Luận án tiến sĩ: Đường và polyol trong aerosol - HKUST

Sugars and Polyol Compounds in Ambient Aerosols and Cooking Fume Aerosols by Wan Chun Hong B. (Hons) in Chemistry, University of Hong Kong, Hong Kong (1999) A Thesis Presented to The Hong Kong University of Science and Technology in Partial Fulfillment of the Requirement for the Degree of Doctor of Philosophy in July 2006 UMI Number: 3240452 INFORMATION TO USERS The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleed-through, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted.

Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. ® UMI UMI Microform 3240452 Copyright 2007 by ProQuest Information and Learning Company. All rights reserved. This microform edition is protected against unauthorized copying under Title 17, United States Code.

ProQuest Information and Learning Company 300 North Zeeb Road P. Box 1346 Ann Arbor, MI 48106-1346 Sugars and Polyol Compounds in Ambient Aerosols and Cooking Fume Aerosols by Wan Chun Hong B. (Hons) in Chemistry, University of Hong Kong, Hong Kong (1999) _ This is to certify that I have examined the above Ph. thesis and have found that it is complete and satisfactory in all respects, and that any and all revisions required by the these examination committee have been made.

Signature of Author ae CL SS Approved by —=>—⁄ iDr. hanchen Yu, supervise” X. Xiao Yuan Li, Prof. Department Head Department of Chemistry The Hong Kong University of Science and Technology July 2006 ii Authorization I here declare that I am the sole author of the thesis.

I authorize the Hong Kong University of Science and Technology to lend this thesis to other institutions or individuals for the purpose of scholarly research I further authorize the Hong Kong University of Science and Technology to reproduce the thesis by photocopying or by other means, in total or in part, at the request of other institutions or individuals for the purpose of scholarly research a Wan Chun Hong Bachelor of Science in Chemistry, University of Hong Kong, Hong Kong (1999) ili Acknowledgements Dr Jianzhen Yu, my supervisor, gains the greatest gratitude for her invaluable support and guidance during the studies in HKUST. She supervises and teaches me the mysteries in aerosol science and gives me a support on problem-solving in my research works. During these years when I have been working in the laboratory, she has given me challenging projects and tasks to do and to improve myself as a researcher. Sincere thanks go to Prof.

Jian Zhen YU, my supervisor; Dr Song Gao; Dr Lam Lung Yeung; Prof. Frank Lee Shun Cheng for being the members of my thesis examination committee. I want to thank all of my colleagues especially, Elber Sit, Hilda Huang and Simon Ip, in my research group for giving me a pleasant environment to work in. In addition, I want to express my gratitude to Dr.

Yeung and Mr. Lau, project assistant to give a great support and assistance in sample collection in kitchen exhaust study and also, the Atmospheric, Marine and Coastal Laboratory to provide a technical support in LC- MS instrument in my research, I heavily thank to all members in Food and Environmental Hygiene C Section in Hong Kong Government Laboratory during my working period in 2003 — 2005 to give patience to teach me the technique and knowledge on LCMS. iv Finally, I’m thankful to all my friends with whom I have been able to discuss topics related to the scientific work as well as enjoy joyful moments. I specially thank to my parents, my sister and my wife, Joyce Ho, for their love and support during my life.

