Department of Environmental Engineering and Science Chia-Nan University of Pharmacy and Science

Thesis for the Degree of Master

Characterization of carboxylic acids and anhydrosugars in dry season ambient aerosol in Chiang Mai Basin, Thailand

(Advisor) Dr. Ying I. Tsai (Co-Advisor)Dr. Khajornsak Sopajaree (Graduate student) Miss Auranee Chotruksa

July 2010


Characterization of carboxylic acids and anhydrosugars in dry season ambient aerosol in Chiang Mai Basin, Thailand

Miss Auranee Chotruksa

Dr. Khajornsak Sopajaree

Department of Environmental Engineering and Science Chia-Nan University of Pharmacy and Science

Thesis for the Degree of Master

Characterization of carboxylic acids and anhydrosugars in dry season ambient aerosol in Chiang Mai Basin, Thailand

Advisor Co-Advisor

: Dr. Ying I. Tsai : Dr. Khajornsak Sopajaree

Graduate student : Miss Auranee Chotruksa

July 2010

ABSTRACT
PM10 aerosol was collected during two periods between February and April of dry season 2010 at urban, suburban and mountain sites in Chiang Mai basin, Thailand. Characteristics and provenance of water-soluble inorganic species, carboxylic acids, anhydrosugars and sugar alcohols in PM10 were investigated. Concentrations of inorganic and organic species in PM10 aerosol at urban site are always higher than at suburban and mountain sites, indicating that more sources were transported to urban area. Acetic acid was the most abundant monocarboxylic acids, followed by formic acid. Oxalic acid was the dominant dicarboxylic acid species during both periods. Concentration of carboxylic acids during the PM10 episode was higher than that during nonepisodic pollution. Carboxylic acids with a peak at daytime during the PM10 episode indicate that carboxylic acids are formed by photochemical reaction and/or are emitted directly by fossil fuels and biomass burning processes. Levoglucosan (Levo) and arabitol were the most dominant anhydrosugar and sugar alcohol, respectively, the ratios of levoglucosan to PM10 in forest fire are 0.53-1.48% by PM10 mass. High concentration of levoglucosan was found at nighttime in both periods, indicating that biomass burning contributed during nighttime. Mass ratio of acetic to formic acids (A/F) > 1 is often used to demonstrate the primary source by wood burning or vehicular emission. This study showed that the contribution of primary sources caused from biomass burning. Moreover, the ratios of M/S in the range of 0.94-1.72 during both periods indicated there exists simultaneously the impaction of primary trafficrelated emissions and secondary photochemical pollution on Chiang Mai ambient environment. The discriminator ratios of biomass burning reported here are 0.78-2.68 of K/Levo, 5.73-36.2 of Levo/Mannosan. Levoglucosan was found to be the most useful marker for biomass burning emitted from forest fire event in the mountain around Chiang Mai basin. The most significant contribution to PM10 in Chiang Mai basin was the photochemical formation of secondary aerosols and primary source from biomass burning contributed by hardwood and softwood of leaves/bark trees. Keywords: Chiang Mai; Biomass burning; Carboxylic acids; Oxalic acid; Levoglucosan; Sugar alcohols; A/F ratio; M/S ratio
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2010 PM10 PM10 PM10 PM10 (Levoglucosan Levo) (arabitol) PM10 0.53-1.48% Levoglucosan PM10 (A/F) 1 malonic/succinic 0.94-1.72 K/Levo= 0.78-2.68, Levo/Mannosan= 5.73-36.2 /

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ACKNOWLEDGEMENTS

This thesis would never have been completed without the help and supports of many people who are gratefully acknowledge here. I would like to express my gratefulness for all of them.

I would like to express my gratitude to all those who gave me the possibility to complete this thesis. I would like to give special thanks to the Department of Environmental and Science of Chia Nan University of Pharmacy and Science, Taiwan and the Department of Environmental Engineering of Chiang Mai University, Thailand, for giving me permission to commence this thesis in the first instance, and do the necessary research work. Moreover, I would like to express my sincere appreciation to all the support and help given from my supervisors Prof. Dr. Ying I. Tsai at Chia Nan University of Pharmacy and Science, Taiwan and Assoc. Prof. Dr. Khajornsak Sopajaree at Chiang Mai University, Thailand who give me helping, suggestions, guidance, warm encouragement and generous supervision throughout my master program. I am grateful to Assist. Prof. Dr. Li-Hao Young and Prof. Dr. Man-Ting Cheng, members of the committees for many valuable suggestions.

I would like to special thank my sampling sites at Faculty of Architecture Chiang Mai University, TOT Public Company Limited and Doi Suthep-Pui National Park Protection Unit, Chiang Mai who allow me to do the necessary research work. And, I would like to thank guards who help me protect collect samplers and take care it.

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In addition, Thanks must go to my entire special person, whom I met in the Atmospheric Research Laboratory at Chia Nan University of Pharmacy and Science, Taiwan. I profoundly indebted to Pei-Ling Wu and Rui-Ling who always help and teach me when I have problem and try to understand me. I would like to thank my best friend, Firstly, Hsin-Ching Wu who help me a lot to do my research work, has been a great consultant for me and take care me when I want to do everything and, June Yu Lee and Yu Ting, who tech and suggest me. I would also like to thank You Cong and Yu-Liang, who thanks for all kind of help of them. I would like to thank all members in the Atmospheric Research Laboratory: Qing-Cheng, Pi-Cheng, Yu-Ru and Yu-Wen.

Especially, I would like to give my special thanks to my parents, my father and my mother who help me for everything for their eternally love, support, encouragement and financial support until the completion of this study.

