAHs) in the Pacific Northwest (PNW), USA Abstract approved: ______________________________________________________ Staci L. Massey Simonich The relative influences of trans-Pacific and regional atmospheric transport on measured concentrations of polycyclic aromatic hydrocarbons (PAHs), PAH derivatives [Nitro- (NPAH) and Oxy-(OPAH)], organic carbon (OC), and Particulate Matter (PM) less than 2.5 μm in diameter (PM ) were investigated in the Pacific 2.5 Northwest, USA in 2010-2011. Ambient high volume PM air samples were 2.5 collected at two sites in the Pacific Northwest: 1.) Mount Bachelor Observatory (MBO) in the Oregon Cascade Range (2763 m above sea level (asl)) and 2.) Confederated Tribes of the Umatilla Indian Reservation (CTUIR) in the Columbia River Gorge (CRG) (954 m asl). Nine trans-Pacific transport events (7 in 2010 and 2 in 2011) were identified at MBO and three of these days had direct acting mutagenicity greater than the negative control. 2-MNAP, 1-MNAP, 2,6-DMNAP, 1,3-DMNAP, 2-MPHE, 1-MPHE, NAP, ACY, ACE, CHR+TRI, and BenzANT, were identified as potential molecular markers for regional transport at MBO. While RET, BghiP, 9-NPH, 3,NPH, 1-NP, 1,8-DNP, and BcdPYRO were identified as potential molecular markers for trans-Pacific transport at MBO. At CTUIR, NOx, CO and SO emissions from a 585 MW coal fired power plant, in Boardman OR, 2, 2 were found to be significantly positively correlated with PAH, OPAH, NPAH, OC, and PM concentrations. By comparing the Boardman Plant operational time frames 2.5 when the plant was operating to when it was shut down, the plant was found to contribute a large percentage of the measured PAH (67%), NPAH (91%), OPAH (54%), PM (39%) and OC (38%) concentrations at CTUIR and the CRG prior to 2.5 Spring 2011 and likely masked trans-Pacific atmospheric transport events to the CRG. Upgrades installed to the Boardman Plant in the spring of 2011 dramatically reduced the plant’s contribution to PAH and OPAH concentrations (by ~72% and ~40%, respectively) at CTUIR and the CRG but not NPAH, PM or OC 2.5 concentrations. Sixteen days in 2010, and only one day in 2011, had direct acting mutagenicity greater than the negative control at CTUIR. ©Copyright by Scott Lafontaine December 12, 2014 All Rights Reserved Relative Influence of Trans-Pacific and Regional Atmospheric Transport of Polycyclic Aromatic Hydrocarbons (PAHs) in the Pacific Northwest (PNW), USA by Scott Lafontaine A THESIS submitted to Oregon State University in partial fulfillment of the requirements for the degree of Master of Science Presented December 12, 2014 Commencement June 2015 Master of Science thesis of Scott Lafontaine presented on December 12, 2014 APPROVED: Major Professor, representing Chemistry Chair of the Department of Chemistry Dean of the Graduate School I understand that my thesis will become part of the permanent collection of Oregon State University libraries. My signature below authorizes release of my thesis to any reader upon request. Scott Lafontaine, Author ACKNOWLEDGEMENTS The author is very appreciative and would like to thank Dr. Staci Simonich for her patience, time, and support. I would also like to thank my graduate committee, Dr. Jennifer Field, Dr. Kim Anderson, and Dr. Neal Sleszynski for their time and guidance. I would also like to express gratitude to Katrina Waters and Lisa Bramer for their statistical advice and analysis. I am also very grateful of all of the help that I have received from past and current lab mates (Jill Schrlau, Narumol Jariyasopit, Christopher Walsh, Oleksii Motorykin, Leah Chibwe, Anna Chlebowski, Melissa McIntosh, Lisandra Delgado, and Ivan Titaley and undergraduates Kevin Kovalchik, Shelby Paulson). Finally, I would like to thank my fiancée, Libbie Goodill, my family, and my friends for their love and care. CONTRIBUTION OF AUTHORS Dr. Staci L. Simonich provided edits and advice on all thesis chapters. Chapter 2. Yuling Jia performed the OC/EC analysis and some of the sample collection in 2010 at MBO. Jill Schrlau performed the PAH analysis, and set up the Hi volume air sampler with Jack Butler and Stuart Harris at CTUIR. Jack Butler collected the air samples at CTUIR. Dr. Barbara L. Harper, Stuart Harris and Dr. Anna Harding represented the Confederated Tribes of the Umatilla Indian Reservation. TABLE OF CONTENTS Page Chapter 1 Introduction .................................................................................................... 1 References ........................................................................................................ 6 Chapter 2. Relative Influence of Trans-Pacific and Regional Atmospheric Transport of Polycyclic Aromatic Hydrocarbons (PAHs) in the Pacific Northwest (PNW), USA………………………………………………….…………...9 Abstract .......................................................................................................... 