Table of Content Title Page Signature Page il Authorization Page iii Acknowledgements Table of contents vi List of Publications Xi List of Figures xii List of Tables xvi Appendix xix Abstract XX Chapter 1 Introduction 1.1 The role of aerosols in the atmosphere 1.2 Chemical composition of atmospheric aerosols Chapter 2 Literature Review 14 2.1 Chemical substances in water-soluble carbohydrate-like 15 compounds 2.2 Sources of carbohydrate-like compounds in the atmosphere 15 2.3 Abundance of target compounds 22 2.2 Other carbohydrate-like compounds 27 2.1 Total carbohydrate content 29 2.2 Analysis of individual carbohydrates by 30 gas chromatography 2.3 Analysis of individual carbohydrates by 33 liquid chromatography Chapter 3 Determination of Total Water-soluble Sugar and 37 Polyol Contents in Ambient Aerosols 3.1 Chemical and reagents 42 3.2 Preparation and analysis of standard solutions 42 3.1 Sampling in Hong Kong 44 3.2 Sampling in Nanjing 45 3.3 Sampling in Jeju Island, South Korea 45 3.4 Extraction and analysis of aerosol samples 49 3.3 Results and Discussion 53 3.2 Limit of detection 35 3.3 Abundance of WSMC in bulk ambient aerosols 35 3.4 Size segregated samples collected in Hong Kong 63 Vii Chapter 4 Determination of Sugars and Polyols by Liquid 70 Chromatography Combined with Positive Electrospray Ionization Mass Spectroscopy 4.1 Reagents and standards 74 4.2 Aerosol sample collection and pre-analysis treatment 74 4.4 LC-MS analysis 75 4.5 Results and Discussion 78 4.1 Ionization and MS conditions 78 4.2 Optimization of chromatographic conditions 81 4.3 Seven-point mass calibration 85 4.4 Method recoveries, precision, and limit of detection 87 4.5 Analysis of aerosol samples 90 4.6 Summary 94 Chapter 5 Analysis of Sugars and Polyols by Chloride 98 Attachment in Liquid Chromatography/Negative Ion Electrospray Mass Secptrometry 3.1 Reagents and Instruments 100 5.2 _ˆ LCMS conditions 100 Viii 5.3 Aerosol sample extraction and analysis 103 3.3 Results and Discussion 105 5.1 Mass spectra characteristics 105 5.2 Selection of Ionization Mode 108 5. Optimization of post-column addition parameter 111 5.4 Optimization of LC separation conditions 113 5.5 Calibration and limits of detection 115 5.6 Analysis of aerosol samples 115 5.4 Summary 124 Chapter 6 Determination of glycerol, levoglucosan, fatty acids 125 and cholesterol in cooking oil emission 6.1 Sample collection from restaurant exhausts 127 6.2 Sample collection from heated cooking oil in 131 controlled chamber experiments 6. Sample extraction and treatment 134 6.3 Analysis of individual organic compounds 139 6.3 Results and Discussion 141 6.1 MS characeteristics 141 ix 6.2 Kinetic of BSTFA derivatization reactions 145 6. Recovery of standard compounds (147 6.4 Calibration curves and minimum detection limits 150 6.5 Relationship between glycerol, levoglucosan and 152 other cooking emission compounds 6.6 Target compounds analysis in commercial kitchen exhausts 157 6.

Assessment of contributions of cooking emissions 168 to ambient levogllucosan and Glycerol 6.4 Summary 172 Conclusions and Future Work 180 7.2 — Future Work 183 Bibliography and Reference 184 List of Publications H. Wang, “The chemical composition of inorganic and carbonaceous materials in PM2.5 in Nanjing, China”, Atmos. Yu, “Chemical characterization of water-soluble organic aerosols at Jeju Island collected during ACE-Asia”, Environ. Eric Chun Hong Wan, Jian Zhen Yu, “Determination of Sugar Compounds in atmospheric aerosols by liquid chromatography combined with positive electrospray ionization mass spectroscopy”, J.

Chromatography A, 1107(1-2), 175 — 181, 2006 Eric Chun hong Wan, Jian Zhen Yu, “Determination of Sugar compounds in atmospheric aerosols by liquid chromatography combined negative electrospray ionization mass spectroscopy”, in preparation. Schauer, “Source areas and chemical composition of fine particulate matter in the Pearl River Delta Region of China”, Atmospheric Environment, 40, 3802 — 3815, 2006. Schauer, “Local and region anthropogenic influence on fine particulate trace elements in Hong Kong”, Atmospheric Environment, in presentation. xi List of Figures Figure 1.1 Overview of aerosol composition at several sites, including the unidentified (UD) fraction.