Auranee Chotruksa

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CONTENTS

ABSTRACT ........................................................................................... I CHINESE ABSTRACT ........................................................................ II ACKNOWLEDGEMENTS ................................................................. III CONTENTS........................................................................................... V LIST OF TABLES .............................................................................. VIII LIST OF FIGURES .............................................................................. X

CHAPTER 1 INTRODUCTION ......................................................... 1 1.1 Introduction............................................................................... 1 1.2 Purpose...................................................................................... 3

CHAPTER 2 LITERATURE REVIEW ............................................. 4 2.1 Aerosol formation mechanism.................................................. 4 2.2 Carboxylic acids in atmospheric aerosols ................................ 5 2.3 Sources of carboxylic acids ...................................................... 8 2.3.1 Direct emissions from anthropogenic sources................... 8 2.3.1.1 Biomass combustion..................................................... 8 2.3.1.2 Motor exhaust emissions .............................................. 9 2.3.2 Emissions from biogenic sources ...................................... 10 2.3.3 Photochemical production of carboxylic acids from precursors .................................................................. 11
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2.4 Anhydrosugars and sugar alcohols ........................................... 19

CHAPTER 3 EXPERIMENTAL ........................................................ 26 3.1 Sampling ................................................................................... 26 3.2 Sampling handing ..................................................................... 29 3.3 Chemical analysis and quality assurance ................................. 29 3.4 Other data.................................................................................. 35

CHAPTER 4 RESULTS AND DISCUSSION ................................... 37 4.1 Meteorological conditions ........................................................ 37 4.2 Mass concentration of PM10 aerosols ....................................... 39 4.3 Aerosol composition of PM10 during non episodic pollution and PM10 episode periods ......................................................... 42 4.4 Concentration of chemical species in daytime and nighttime during non episodic pollution period and PM10 episode...................................................................... 47 4.5 Contribution of chemical species ............................................. 53 4.6 Composition of mass ratios with other studies......................... 63 4.6.1 Carboxylic acids ................................................................ 63 4.6.2 Anhydrosugars................................................................... 65 4.7 Relationships among chemical species in daily PM10 and gaseous pollutants .............................................................. 67 4.8 Comparison with literature data ............................................... 69
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CHAPTER 5 CONCLUSIONS ........................................................... 74 5.1 Conclusion ................................................................................ 74 5.2 Suggestions for the future work................................................ 77 REFERENCE ........................................................................................ 78

VII

LIST OF TABLES

Table 2.1 Saccharides commonly found in atmospheric aerosol and their sources (Caseiro et al., 2007).................... 25 Table 3.1 Ion Chromatography Dionex DX-600 gradient elution ratio............................................................. 31 Table 3.2 The names and chemical structures of carboxylic acids ........ 33 Table 3.3 The names and chemical structures of anhydrosugars and sugar alcohols ................................................................ 34 Table 3.4 Method detection limits (MDLs) of four chemical compound groups measured using IC systems..................... 35 Table 4.1 Meteorological and related air pollution information during the period of study at the suburban site .................... 38 Table 4.2 Mean (SD) chemical composition of PM10 aerosol during non-episode pollution period and PM10 episode emitted from sampling site ............................ 43 Table 4.3 Summary presentation of research findings related to acetic/formic and malonic/succinic ratios in aerosol..................................................................... 64 Table 4.4 Comparison of ratios for various wood burning and atmosphere aerosols (reported in the literature) .............. 66

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Table 4.5 Varimax-rotated principal component loadings of daily PM10 chemical species, gaseous pollutants and wind during intensive observation period of this study .......................................................................... 68 Table 4.6 Inorganic salt concentrations (g m-3) measured at various sampling sites around the world in recent years .................. 71 Table 4.7 Carboxylic acids concentrations (ng m-3) measured at various sampling sites around the world in recent years .......................................... 72 Table 4.8 Anhydrosugars and sugar alcohols concentrations (ng m-3) measured at various sampling sites around the world in recent years .................. 73

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LIST OF FIGURES

Figure 2.1 Idealized schematic of the distribution of surface area of an atmospheric aerosol (Whitby and Cantrell, 1976)............................................... 4 Figure 2.2 Production cycle of carboxylic acids in the atmosphere (Sun and Ariya, 2006) .......................... 7 Figure 3.1 Ecotech MicroVol 1100 Particulate Samplers .................... 28 Figure 3.2 Map of Chiang Mai Basin areas identifying the location of air sampling sites ..................... 28 Figure 3.3 Step for MicroVol sampling and analysis flow chart.......... 32 Figure 3.4 Wind rose charts during intensive observation period (a) IOP1 and IOP2 ................................ 36 Figure 4.1 PM10 mass concentration of intensive observation period with PCD data during period of study .................... 40 Figure 4.2 Correlation of PM10 concentration from PCD data with PM10 concentration from observed site during period of this study.................................................. 41 Figure 4.3 Mean of inorganic species concentration in daytime and nighttime (a) during non episodic pollution period and (b) during the PM10 episode emitted from sampling sites ............................................... 48

Figure 4.4 Mean of carboxylic acids concentration in daytime and nighttime (a) during non episodic pollution period and (b) during the PM10 episode emitted from sampling sites ............................................... 50 Figure 4.5 Mean of anhydrosugar and sugar alcohols concentration in daytime and nighttime (a) during non episodic pollution period and (b) during the PM10 episode emitted from sampling sites ..................................................................... 52 Figure 4.6 Contribution of individual species to total composition in PM10 during intensive observation period of each sites............................................................. 54 Figure 4.7 Contribution of individual species to total amount of inorganic species in PM10 during intensive observation period of each sites .............. 55 Figure 4.8 Contribution of individual species to total amount of carboxylic acids in PM10 during intensive observation period of each sites.......................... 57 Figure 4.9 Correlation of potassium concentration with oxalic acid concentration of each site sampling................. 58 Figure 4.10 Contribution of individual species to total amount of anhydrosugars in PM10 during intensive observation period of each sites .............. 60
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Figure 4.11 Correlation of levoglucosan concentration with potassium concentration of each site sampling.................. 61 Figure 4.12 Contribution of individual species to total amount of sugar alcohols in PM10 during intensive observation period of each sites.......................... 62

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Chapter 1 Introduction
1.1 Introduction

Atmospheric particulate matter are a complicated mixture which are composed by inorganic substances (such as, sulfate, nitrate, ammonium, and potassium) and organic matter, are important resulting from the marine pathway, biomass burning, agriculture burning, automotive exhaust emission and anthropogenic emission (Khwaja, 1995; Chebbi and Carlier, 1996; Souza et al., 1999; Hsieh et al., 2008; Lee et al., 2008; Zhang et al., 2008;). These emissions are impacts on regional air quality and visibility, ecosystems and human health, and climate change (Khwaja, 1995; Souza et al., 1999; Tsai, 2005).