10 Introduction .................................................................................................... 11 Experimentail Methods .................................................................................. 12 Results and Disscussion ................................................................................. 21 Conclusions .................................................................................................... 72 Acknowledgements ........................................................................................ 75 References ...................................................................................................... 76 Chapter 3. Conclusion .................................................................................................. 80 LIST OF FIGURES Figure Page 2.1 Map of the sampling locations (MBO and CTUIR) ………………...………15 2.2 SRIF boxes for MBO and CTUIR…………………………………………...20 2.3 Temporal variation of and mean concentrations of ∑PAH , ∑OPAH , and 32 10 ∑NPAH concentrations at MBO over the sampling period…............…….22 27 2.4 Temporal variation and mean concentrations of 24 hr sum of PM , OC, and 1 EC measured at MBO over the sampling period……….………….……...…24 2.5 Source region impact factors (SRIFs), calculated using the 10 day back trajectories for MBO over the entire sampling period ……………...……….26 2.6 The determined frantiocal abundces plots for the PAHs measured on the Trans-Pacific atmopheirc transport events that occurred during the sampling peiord…………………………………………………………………….…..35 2.7 AMES Assay Direct Acting Mutagetagenticy Assay (-S9 rat liver enzyme) for sampling period A.) 2010 and B.) 2011 at MBO ……………….…...………37 2.8 Temporal variation of mean ∑PAH (gray bars), ∑OPAH (red line with 32 10 triangles) and ∑NPAH (blue line with squares) concentrations at CTUIR 27 over the sampling period …………………...……………...………………...39 2.9 Temporal variation and mean concentrations of 24 hr sum of PM [at 2.5 Mission (bars) and ODEQ (pink line and hexagons)] and OC (black line and stars) concentrations at Cabbage Hill in CTUIR over the sampling period....40 2.10 Source region impact factors (SRIFs), calculated using the 10 day back trajectories for CTUIR over the entire sampling period……………….....….42 2.11 Average wind roses for 2010 and 2011 for the duration of the sampling period at Eastern Oregon airport 20 km north of CTUIR using the hourly site wind speed and direction data from NOAA. ……………………………………...45 2.12 PAH isomer cross plot (BaA/(BaA+CHR) vs IcdP/(IcdP+BghiP)) at Cabbage Hill…………………………………………………...………………………46 2.13 Three operational timeframes (plant on (Before Upgrade), plant on (After Upgrade) and plant off) and ∑PAH , ∑OPAH , and ∑NPAH 32 10 27 concentrations during the sampling period……………………………..……49 LIST OF FIGURES (Continued) Figure Page 2.14 Three operational timeframes (plant on (Before Upgrade), plant on (After Upgrade) and plant off) of PM and ODEQ concentrations and OC 2.5 (concentrations during the sampling period………………...…………..……50 2.15 PAH isomer cross plot (BaA/(BaA+CHR) vs IcdP/(IcdP+BghiP)) using thresholds from CTUIR Plant on (Before upgrade) and CTUIR plant off and CTUIR plant on (After Upgrades) ……………………………………….….52 2.16 The 24 hr CO emission from the Boardman Power Plant correlated with A.) 2 ∑PAH , ∑OPAH , ∑NPAH concentrations and B.) PM and OC 32 10 27 2.5 concentrations ………………...…………………………………………..…53 2.17 The 24 hr SO emission from the Boardman Power Plant correlated with A.) 2 ∑PAH , ∑OPAH , ∑NPAH concentrations and B.) PM and OC 32 10 27 2.5 concentrations……………………………………..…………………………54 2.18 The 24 hr NOx emission from the Boardman Power Plant correlated with A.) ∑PAH , ∑OPAH , ∑NPAH concentrations and B.) PM and OC 32 10 27 2.5 concentrations ……………………………………..………………………...55 2.19 The 24 hr ∑CO emission from the Boardman Power Plant A.) ∑PAH , 2 32 ∑OPAH , ∑NPAH and B.) PM and OC using only days when the plant 10 27 2.5 was off and days when the plant was on (Before Upgrade) ..…………….…58 2.20 The 24 hr total CO emissions from the Boardman Power Plant for each 2 sampling period A.) ∑PAH , ∑OPAH , ∑NPAH and B.) PM and OC 32 10 27 2.5 using only days when the plant was off and days when the plant was on (After Upgrade)………………………………………………………………...…...59 2.21 Statistically significant outlier of PM2.5 (at ODEQ and Mission) measured on August 6th 2010 (outlined by red oval) during the operational time frame when the plant was on (Before Upgrade)………………..…………….…….66 2.22 NASA FIRMS MODIS 10 Day fire detects overlaid with 10-Day air mass back trajectory and corresponding normalized PAH, OPAH, NPAH plots measured at CTUIR for the concurrent sampling occurring on August 6th 2010. In July and August of 2010, wildfires in Siberia burned over 200,000 ha (1,885 km2)………………………………………………………………......67