Photochemical Reaction Products of Polycyclic Aromatic Hydrocarbons Adsorbed at an Air-Water

180 Pages·2017·2.72 MB·English

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LSU Doctoral Dissertations Graduate School
2011
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Franz Stefan Ehrenhauser
Louisiana State University and Agricultural and Mechanical College
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PHOTOCHEMICAL REACTION PRODUCTS
OF POLYCYCLIC AROMATIC
HYDROCARBONS ADSORBED AT AN
AIR-WATER INTERFACE

A Dissertation
Submitted to the Graduate Faculty of the
Louisiana State University and
Agricultural and Mechanical College
in partial fulfillment of the
requirements for the degree of
Doctor of Philosophy
in
The Cain Department of Chemical Engineering

by
Franz Stefan Ehrenhauser
Dipl. Ing., Johannes Kepler University, Linz, Austria, 2009

December 2011
Die hohe Kraft
Der Wissenschaft,
Der ganzen Welt verborgen!
Und wer nicht denkt,
Dem wird sie geschenkt,
Er hat sie ohne Sorgen.

Johann Wolfgang von Goethe, Faust, 1808

To the patience of my parents and my loving wife
ii
ACKNOWLEDGEMENTS

I would like to thank first and foremost my advisor Dr. Mary J. Wornat for her support and her
guidance. Thanks to her, doors and opportunities have opened for me, which I would have
otherwise never realized. I also have to express my deepest gratitude to Dr. Kalliat T. Valsaraj,
who acted as my co-advisor during these years, for his patience and continuous support. I would
also like to thank my committee members, Dr. James J. Spivey, Dr. Francisco Hung and Dr.
Maud Walsh for their time.
I have to thank all my colleagues and co-workers for their help, their inspirations through
fruitful discussions and their additional perspectives. I want to especially thank Dr. Jing Chen, to
whom I am greatly indebted to, as without her work the extent of this dissertation would not have
been possible. I also owe gratitude to all the members of the department of chemical engineering,
which took care, that either ideas could be realized in the laboratory (Paul Rodriguez, Joe Bell,
Fred McKenzie), or that the bureaucracy did not stand in the way (Darla Dao, Melanie
McCandless and Danny Fontenot).
I want to thank my parents for their patience and their continuous support. A very special
thanks bears to my beloved wife Daira, who stood by me these years, being my big support in
any difficult situation.
I would like to acknowledge funding from NSF (Grant ATM 0355291 and Grant ATM
0907261), the Air Force Office of Scientific Research for providing funding for two HPLC
instruments (DURIP Grant FA9550-05-1-0253 and DURIP Grant FA9550-08-1-0281), the LSU
Graduate School for providing additional scholarships, as well Dr. Charles Coates, whose
generosity in form of the Dr. Charles E. Coates Scholar Research Award allowed me to collect
new experiences and present my work worldwide.
iii
TABLE OF CONTENTS
ACKNOWLEDGEMENTS ........................................................................................................... iii
LIST OF TABLES ........................................................................................................................ vii
LIST OF FIGURES ..................................................................................................................... viii
ABSTRACT ................................................................................................................................. xiv
1. INTRODUCTION .......................................................................................................................1
1.1 Polycyclic Aromatic Hydrocarbons .......................................................................................2
1.2. PAH Photodegradation .........................................................................................................5
1.2.1. Degradation Products of PAH in Bulk Phases ...................................................................9
1.2.2. Degradation Products of PAH in Thin Water Films ........................................................10
1.3. Environmental Impacts of Volatile PAH and Their Oxidation Products ...........................12
1.3.1. Health Effects of Volatile PAH and Their Oxidation Products ...................................12
1.3.2. Environmental Effects of Volatile PAH and Oxidation Products ...............................13
1.4. Objective and Structure of Thesis .......................................................................................14
2. ANALYSIS OF UV-OXIDATION PRODUCTS
OF PAH – METHOD DEVELOPMENT .................................................................................15
2.1 HPLC – Method Development ............................................................................................17
2.2. Online Sample Concentration .............................................................................................21
2.3. UV Absorption as Detection Method for Oxygenated Polycyclic
Aromatic Compounds ........................................................................................................25
2.4. APPI-MS .............................................................................................................................29
2.5. APPI-MS Method Development .........................................................................................31
2.5.1. APPI Source Optimization ...............................................................................................33
2.5.2. Dopant Delivery System ..................................................................................................39
2.5.2.1. Design of the Dopant Delivery System ....................................................................40
2.5.2.2. Dopant Selection .......................................................................................................45
2.5.2.3. Ionization Performance of Benzene as Dopant .........................................................49
2.6. APPI-MS Spectra ................................................................................................................53
2.6.1. Polycyclic Aromatic Hydrocarbons .............................................................................54
2.6.2. Hydroxyl-Substituted Polycyclic Aromatic Hydrocarbons .........................................55
2.6.3. Alcohols .......................................................................................................................56
2.6.4. Aromatic Ketones ........................................................................................................57
2.6.5. Carboxylic Acids and Esters ........................................................................................58
2.6.6. Aldehydes ....................................................................................................................60
2.6.7. APPI-MS Spectra for the Identification of OPAC .......................................................61
3. EXPERIMENTAL SETUP ........................................................................................................64