Low molecular weight carboxylic acids are ubiquitous and important components in the tropospheric aqueous and gaseous phases, and in aerosol particles (Chebbi and Carlier, 1996). The carboxylic acids in the particle phase, have the presence in the atmosphere may be result from primary emission (Kawamura and Kaplan, 1987) or from secondary photochemical reactions (Yao et al., 2004). Monocarboxylic acids were observed with a daytime maximum and a nighttime minimum (Khawaja, 1995; Chebbi and Carlier, 1996). Formic and acetic acids constitute the most abundant carboxylic acids in the global troposphere (Khwaja, 1995; Souza et al., 1999). During daytime, vehicular emission appeared to be the primary source of acetic acid, whereas formic and pyruvic acids should be formed photochemically (Souza et al., 1999). In addition, formic acid is one of the photochemical oxidation products from volatile
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organic compounds (VOC), the results show that 80-100% of formic acid stems from biogenic VOC emitted from terrestrial sources (Glasius et al., 2000). Besides that, dicarboxylic acids are among the most abundant organic constituents of ambient particulate matter (Ray and McDow, 2005). Dicarboxylic acids are widely present in the urban, rural and marine atmosphere. Oxalic acid was found as the most abundant species, followed by succinic and/or malonic (Khawaja, 1995; Chebbi and Carlier, 1996; Ho et al., 2006; Hsieh et al., 2008; Tsai et al., 2008; Hsieh et al., 2009).

The biomarker levoglucosan (1,6-anhydro--D-glucopyranose) is formed as a result of the thermal breakdown alteration of the cellulose, accompanied by generally lesser amounts of straight-chain, aliphatic and oxygenated compounds and terpenoids present in the vegetation subjected to biomass burning. The biopolymer (cellulose) decomposes during combustion, yielding a tarry material containing anhydrosugars (Simoneit et al.,1999; Santos et al., 2002; Lee et al., 2008). This compound, together with other thermal decomposition products from cellulose and hemicelluloses (e.g. mannosan, galactosan and levoglucosan) were utilized as tracers for biomass burning (Santos et al., 2002; Schmidl et al., 2008; Bari et al., 2009; Caseiro et al., 2009; Fabbri et al., 2009). It has a large impact on the biomass burning attribution as it is emitted at high concentrations. (Simoneit et al., 1999; Jordan et al., 2006; Zhang et al., 2008). Moreover, Jordan et al., (2006) reported that woodsmoke was estimated to comprise about 95% of wintertime air pollution in Launceston, and the resulting average levoglucosan woodburning emission factor of around 140 mg g-1 particulate matter was found to be consistent with previously determined woodheater emissions.
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1.2 Purpose

In northern of Thailand, few studies describe atmospheric measurements of particulate matter during the dry season (December to March), levels of PM2.5 and PM10 in the Chiang Mai atmosphere are very high, daily PM2.5 (24 h values) during the winter months in Chiang Mai frequently exceeded 200-300 g m-3, and there may be significant health implications associated with these high concentrations (Vinitketkumnuen et al.,2002). In addition, have some studies and data on the water-soluble inorganic species in atmospheric particles and wet deposition are carried out, which no study atmospheric particulate matter (Chantara and Chunsuk, 2008). This can be implied that a comparison of carboxylic acids, anhydrosugars and sugar alcohols in PM10 aerosol has not been reported in the literature.

The purpose of this study is to characterize of inorganic and organic composition (carboxylic acids, anhydrosugars and sugar alcohols) in aerosol during dry season at Chiang Mai Basin were investigated, with a view to explaining differences and identifying the source of pollution in Chiang Mai. Ultimately, this research can be contributed to a better understanding of health effects caused from sources of aerosol.

Chapter 2 Literature review

2.1 Aerosol formation mechanism

Aerosol can either be produced by ejection into the atmosphere, or by physical and chemical processes within the atmosphere (called primary and secondary aerosol production respectively). Examples of primary aerosol are sea spray and windblown dust. Secondary aerosols are often produced by atmospheric gases reacting and condensing, or by cooling vapor condensation (gas to particle conversion). Figure 2.1 shows some of these processes, along with the three sizes ranges (modes) where high aerosol concentrations are often observed.

Figure 2.1 Idealised schematic of the distribution of surface area of an atmospheric aerosol (Whitby and Cantrell, 1976)

Tsai and Cheng (2004) observed the average mass concentration of PM10 was 109.054.1 g m-3. Carbonaceous materials, sulfate, nitrate, and ammonium were the most important contributors to the PM10 component. Concentrations of total carbon in PM10 were significantly high, averaging 37.9 g m-3. By contrast, concentrations of SO42-, NO3-, and NH4+ in PM10 were lower, averaging 10.2, 6.6, and 6.0 g m-3, respectively, 64% of PM10 was made up of fine particles. Coarse particle mass concentrations were approximately 56% of PM2.5 mass concentrations. The most significant contribution to PM10 in the Taichung urban basin was from the photochemical formation of secondary aerosols and carbonaceous materials in the atmospheric environment.

Hsieh et al. (2009) described inorganic species, especially nitrate, were present in higher concentrations during the PM episode. A combination of gas-to-nuclei conversion of nitrate particles and accumulation of secondary photochemical products originating from traffic-related emissions was likely a crucial cause of the PM episode. Sulfate, ammonium, and oxalic acid were the dominant anion, cation, and dicarboxylic acid, respectively, accounting for a minimum of 49% of the total anion, cation or dicarboxylic acid mass.

2.2 Carboxylic acids in atmospheric aerosols

Monocarboxylic acids and dicarboxylic acids are the major constituents of the organic aerosol (Limbeck et al., 2001). Low molecular weight carboxylic acids are ubiquitous and important components in the tropospheric aqueous and gaseous phases, and in
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aerosol particles (Chebbi and Carlier, 1996). The relatively high concentrations of dicarboxylic acids and their identification as atmospheric reaction products from variety of different precursors make it useful to investigate their potential as indicators of secondary organic aerosol formation (Ray and McDow, 2005). Monocarboxylic acids were observed with a daytime maximum and nighttime minimum. Moreover, acetic acid was the most abundant monocarboxylic acid followed by formic, pyruvic and glyoxalic acid, while formic and acetic acid mostly in gaseous (Khwaja, 1995). Dicarboxylic acids were mostly associated with particles. Oxalic acid was the dominant dicarboxylic acid species, followed by succinic acid and malonic acid (Khawaja, 1995; Chebbi and Carlier, 1996; Hsieh et al., 2008; Tsai et al., 2008; Hsieh et al., 2009). Dicarboxylic acid concentrations, particularly oxalic acid, peaked at night during the PM episode, due to accumulation of daytime oxalic acid combined with low wind velocity and low mixing layer height at this time (Hsieh et al., 2008).

