Relative influence of trans-Pacific and regional atmospheric transport of polycyclic aromatic ...

115 Pages·2015·5.92 MB·English

by  Lafontaine, Scott

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