Traffic relate emphasis on polycyclic ar Traffic related emphasis on pa polycyclic arom Traffic ...

105 Pages·2016·7.71 MB·English

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© Ioannis Sadiktsis, Stockholm University, 2016

ISBN 978-91-7649-374-8
Front cover: Photo by Carolina Gustafsson
Printed in Sweden by Holmbergs, Malmö 2016
Distributor: Department of Environmental Science and Analytical Chemistry
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Till min familj
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List of publications
This doctoral thesis is based upon the following publications, which are referred to
its corresponding Roman numeral throughout the thesis:

I. Automobile tires – a potential source of highly carcinogenic
dibenzopyrenes to the environment, Ioannis Sadiktsis, Christoffer
Bergvall, Christer Johansson, and Roger Westerholm. Environmental
Science & Technology, 46, 2012, 3326–3334. Reprinted with
permission from American Chemical Society. © 2012 American
Chemical Society.

II. Particulate associated polycyclic aromatic hydrocarbon exhaust
emissions from a portable power generator fueled with three different
fuels – a comparison between petroleum diesel and two biodiesels,
Ioannis Sadiktsis, Johannes H. Koegler, Timothy Benham, Christoffer
Bergvall, and Roger Westerholm. Fuel, 115, 2014, 573–580. Reprinted
with permission from Elsevier.

III. Tire tread wear particles in ambient air – a previously unknown source
of human exposure to the biocide 2-mercaptobenzothiazole, Rozanna
Avagyan, Ioannis Sadiktsis, Christoffer Bergvall, and Roger
Westerholm. Environmental Science and Pollution Research, 21, 2014,
11580–11586. Reprinted with permission from Springer Science and
Business Media.

IV. Class separation of lipids and polycyclic aromatic hydrocarbons in
normal phase High Performance Liquid Chromatography – A prospect
for analysis of aromatics in edible vegetable oils and biodiesel exhaust
particulates, Petter Olsson*, Ioannis Sadiktsis*, Jan Holmbäck, and
Roger Westerholm. Journal of Chromatography A, 1360, 2014, 39–46.
Reprinted with permission from Elsevier.

V. Physical and chemical properties of RME biodiesel exhaust particles
without engine modifications, Robin Nyström, Ioannis Sadiktsis,
Trifa M. Ahmed, Roger Westerholm, Johannes H. Koegler, Anders
Blomberg, Thomas Sandström, and Christoffer Boman. Manuscript
submitted to Fuel.

*
These authors contributed equally to the paper.
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The author’s contribution to the above mentioned publications are as follows:

Paper I: The author was responsible for the experimental work, majority of
the data analysis, some of the statistical analyses, and majority of
writing the paper.
Paper II: The author was partly responsible for outlining the experimental
work and responsible for the majority of the experimental work, data
analysis and writing of the paper.
Paper III: The author was responsible for conceiving the idea and partly
responsible for outlining the experimental work and a minor part of
writing the paper.
Paper IV: The author was responsible for conceiving the idea and outlining the
experimental work and minor part of the experimental work and data
analysis, and partly responsible for writing the paper.
Paper V: The author was partly responsible for the chemical analysis, and
writing a minor part of the paper.

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Aim of thesis
With the growing importance of non-exhaust particles relative to vehicular
tail-pipe emissions in urban air, it is necessary to investigate the possible
contribution of polycyclic aromatic hydrocarbons (PAHs) from the different
non-exhaust sources as these inputs are far less characterized than tail-pipe
emissions. Tire wear is a contributor to particles in urban air, alongside road
dust resuspension and brake wear. Due to its constituents i.e., extender oils
and carbon black filler material, tires contain PAHs. Studies regarding the
PAH contents in tire rubber are scarce and no study has focused on the
highly carcinogenic dibenzopyrenes.
One of the aims of this thesis has been to explore the possibilities of
whether tire wear could be a source of PAHs, in particular to the highly
carcinogenic dibenzopyrenes in urban air. To be able to quantitatively
measure the tire wear contribution to urban air, it is necessary to identify a
chemical marker compound or several marker compounds that ideally are
unique for that particular source and stable enough to be measured.
Benzothiazoles, used as vulcanization accelerators in tire manufacture, were
evaluated for their suitability as marker compounds for tire wear particles in
urban air.
Diminishing oil reserves and concern for global warming caused by
atmospheric inputs of CO from fossil fuel combustion has led to intensified
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efforts to find a suitable renewable alternative to petroleum based fuels. The
worldwide production volume of biofuels has increased considerably during
the last decade. Biodiesel, a biofuel produced from plant and animal fats, has
been suggested as a suitable replacement for conventional petroleum based
diesel fuels. While the majority of studies have focused on health outcomes
from petroleum diesel exhaust exposure, human health effects related to
biodiesel exhaust exposure is much less investigated.
The second aim of this thesis has been to investigate how biodiesel fuel
influence the emissions of PAHs from diesel engines in comparison to
petroleum based diesel. Particles collected on filters where analyzed for >40
PAHs in two separate studies on two different diesel engines, running on
neat rapeseed methyl ester (RME), petroleum diesel and a 30 % RME fuel
blend. One of the studies also included determination of four oxygenated
PAHs.
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List of publications not included in this thesis
The author has also contributed to the following peer-reviewed publications:

VI. Comparing columns for gas chromatography with the two–parameter
model for retention prediction, Yasar Thewalim, Ioannis Sadiktsis,
and Anders Colmsjö. Journal of Chromatography A, 1218, 2011,
5305–5310

VII. Determination of benzothiazole and benzotriazole derivates in tire and
textile samples by high performance liquid chromatography –
electrospray ionization tandem mass spectrometry, Rozanna Avagyan,
Ioannis Sadiktsis, Gunnar Thorsén, Conny Östman, and Roger
Westerholm. Journal of Chromatography A, 1307, 2013, 119–125

VIII. Effect of Wood Smoke Exposure on Vascular Function and Thrombus
Formation in Healthy Fire Fighters, Amanda L Hunter, Jon Unosson,
Jenny A Bosson, Jeremy P Langrish, Jamshid Pourazar, Jennifer B
Raftis, Mark R Miller, Andrew J Lucking, Christoffer Boman, Robin
Nyström, Kenneth Donaldson, Andrew D Flapan, Anoop SV Shah,
Louis Pung, Ioannis Sadiktsis, Silvia Masala, Roger Westerholm,
Thomas Sandström, Anders Blomberg, David E Newby, and Nicholas
L Mills. Particle and Fibre Toxicology, 11(62), 2014

IX. Removal of polycyclic aromatic hydrocarbons and genotoxic
compounds in urban air using air filter materials for mechanical
ventilation in buildings, Ioannis Sadiktsis, Gertrud Nilsson, Ulf
Johansson, Ulf Rannug, and Roger Westerholm. Science and
Technology for the Built Environment (In press). DOI:
10.1080/23744731.2016.1152155

X. Rapeseed Methyl Ester Biodiesel Exhaust Exposure Causes Vascular
Dysfunction in Man, Jon Unosson, Anders Blomberg, Thomas
Sandström, Christoffer Boman, Robin Nyström, Mikael Kabele,
Ioannis Sadiktsis, Roger Westerholm, Ian Mudway, Jennifer Raftis,
Nicholas L Mills, David E Newby, Jeremy P Langrish, and Jenny A
Bosson. Manuscript (preprint).
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Contents
1. Introduction ................................................................................. 13
Air pollution ..................................................................................................................... 13
2. Particulate matter ...................................................................... 15
Physicochemical characteristics .................................................................................. 15
Particle toxicity ............................................................................................................... 17
Traffic-related particles ................................................................................................. 19
Exhaust emissions ......................................................................................................... 20
Non-exhaust emissions ................................................................................................. 23
Health effects from non-exhaust particles ................................................................ 26
3. Polycyclic aromatic hydrocarbons (PAHs) ............................. 27
Exposure situations and monitoring ........................................................................... 30
Risk assessment ............................................................................................................. 31
Sources of PAH compounds in the atmosphere ....................................................... 33
PAH derivatives .............................................................................................................. 35
4. Analytical methodology for PAHs ............................................ 38
Particle sampling ............................................................................................................ 38
Sample extraction .......................................................................................................... 39
Soxhlet extraction .......................................................................................................... 40
Ultrasound-assisted solvent extraction ..................................................................... 42
Pressurized fluid extraction .......................................................................................... 42
Sample cleanup/isolation ............................................................................................. 44
Solid phase extraction................................................................................................... 44
HPLC fractionation techniques ..................................................................................... 45
Instrumental analysis .................................................................................................... 48
Large volume injection ................................................................................................. 48
Gas chromatographic separations .............................................................................. 49
Mass spectrometry of PAHs ......................................................................................... 55
Coupled HPLC/GC/MS for PAH determination .......................................................... 59
5. Results .......................................................................................... 61
Paper I .............................................................................................................................. 61
Paper II ............................................................................................................................ 62
Paper III ........................................................................................................................... 64
Paper IV ........................................................................................................................... 65
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Paper V ............................................................................................................................. 70
6. Discussions .................................................................................. 71
Tire wear .......................................................................................................................... 71
Biodiesel exhaust ........................................................................................................... 73
The analytical challenge ............................................................................................... 77
7. Conclusions and future perspectives ...................................... 79
8. Sammanfattning på svenska.................................................... 81
9. Acknowledgements .................................................................... 84
10. References ................................................................................... 87

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