By the Figure 2.2 describes the atmosphere organic aerosol conversion performance (Sun and Ariya, 2006), most of the aerosol composition of the mixed chemical species, including a variety of inorganic and organic species, including nature, lakes, oceans and the emissions of volatile organic compounds through the snow will change the formation of aerosols, and aerosols in the atmosphere will combine with inorganic or organic matter into the chemical mixture, and then generate organic aerosols into organic cloud condensation nuclei and ice nuclei (Ice nuclei, IN ), affect the composition of clouds.

hv Cloud Chemical Transformation Transportation Volatile Compounds Gas/Particle Partition Fine Aerosols Coarse Aerosols Organic and inorganic Mixed aerosols Dry Emission Deposition Surface (land, ocean, snow)
Ice Nuclei (IN) IN Cloud Condensation CCN Nuclei (CCN)

Organic aerosols

Emission

Wet Deposition

Emission

Figure 2.2 Production cycle of carboxylic acids in the atmosphere (Sun and Ariya, 2006)

2.3 Sources of carboxylic acids

2.3.1 Direct emissions from anthropogenic sources

The observed amounts of dicarboxylic acids in the particle phase accounted for a small fraction of the organic carbon. Results indicated that photochemical processes and anthropogenic emissions (Yao et al., 2004) such as automobile exhaust, animal wastes, plastic combustions, chemical plants emissions, lacquer minifactory emissions, tinned food plants emissions (starchy foods, fishes, ...), tobacco smoke, refuse incineration factories are major sources of atmospheric dicarboxylic acids. Rhrl and Lammel (2002) reported anthropogenic sources are important for the precursors of succinic, maleic and fumaric acids, namely toluene emissions (from vehicle exhaust, besides other), can be considered as a significant source of maleic and fumaric acids. Wang and Shooter (2004) suggested that solid fuel burning had large influence on the occurrence of these low molecular weight dicarboxylic acids resulting insignificantly higher wintertime concentrations of maleic acid. All of these sources are of local importance and their global contribution seems to be minor. Moreover, only the anthropogenic sources which have an important contribution to atmospheric concentrations of carboxylic acids.

2.3.1.1 Biomass combustion

Primary emissions from wood and coal burning, biomass combustion including wood burning stoves, forest fires, and agricultural
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burnings. (Chebbi and Carlier, 1996) proved that direct emissions of dicarboxylic acids from forest fires represent dicarboxylic acids, dominated by oxalic (C2) followed by succinic (C4) and malonic (C3) acids, also showed a concentration increase. Research has found that forest fires can produce large amounts of DCAs (Narukawa et al., 1999). Whether coal burning is also an important primary source of DCAs remains uncertain. Dicarboxylic acids have several source in cluding primary emission from burning of biomass and fossil fuel, as well as photochemical oxidation of organic precursors (Xingru et al., 2009). Formic and oxalic acids was estimated to contribute from biomass burning about 30-60% (Wang et al., 2007a). Wang and Shooter (2004) suggest that the primary emission from coal and wood burning was the dominant source of maleic acids in an urban atmosphere. Tsai et al. (2010) reported wood burning is the dominant source of maleic acid in atmospheric aerosols.

2.3.1.2 Motor exhaust emissions

Primary emissions from vehicles was the major anthropogenic source of Nonmethane Hydrocarbons (NMHCs) include mobile and stationary source fuel usage and combustion, petroleum refining and petrochemical manufacturing, industrial, commercial, and individual solvent use, gas and oil production. Emissions have been of particular concern in urban areas. In source apportionment of NMHC emissions conducted in Los Angeles in 1976, the weight percentage of emissions (not including industrial emissions and solvent use) was estimated to be 49% motor vehicle exhaust, 16% gasoline spillage, 13% gasoline
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evaporation, 15% natural gas and oil fuel production, and 5% natural gas distribution and use (Godish, 1997). Moreover, Sources of carboxylic acids in the particulate phase. During daytime, vehicular emission appeared to be the primary source of acetic and oxalic acid from both source (Souza et al., 1999). Kawamura et al. (1987) detected very high concentrations of DCAs in automobile exhausts and found that the molecular distributions of DCAs in the Los Angeles air were similar to those in vehicle exhausts.

2.3.2 Emissions from biogenic sources

Emissions from biogenic source which include foliar emissions from forest trees and grasslands and emissions from soils and ocean water are approximately an order of magnitude higher on a global basis than anthropogenic emissions. Foliar emissions from forest trees are comprised mainly of isoprene and monoterpenes with some paraffins and olefins; grasslands, light paraffins and higher HCs; soils, mainly ethane; and ocean water, light paraffins, olefins, and C9-C28 paraffins. Biogenic sources seem to influence the occurrence of malic acid significantly (Rhrl and Lammel, 2002). In addition, emission from biogenic primary sources appeared to be an important contribution to atmospheric concentration of formic and glycolic acids (Souza et al., 1999). During the formic acid sampling period, the air masses were influenced by both direct anthropogenic emissions (benzene, toluene, nitrogen dioxide and acetone) and compounds formed during long-range transport of anthropogenic hydrocarbons (formaldehyde and acetaldehyde).

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Nevertheless, formic acid still had a predominantly (895%) biogenic origin (Glasius et al., 2000).

2.3.3 Photochemical production of carboxylic acids from precursors

Water-soluble organic compounds (WSOC) have several different sources, including primary emissions from biomass burning and fossil fuel combustion, as well as photochemical oxidation of organic precursors of both anthropogenic and biogenic origin (Chebbi and Carlier, 1996). The diacids are largely produced in spring by photochemical oxidation of hydrocarbons and other precursors that are transported long distances from the mid- and low-latitudes to the Arctic, but the production of oxalic acid is in part counteracted by photo-induced degradation possibly associated with bromine chemistry (Narukawa et al., 2002). The precise mechanisms of the production of carboxylic acids by the ozone reactions with atmospheric olefins and, in particular the production of dicarboxylic acids by the reactions of ozone with cycloolefins and with aliphatic diolefins (Chebbi and Carlier, 1996). Wang and Shooter (2004) noted that in summer, oxalic and malonic acids, and the sum of glutaric and adipic acids has strong positive correlations with NO3- (having dominant precursors from vehicle emissions in summer) and temperature. It is therefore suggested that in summer these acids may be formed mainly through photochemical oxidation with vehicle exhausts being the dominant precursors. Phthalic acid has been identified as photochemical product, attributed to anthropogenic precursors (Ray and McDow, 2005). However, as the
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simplest short-chain dicarboxylic acids, oxalic acid is the final product of photochemical decomposition of other dicarboxylic acids in atmospheric aerosol. Consequently, it is the most abundant dicarboxylic acids in atmospheric aerosol (Hsieh et al., 2008; Tsai et al., 2010).