3.1. Thin-Film Reactor ...............................................................................................................64
3.2. Bulk-Phase Reactor .............................................................................................................69
3.3. Sample Analysis .................................................................................................................70
iv
4. PHOTOOXIDATION PRODUCTS OF POLYCYCLIC
AROMATIC HYDROCARBONS ............................................................................................72
4.1. Naphthalene ........................................................................................................................72
4.2. Phenanthrene .......................................................................................................................74
4.3. Pyrene .................................................................................................................................81
4.4. Acenaphthene ......................................................................................................................83
4.5. 9H-Fluorene ........................................................................................................................85
4.6. Summary .............................................................................................................................93
5. PHOTOOXIDATION OF 9H-FLUORENE IN THIN WATER FILMS ..................................95
5.1. Uptake of 9H-Fluorene onto Water Films ..........................................................................95
5.2 Photooxidation of 9H-Fluorene in Thin-Water Films .........................................................98
5.3. Discussion .........................................................................................................................103
6. CONCLUSIONS......................................................................................................................107
6.1. Advances in the Analytical Methodology of OPAC.........................................................107
6.2. Newly Identified UV Oxidation Products.........................................................................108
6.3. Interfacial Degradation of 9H-Fluorene ............................................................................109
6.4. Suggested Future Work ....................................................................................................109
REFERENCES ............................................................................................................................111
APPENDIX A: HPLC METHODS .............................................................................................122
APPENDIX B: GLASS SLIDE PREPARATION ......................................................................128
APPENDIX C: PURIFICATION OF POLYCYCLIC AROMATIC HYDROCARBONS .......132
Naphthalene .............................................................................................................................132
Phenanthrene ............................................................................................................................132
9H-Fluorene .............................................................................................................................134
Acenaphthene ...........................................................................................................................135
Pyrene ......................................................................................................................................135
APPENDIX D: UV SPECTRAL MATCHES .............................................................................136
APPENDIX E: SYNTHETIC PROCEDURES ...........................................................................140
Synthesis of 6H-Dibenzo[b,d]pyran-6-one ..............................................................................141
Synthesis of 6H-Dibenzo[b,d]pyran-6-ol.................................................................................143
Synthesis of 2-(2’-Hydroxy-phenyl)-benzyl alcohol ...............................................................145
Synthesis of 2- and 3- Hydroxy-9,10-phenanthrenequinone ...................................................148
Synthesis of 2- and 3-Phenanthrene Sulfonates .......................................................................149
Synthesis of 2-Hydroxyphenanthrene ......................................................................................150
Synthesis of 2-Acetoxyphenanthrene and 2-Acetoxy-9,10-phenanthrenequinone ..................152
Synthesis of 2-Hydroxy-9,10-phenanthrenequinone ...............................................................153
Synthesis of 3-Hydroxyphenanthrene ......................................................................................155
Synthesis of 3-Acetoxyphenanthrene ......................................................................................157
Synthesis of 3-Acetoxy-9,10-phenanthrenequinone ................................................................158
Synthesis of 3-Hydroxy-9,10-phenanthrenequinone ...............................................................159
v
Synthesis of 1-Acenaphthenone ...............................................................................................161
APPENDIX F: PERMISSION TO REPRINT .............................................................................163
VITA ............................................................................................................................................164
vi
LIST OF TABLES
Table 1. Properties of 16 PAH ........................................................................................... 4
Table 2. Relative potency factors of some PAH18 ............................................................. 4
Table 3. First-order kinetic constants for 9H-fluorene degradation in pure water ........... 10
Table 4. Photodegradation products of volatile PAH in pure water (bulk) ...................... 11
Table 5. LOD and recoveries of PAH and OPAC with a 5-mL injection
volume with online concentration, compared to traditional liquid-liquid
extraction with GC-MS analysis ....................................................................................... 25
Table 6. Ionization mechanisms104,108-116 in APPI mass spectrometry............................. 32
Table 7. Optimized APPI-MS parameters for qualitative analysis at
0.2 mL/min mobile phase flow (methanol) ....................................................................... 53
Table 8. Observed APPI-MS ionization patterns of polycyclic aromatic compounds..... 62
Table 9. Kinetic constants for 9H-fluorene oxidation products
formed in a 185-µm water film and a 37-µm water film at 19.8°C ................................ 102
Table 10. Mask material for HF etching ........................................................................ 129