Data were from (a) Pakkanen et al., 1999, (b) Kuhlbush et al., 2000, and (c) Rodriquez et al.2 Chemical composition of PM¿; in Hong Kong (a) Mong Kok (roadside); (b) Tsuen Wan (urban); (c) Hok Tsui (rural) Figure 1.3 Mass balance on the chemical composition of annual mean fine concentrations, 1982, for (a) West Los Angeles and (b) Rubidoux (Riverside) from Rogge et al.1 Mechanism of the formation of levoglucosan in the pyrolysis 19 of cellulose Figure 2.2 Chemica! reaction of BSTFA with —OH containing compounds 32 Figure 3.1 Reaction sequence of the formation of two molecules 41 of formaldehyde from one molecule of monosaccharide using glucose as an example Figure 3.2 Derivatization of formaldehyde with DNPH 41 Figure 3.3 Extraction and analysis procedure for determination 31 of water-soluble monomeric carbohydrate in aerosol samples.4 Example HPLC chromatogram of the DNPH-derivatives 52 Figure 3.5 Individual size distribution of aerosol mass 65 Figure 3.6 Size distribution of total water-soluble mono-carbohydrates 68 xii Figure 3.7 Average size distribution of the total water-soluble 69 mono-carboydrate Figure 3.8 The carbon-mass percentage contributions of WSMC to 69 total WSOC in different size bins Figure 4.1 Structures of the target sugar analysis 73 Figure 4.2 Background subtracted mass spectra of the target sugar 80 compounds in positive ionization.3 Peak areas of [M+NHg]" ions versus different compositions 83 of methanol (a) and acetonitrile (b) in mobile phase.4 SIM chromatograms of an aerosol sample. 84 (Note levoglucosan is scaled by a factor of 0.5 Calibration curves of individual analytes 86 Figure 5.1 Background subtracted ESI- mass spectra of the target 106 sugar compounds in the presence of CH;C].2 Comparison of detection sensitivity between with an 110 without addition of CHCl; under two ionization modes, (a) ESI- and (b) APCT-.3 Comparison of detection sensitivity of three post-column 112 addition solution compositions as a function of the post-column addition flow rate.4 Chromatograms of a standard mixture of 12 sugars and 114 sugar alcohols.5 SIM chromatograms of an aerosol sample analyzed using 120 xiii the carbohydrate column.1 Schematic diagram of the particulate matter sampling system 130 Figure 6.2 Controlled chamber experiment set-up. Top: chamber; 132 Bottom: emission collection setup Figure 6.3 Temperature profile of the heating oil in a controlled 133 chamber experiment Figure 6.4 Flow chart of the filter extraction protocol 137 Figure 6.5 Mass spectra of the TMS derivatives of (a) glycerol, 142 (b) levoglucosan, (c) oleic acid, (đ) myristin, and (e) cholesterol Figure 6.6 Kinetic reaction of glycerol (A) and levoglucosan (B) in 146 BSTFA reaction Figure 6.7 Scatter plots for glycerol versus the fatty acids in nmol/m? 155 (a) tridecanoic acid; (b) myristic acid; (c) pentadecanoic (b) acid; (d) palmitic acid; (e) heptadecanoic acid; (c) (f) oleic acid; (g) stearic acid; (h) myristin; (d) (i) 2-palmitin; (j) 1-palmitin; (k) stearin Figure 6.8 Typical ECOC thermogram of kitchen exhaust samples 160 Figure 6.9 The 73 ion chromatogram for a sample compounds 161 Figure 6.10 Correlation of glycerol with fatty acids and glycerides 164 compounds (a) tridecanoic acid; (b) myristic acid; (c) pentadecanoic acid; (d) palmitic acid; (e) palmitoleic acid; (f) heptadecanoic acid; (g) stearic acid; (h) oleic acid; XIV (i) myristin; (j) 2-palmitin; (k) 1-palmitin; (1) stearin Figure 6.11 Correlation of levoglucosan with fatty acids and glycerides 166 compounds (a) tridecanoic acid; (b) myristic acid; (c) pentadecanoic acid; (d) palmitic acid; (e) palmitoleic acid; (f) heptadecanoic acid; (g) stearic acid; (h) oleic acid; @ myristin; (J) 2-palmitin; (k) 1-palmitin; (1) stearin Figure 6.12 Correlation of levoglucosan with TC 167 Figure 6.13 Comparison of levoglucosan/OC ratios in ambient 171 aerosol samples with those in cooking aerosols and biomass burning aerosols Figure 6.14 Comparison of glycerol/OC ratios in ambient 171 aerosol samples with those in cooking aerosols and biomass burning aerosols XV List of Tables Table 1.1 Ambient annual average concentration (ng/m”) for fine 10 particle organic compounds found in West Los Angeles, downtown Los Angeles, Pasadena, Riverside and San Nicolas Island for 1982 Table 2.1 Structure information on those target compounds 17 Table 2.2 Ambient levoglucosan concentration (ng/m”) in 24 different locations in the world (2002 — 2006).4 Examples of GC analysis of carbohydrates 32 Table 2.5 Applications of using LC for determination of individual 36 carbohydrates Table 3.1 Summary information of aerosol samples collected in 47 Jeju Island Table 3.2 Information on portions of filter used for water extraction 52 and final volume of water extracts.