The mass ratio of oxalic to sulfate are present as the end products of organic and inorganic species, the oxalic acid/sulfate mass ratio is informative for determining the formation of dicarboxylic acids from inorganic salts. The ratio for ambient aerosol was higher during PM episode in range 0.504-0.603, while during non-episodic period in range 0.405-0.486 (Hsieh et al., 2008). The oxalic/sulfate ratio has been reported of 0.80-0.83 from incense emissions (Tsai et al., 2010).

The concentration ratios of these acids in atmospheric particles, in particular the malonic acid (C3)/succinic acid (C4) mass ratio, are useful to understanding their importance in the atmosphere. The C3/C4 ratio has been reported to be 0.3-0.5 from vehicular emissions (Kawamura and Kaplan, 1987). Relatively low C3/C4 ratios have been found to be associated with the overwhelming contributions from vehicular exhaust to these acids in some studies, e.g., in downtown and west Los Angeles, in winters in Tokyo, and in Nanjing, China (Kawamura and Kaplan, 1987; Kawamura and Ikushima, 1993; Wang et al., 2002). On the other hand, the mass ratio of C3/C4 in secondary atmospheric particles is much larger than unity (Kawamura and Ikushima, 1993; Kawamura and Sakaguchi, 1999; Yao et al., 2002). For example, Kawamura and Ikushima (1993) reported a maximum mass ratio of 3 in the summer in Tokyo. They found ratios larger than unity concurrent with elevated concentrations of
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oxidants and attributed the source of dicarboxylic acids to secondary atmospheric reactions. Kawamura and Sakaguchi (1999) observed a mass ratio of 3 in the Pacific Ocean, where dicarboxylic acids are expected to originate from secondary reactions. Hence, the ratio of C3/C4 in atmospheric particles is a useful indictor to differentiate primary (vehicular) sources and secondary sources.

The acetic acid/formic acid (A/F) mass ratio was used to distinguish the primary (A/F>1) and the secondary (A/F<1) sources (Villanueva-Fierro et al., 2004; Wang et al., 2007b). Acetic was mainly from primary emissions, while formic acid was largely from secondary transformations, A/F values were collected from major primary emission source including vehicular emission, biomass burning, and soil and vegetation emissions, and from secondary source were reported A/F values.

Khwaja (1995) investigated atmospheric concentrations of carboxylic acids in the gas and particle phases were collected during October 1991 in a semiurban site in the northeastern United States. Formic and acetic acids were the most abundant species and dominant acid in the daytime(most likely resulted from anthropogenic emissions and atmospheric processes), showed notable diurnal variations, with the lowest values in the morning, increased steadily to peak levels during afternoon hours, followed by a decrease in the late afternoon. These variations were similar to that of O3, implying a photochemical production. Concentrations of formic acid (0.80-2.5 ppbv) and acetic acid (0.60-3.4 ppbv), which the low formic/acetic acid ratio (0.23-2.4) in the
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present this study is reflective of the influence of anthropogenic source rich in acetic acid. Formaldehyde concentrations varied from 0.63 to 3.7 ppbv which levels decrease after the mid-afternoon maxima and increase during nighttime. Formic and acetic acids were present mainly in the size fraction below 1.0 m diameter, the acids in particulates have gaseous precursors. Seven carboxylic acids (formic, acetic, pyruvic, glyoxalic, oxalic, succinic, and malonic) have been identified in airborne aerosols. Acetic acid was the most abundant monocarboxylic acid in the particulate phase followed by formic acid, pyruvic and glyoxalic. Dicarboxylic acids were mostly associated with particles, oxalic acid was the most abundant species, followed by succinic acid and malonic acid. It appears that the photooxidation of anthropogenic compounds represents a major source of carboxylic acids in airborne particulate.

Chebbi and Carlier (1996) show that low molecular weight carboxylic acids are ubiquitous components in the tropospheric aqueous phase (found in fog water, rain water, snow, ice water and in cloud water), gas phase and aerosol particles. Formic and acetic acids, the more abundant species in aqueous and gaseous phase, are also ubiquitous in aerosol particles collected in various areas over the world. In addition dicarboxylic acids are mostly present in particle phase, they found that oxalic acid was dominant species followed by succinic, malonic, maleic, adipic and phthalic acids. They observed diurnal variations of carboxylic acids in the atmosphere, with higher concentration during the day than at night. Moreover carboxylic acids found in the dry season higher than in the wet season. Sources of carboxylic acids are comprise anthrogenic emissions (including; wood and biomass burning, motor exhaust emissions), biogenic emissions emitted by vegetations and soils and
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chemical transformations of precursors production photochemical which the precise mechanisms of production of carboxylic acid by the ozone reactions with atmospheric olefin and, in particular the production of dicarboxylic acids by reactions of ozone with cycloolefins and with aliphatic diolefins. As the major source and sinks of these compounds are well-known and their relative importance for local or regional environments are becoming elucidated.