vii
LIST OF FIGURES

Figure 1. 16 polycyclic aromatic hydrocarbons as EPA priority pollutants: I naphthalene, II
acenaphthylene, III acenaphthene, IV 9H-fluorene, V anthracene, VI phenanthrene, VII
fluoranthene, VIII pyrene, IX benzo[k]fluoranthene, X benzo[b]fluoranthene, XI chrysene, XII
benz[a]anthracene, XIII benzo[a]pyrene, XIV benzo[ghi]perylene, XV dibenz[a,h]anthracene,
XVI indeno[1,2,3-cd]pyrene ............................................................................................................3
Figure 2. Emission spectrum of sunlight at air mass 1.5 (AM 1.5 ground-level), UVB-Lamp
(UVP Inc., Cambridge, UK) and absorbance spectra of volatile PAH. ...........................................6
Figure 3. Generalized reaction pathways of PAH degradation with singlet oxygen, with hydroxyl
radicals and by direct ionization (1O singlet oxygen, 3O triplet oxygen) ......................................7
2 2
Figure 4. Riedl Pfleiderer process for the commercial production of hydrogen peroxide ..............8
Figure 5. Self condensation of anthracene adsorbed on silica ........................................................9
Figure 6. HPLC chromatogram of naphthalene photooxidation mixture analyzed with PAH
standard method (Method A in Appendix A). ...............................................................................18
Figure 7. HPLC chromatogram of naphthalene photooxidation mixture analyzed on a Pinnacle II
Phenyl column (Restek Corp., Bellefonte, PA, USA) ...................................................................20
Figure 8. HPLC chromatogram of naphthalene photooxidation mixture analyzed on a Ultra
Aqueous C18 column (Restek Corp. Bellefonte, PA, USA) .........................................................21
Figure 9. Six-port switching valve configuration; for online micro solid-phase extraction system
a) loading the large volume sample into the sample loop, b) loading the sample onto the guard
column c) switching the guard column into the analytical flow path ............................................23
Figure 10. UV absorbance spectra of pyrene (black), 4,5-pyrenequinone (green), 1,8-
pyrenequinone (blue) and 1,6-pyrenequinone (red) .......................................................................27
Figure 11. UV absorbance spectra of naphthalic acid anhydride (red), naphthalic acid (black)
and naphthalic acid dianion (blue) .................................................................................................28
Figure 12. Two commercially available ionization sources: (a) linear PhotoSpray® and (b)
orthogonal PhotoMate® .................................................................................................................33
Figure 13. Naphthalene (m/z 128) ionization dependency on the nebulizer pressure ...................35
Figure 14. Naphthalene (m/z 128) ionization dependency on the vaporizer temperature .............36
Figure 15. Efficiency of naphthalene ionization as a function of drying gas flow and
drying gas temperature. ..................................................................................................................37
viii
Figure 16. Peak area obtained from extracted positive ion chromatograms [M-2 to M+2] of
polycyclic aromatic compounds versus the capillary voltage........................................................38
Figure 17. The effect of the capillary voltage on the ionization pattern of 9,10-
phenanthrenequinone without a dopant. ........................................................................................39
Figure 18. Schematic of the gas-phase dopant delivery system ...................................................42
Figure 19. Benzene delivery rate at 40°C saturator temperature. .................................................46
Figure 20. Positive (a) and negative (b) ionization efficiencies with anisole, acetone, benzene
and toluene as dopants; for the negative ions of 1-naphthoic acid m/z 125-129 was used
instead of m/z 170-174 ...................................................................................................................48
Figure 21. Peak area obtained from extracted positive ion chromatogram [M-2 to M+2] of
polycyclic aromatic compounds versus the capillary voltage. Benzene was deployed as a
dopant at 40 mg/min. .....................................................................................................................50
Figure 22. The effect of the capillary voltage on the ionization pattern of 9,10-
phenanthrenequinone [PHQ] with 40 mg/min benzene as dopant.................................................51
Figure 23. APPI-MS spectra of 9H-fluorene (a) and phenanthrene (b) with benzene as dopant;
the red line marks the abundance of the positive and the blue line the abundance of the negative
ions .................................................................................................................................................55
Figure 24. APPI-MS spectra of phenol (a) and naphthalene-1-ol (b) with benzene as dopant;
the red line marks the abundance of the positive and the blue line the abundance
of the negative ions ........................................................................................................................56
Figure 25. APPI-MS spectra of 1-indanol (a) and 9-hydroxy-9H-fluorene (b) with benzene as
dopant; the red line marks the abundance of the positive and the blue line the abundance of the
negative ions ..................................................................................................................................57
Figure 26. APPI-MS spectra of 9H-fluorene-9-one (a) and 9,10-phenanthrenequinone (b) with
benzene as dopant; the red line marks the abundance of the positive and the blue line the
abundance of the negative ions ......................................................................................................58
Figure 27. APPI-MS spectra of 1-naphthoic acid (a) and 6H-dibenzo[b,d]pyran-6-one (b) with
benzene as dopant; the red line marks the abundance of the positive and the blue line the
abundance of the negative ions ......................................................................................................59
Figure 28. APPI-MS spectra of trans-cinnamaldehyde (a) and 1-naphthaldehyde (b) with
benzene as dopant; the red line marks the abundance of the positive and the blue line the
abundance of the negative ions ......................................................................................................60
Figure 29. Thin-film reactor (schematic). Solid arrows represent gas flow; dashed lines represent
coolant flow ...................................................................................................................................66
ix