Souza et al. (1999) observed low molecular weight carboxylic acids found in the atmospheric gas and particle-phase were measured during July 1996, Winter, in an urban of So Paulo City, Brazil. Ambient level measurements of formic, acetic, -hydroxy-acetic (glycolic), hydroxy-butyric, oxalic and pyruvic acids in airborne particulate and formic and acetic acids in the gas phase are these reported. Approximately 98% of the total acetic and formic acids were in the gasphase and the gas-aerosol equilibrium was influenced by high levels of relative humidity. Gaseous formic-to-acetic ratio has been used to suggest sources (direct emission; low ratio<1 and in situ formation by photochemical processed; high ratio>1). These acid ratios fell in the 0.941.85 range (avg. 1.24) showed that direct emission from vehicles also contributed to their presence in air. Gaseous formic and acetic were strongly correlation (r=0.93). Thus, photochemical activity to carboxylic acid production appeared to be a very likely source of the gaseous formic and acetic acid level. Particulate total organic compounds (TOC) exhibited a concentration range of 0.34-3.18 mol C/m3. Particulate formic acid was most abundant acid followed by acetic, pyruvic, hydroxylbutyric and glycolic. Among the organic acids studied, oxalic acid was the most abundant. In addition, correlation between oxalic and pyruvic
15

acid concentrations was high (r=0.67) indicated that these acids arise from photochemical. During daytime, vehicular emission appeared to be the primary source of acetic acid, whereas formic and pyruvic acids appeared to be formed photochemically. Beside, emissions from biogenic primary sources were also important contribution to atmospheric concentrations of formic and glycolic acids. Presumably, the photooxidation of pyruvic and glycolic acids gave rise to the oxalic acid. At night, hydroxy-butyric acid levels decreased were similar formic, acetic and pyruvic. Direct vehicular and biogenic emissions seem to be the major sources of TOC in nocturnal measurements. Oxalic acid might arise from vehicular emission, glycolic acid from biogenic emission and formic acid from both sources.

Rhrl and Lammel (2002) determined of malic acid and other C4 dicarboxylic acids in atmospheric aerosol samples. It was found for both rural and urban sites and for various types of air masses that in the summer-time malic acid is the most prominent C4 diacid (64 ngm-3 by average), exceeding succinic acid concentration (28 ng m-3 by average) considerably. In winter-time considerably less, a factor of 4-15, C4 acids occurred and succinic acid was more concentrated than malic acid. Tartaric, fumaric and maleic acids were less concentrated (5.1, 5.0and 4:5 ngm-3 by average, respectively). Tartaric acid was observed for the first time in ambient air. The results indicate that in particular anthropogenic sources are important for the precursors of succinic, maleic and fumaric acids. Biogenic sources seem to influence the occurrence of malic acid significantly.

16

Yao et al. (2002) reported that the C3/C4 mass ratios from a suburban site and two urban sites in Hong Kong were generally larger than unity, suggesting that the primary vehicle emissions were not the major source of dicarboxylic acids in the atmospheric particles at these sites. Instead, secondary sources, such as in-cloud processes, were found to be a major route of formation of dicarboxylic acids, based on the similarity of the size distributions of these dicarboxylic acids and sulfate. The urban measurements reported were made at sites 20-25m above the ground level and not close to the heavy traffic, which may explain the lower contribution of primary vehicular emissions to dicarboxylic acids than when measured at the ground level close to the heavy traffic.

Ho et al. (2003) recently examined the chemical characterizations of PM2.5 and PM10 at three different sites in Hong Kong: Hong Kong Polytechnic University (HKPU), Kwun Tong (KT) and Hok Tsui (HT). HKPU and KT are urban sites and close to the heavy traffic while HT is a remote background site. Ho et al. (2003) found that the ratio of organic carbon to elemental carbon was higher at HT than at HKPU and KT. The organic carbon to elemental carbon ratio in winter was higher than that in summer. Gas-aerosol equilibrium, favoring the partitioning of semi-volatile organic species in the particulate phase under the lower temperatures in the winter, may be an explanation for the observed seasonal differences. The elevated ratio of organic carbon to elemental carbon at HT could be due to a number of possible factors, including a significant secondary source of organic carbon, a lower ambient temperature and a higher biological emission flux at HT. We examine the contribution of secondary chemical reactions to organic acids at HT using the C3/C4 mass ratio.
17

Hsieh et al. (2008) studied speciation and temporal characterization of dicarboxylic acids in PM2.5 during a PM episode and a period of nonepisodic pollution. Period between September and November 2004 in suburban southern Taiwan and dicarboxylic acid and inorganic species content and provenance were investigated. Oxalic acid was the dominant dicarboxylic acid species, followed by succinic acid and malonic acid. Tartaric acid concentrations were the lowest. There was 49.3% more dicarboxylic acid in PM episode aerosol than in non-episodic aerosol. However, daily oxalic acid concentration increased 72.7% in PM episode aerosol, while succinic acid fell 20.9% and malonic acid fell 21.6%, indicating higher conversion of these acids into oxalic acid in PM episode aerosol. Dicarboxylic acid concentrations, particularly oxalic acid, peaked at night during the PM episode. SO42-, NO3-, and NH4+ were also major contributors to nighttime PM episode aerosol. The mass ratio of oxalic acid to sulfate at this time was as high as 60.3%, substantially higher than the 44.5% in non episodic aerosol. High correlations between Cl-, K+, and Na+ and oxalic acid plus backward trajectory data indicate that biomass burning in paddy fields may contribute to oxalic acid content in PM episode aerosol in the study area, especially during nighttime

18

2.4 Anhydrosugars and sugar alcohols

Sugars

or

saccharides

represent

the

major

form

of

photosynthetically assimilated carbon in the biosphere. The plant tissues as structural polysaccharides like cellulose, hemicellulose and pectin. In aerosols, the saccharides are comprised of three main groups: (1) primary saccharides consisting of mono- and disaccharides, (2) saccharide polyols or sugar alcohols (reduced sugars), and (3) anhydrosaccharide or anhydrosugars derivatives such as mainly levoglucosan (1,6-anhydro-D-glucopyranose). Saccharides are ubiquitous in urban, rural and remote aerosol and, therefore, are potentially powerful tools in elucidating organic carbon sources and atmospheric transport pathways (Simoneit et al., 1999; Medeiros et al., 2006). In this study were found sugar alcohols and anhydrosugars in ambient aerosol.

Sugar alcohols are produced in large amounts by many fungi, and several functions have been proposed for these compounds, such as storage or transport carbohydrates. Sugar alcohols often found on the bark of trees, branches and leaves. Bacteria can also form and accumulate polyols (e.g., sorbitol) in order to overcome osmotic stress. Polyols are known component of bacteria, fungi, lichens, invertebrates and lower plants, acting as osmoregulators, stress inhibitors or carbohydrate suppliers (Medeiros et al., 2006). In general, sugar alcohols were found to be most prevalent in the coarse fraction (Pio et al., 2008). Sugar alcohols, such as arabitol and mannitol, are structurally related to levoglucosan. These compounds are markers for fungal spores and mainly occur in the coarse size fraction (Bauer et al., 2008).The sugar alcohols arabitol and
19

sorbitol were found in relative high concentration in leaf smoke samples yielding around 0.14% (arabitol) and 0.25% (sorbitol) of the PM10. The seasonal variation for arabitol, fungal spore production is the highest during summer, is an excellent marker for airborne fungal spores (Zhang et al., 2008).

Anhydrosugars, such as levoglucosan and mannosan, are formed in pyrolysis process of cellulose and hemicelluloses containing materials, and thus are important tracers for biomass burning emission (e.g. wood, rice straw, leaves and biomass). Highly varying patterns were observed in the emission profiles of various molecular markers as a function of fuel type and combustion conditions (Engling et al., 2006; Schmidl et al., 2008; Bari et al., 2009; Caseiro et al., 2009). Schmidl et al.(2008a) described levoglucosan, mannosan and galactosan were found in high concentrations (0.2-15% w/w) in all wood smoke samples. As expected the anhydrosugar levoglucosan, which has long been known as a byproduct from the pyrolysis of cellulose was the most abundant organic compound and was found in all analysed wood smoke samples. Average concentrations ranged from 4.1% in beech wood smoke to 15.1% of total particulate mass in larch wood smoke which is in general agreement with levoglucosan contents of 0.797-31.82% found for American tree species by Fine et al. (2001, 2002, and 2004). A sampling program was implemented to study the chemical markers of wood smoke, including monosaccharide anhydrides (MAs), soluble potassium, and several methoxyphenols. Levoglucosan (1,6-anhydro--D-glucopyranose) has been identified as a major constituent originating from pyrolysis of cellulose. Levoglucosan is emitted at such high concentrations that it can be detected at considerable distances from the original combustion source
20

(Simoneit et al., 1999). Levoglucosan and other anhydrosaccharides are products from the thermal degradation of cellulose and hemicellulose and are commonly used as tracers for wood smoke in the atmosphere (Fabbri et al., 2009). Levoglucosan was measured with peak concentrations of 234 ng m-3 during periods with smoke influence from local fires, and primary biomass burning smoke contributions to fine particle organic carbon were estimated to be as high as 100% on individual days during that period (Engling et al., 2006). The levoglucosan concentration exhibited a strong annual cycle with higher concentrations in the cold season. The minor anhydrosugars had a similar annual trend, but their concentrations were lower by a factor of about 5 and about 25 in the cold season for mannosan and galactosan, respectively.

Mannosan, another anhydrosugar emitted during pyrolyses of cellulosic material, was found to be a useful compound for distinguishing between soft- and hardwood combustion. Mannosan is formed in the pyrolysis of hemicelluloses containing mannose, which occur mainly in conifers. Mannosan is the second most abundant anhydrosugar in the wood smoke samples. Biomass smoke PM from conifers contains around five times higher concentrations of mannosan than smoke PM from deciduous trees The mannosan level of around 0.4% found in leaf smoke PM10 is very similar to that from hardwood log combustion reported by Schmidl et al. (2008a). Mannosan average concentration in the background area was 16889 ng m-3, while the average concentration in the residential area was 313237 ng m-3 (Glasius et al., 2008)

21

The use of levoglucosan as a tracer for wood burning in general and the levoglucosan and mannosan ratio to differentiate between hardwood and softwood smoke to PM load. Considering the ratio of levoglucosan to mannosan the difference between hard- and softwood types becomes even more marked. Hardwoods give high ratios, around 14-15, while softwoods give low ratios, 3.6-3.9 (Schmidl et al., 2008a). The average ratio and standard deviation of the ratio levoglucosan and mannosan was found to be 4.60.7 (Ward et al., 2006). The ratio between levoglucosan and mannosan in the particulate emission from forest fire was found to be 3.50.8 (Pio et al., 2008).

Moreover, relationships between the different anhydrosugars the combustion of softwood was found to be dominant for the wood smoke occurrence in ambient air at the investigated sites. Potassium, a commonly used tracer for biomass burning, correlated well to levoglucosan, with a mass ratio of around 0.80 in the cold season. (Caseiro et al., 2009). Schmidl et al. (2008a) found K/levoglucosan ratios of 0.005 and 0.05 for the major Austrian wood types beech and spruce, espectively, when burnt in a small ceramic stove. In US studies burning north American wood types in fireplaces (e.g. Fine et al., 2002, 2004) K/levoglucosan ratios were in the range of 0.017-0.23. Despite those low K/levoglucosan values from source (fireplaces, stoves,.) studies, authors have reported higher ratios from smoke-impacted or non smoke-impacted ambient aerosol.

Jordan et al. (2006) describes levoglucosan major constituent of woodsmoke in ambient air collected in Launceston, Australia during the
22

winter months (May-September) of 2002-2003 were analyzed for organic compounds. The proportion of radiocarbon (14C) in aerosols used to apportion biomass which analyzes having relatively high precision and accuracy. Levoglucosan is a suitable tracer species for quantifying the contribution of wood smoke to air pollution. This report show levoglucosan emissions from a woodsmoke averaged 14055 mg g-1 PM indicated that woodheaters is major source of air pollution in Launceston.

Zhang et al. (2008) estimated that levoglucosan as a molecular marker are increasingly employed as biomass burning, were collect samples PM2.5 and PM10 in Beijing from July 2002 to July 2003. The samples were analyzed for levoglucosan, related saccharidic compounds, organic and elemental carbon, and ionic species. Levoglucosan and biomass burning particles are mainly present in the fine aerosol fraction. The seasonal variation for arabitol suggests that fungal spore production is the highest during summer. A long-range transported biomass burning event was indentified for the case of 7 May 2003. Besides, some other episodes were discussed. So, biomass burning is the only source for levoglucosan, this phenomenon may be explained by biofuel combustion in the countryside of suburban Beijing and neighboring provinces.

Caseiro et al., 2007 described for the quantification of primary sugars, sugar alcohols and anhydrosugars in atmospheric aerosols. The determination of saccharides in atmospheric aerosol could use as specific tracers show in Table 2.1 provides a list of important saccharides found in atmospheric aerosols. Saccharides present in atmospheric particulates originate from different source types. Micro-organisms, plants and
23

animals

can

release

into

the

atmosphere

primary

saccharides

(monosaccharides including glucose, fructose, xylose and disaccharides such as sucrose and trehalose) while fungi, lichens and bacteria produce saccharidic polyols, also denoted as sugar alcohols, such as arabitol, mannitol and sorbitol. Anhydrosaccharides on the other hand, such as levoglucosan, derived from cellulose, and galactosan and mannosan, derived from hemicelluloses, are the primary thermal degradation products of structural polysaccharides present in biomass.

Caseiro et al. (2009) reported that levoglucosan yearly averages ranged from 0.12 to 0.48 g m-3. The sites in Graz showed higher concentrations compared to the other regions, while background sites, in general, evidenced slightly lower concentrations than urban sites. The ratios between levoglucosan and mannosan and between levoglucosan and galactosan showed a range of 4.1-6.4 and 11-22, respectively, in the periods where biomass burning is expected to be a strong source. Moreover, the ratio of levoglucosan and potassium, another tracer for biomass burning, were well correlated at all sites. The ratios between those two species were rather below 1 in the cold season and around 3 in the warm season.

24

Table 2.1 Saccharides commonly found in atmospheric aerosol and their sources (Caseiro et al., 2007)
Compound Primary sugars (mono- and disaccharides) Arabinose Fructose Galactose Glucose Source Lichens Lichens Soil biota Soil biota Fungi Lichens Soil biota Wood burning Soil biota Soil biota Soil biota Plants Soil biota Yeast Bacteria, fungi Soil biota Fungi, Lichens Lichens Soil biota Soil biota Soil biota Fungal spores Fungi Lichens Soil biota Bacteria Lichens Soil biota Fruits, berries, hardwood Soil biota Wood burning Wood burning Wood burning Wood burning

Mannose Xylose Maltose (monohydrated) Sucrose Mycose (Trehalose) Sugar alcohols Arabitol Erythritol Glycerol Inositol Mannitol

Sorbitol Xylitol Anhydrosugars Galactosan (1,6-anhydro--D-galactopyranose) Levoglucosan (1,6-anhydro--D-glucose, 1,6-anhydro--D-glucopyranose) Mannosan (1,6-anhydro--Dmannopyranose) 1,6-Anhydrogluco-furanose

25

Chapter 3 Experimental

3.1 Sampling and sampling sites

Chiang Mai is the big city northern part of Thailand and with a population of about 82,000 inhabitants in the city. It is most important biomass burning producers in the country during dry season. To facilitate manual harvesting, its farmers still burning straw/leaves/agriculture waste, or forest fire. This generates a great cloud of smoke that spread over the city and its surrounding area.

Aerosol samples were collected on a 47-mm Teflon filters(Zefluor, Pall) using a Ecotech MicroVol 1100 Particulate Sampler (Figure 3.1) with a total flow rate of 3 L min-1, between February to April 2010. Three sampling sites including Faculty of Architecture Chiang Mai University (CMU site), TOT Public Company Limited (TOT site) and Doi SuthepPui National Park Protection Unit (STM site) were selected for particulate matter monitoring. The field descriptions were given as follows and locations of the sites are shown in Figure 3.2.

Faculty of Architecture Chiang Mai University (CMU; Located at latitude 18o4754.90 N and longitude 98o5655.75 E) was urban, located about 2 km western of Chiang Mai City, medium traffic, hardly impacted by anthropogenic activities, near the Suthep mountain and excellent ventilation. The sampling monitors were placed on the rooftop, set at a height of 12 m above ground.
26

TOT Public Company Limited (TOT; Located at latitude 18o 41 40.04 N and longitude 99o 2 59.45 E) was suburban. The former is located about 15 km southeast of the city, alongside a busy street and within the busy highway No. 11, are the traffic-impacted site. Industrial zone (such as petrochemical, cement, ceramic and metal industrial) was about 2 km eastern from sampling site.

Doi Suthep-Pui National Park Protection Unit (STM; Locate at latitude 18o 48 32.71 N and longitude 98o 53 27.81 E), is surrounded by mountains, the sampling set at the Suthep-Pui mountain, 1400 m above sea level, located near the Bhubing Palace is Chiang Mai most famous travel place, with a little traffic. STM site is a sampling site situated outside the city and representative for regional moutain conditions.

Intensive observation periods (IOP) of dry season were observed during the two period of sampling. Firth period were collected between 2 March to 2 April 2010 (IOP1), which sampling at two sites, CMU and TOT site. Second period were collected between 9 to 21 April 2010 (IOP2), sampling at two sites, CMU and STM site. Each sampling collected two sets of aerosol samples were collected daily, one from 7 am to 7 pm (12 h: daytime) every 3 days and another from 7 pm to 7 am (12 h: nighttime) every 3 days.

27

Figure 3.1 Ecotech MicroVol 1100 Particulate Sampler

Chiang Mai

N STM site
latitude 18o 48?32.71? N longitude 98o 53?27.81? E

Bangkok

CMU site Chiang Mai City

latitude 18o4754.90? N longitude 98o5655.75? E

Thailand

Cement industrial Metal industrial

2 km 2 mile

TOT site
latitude 18o 41?40.04? N Ceramic longitude 99o 2?59.45? E industrial

Figure 3.2 Map of Chiang Mai Basin areas identifying the location of air sampling sites.

28

3.2 Sampling handing

Before and after sample collection, filters were conditioned at 405% RH for 24 hours and subsequently weighed at 503% RH using a Mettler Toledo AT261 analytical balance with a sensitivity of 10 g and a Sartorius CP2P analytical balance with a sensitivity of 1 g. All weight measurements were repeated three or more times and the Shewart control procedures were followed to ensure reliability. Additionally, blank filters were prepared by purging in 99.995% pure nitrogen for 30 seconds and then processed as for sample-containing filters.

3.3 Chemical analysis and quality assurance

The sample-containing filters, unexposed blanks will be stored in petri dishes placed inside an unlit refrigerator below -18C to prevent loss of semi-volatile species. For analyzing compounds, the filter paper will be placed in a PE bottle, 10.0 mL of deionized water (resistivity >18.0 M cm-1 at 25C, Barnstead) will be added and the contents will be shaken (Yihder TS-500 Shaker) in an unlit refrigerator at 4 C for 90 min to prevent the decomposition of the extracted carboxylic acid species. The liquid is then filtered through a 0.2 m ester acetate filter and the aqueous filtrate will be is characterized using IC, following a slightly modified version of the method of Hsieh et al. (2008) and Tsai et al. (2010).

29

The ion chromatography system (IC) model DX-600, Dionex is equipped with a gradient pump (Model GP50), an ASRS-Ultra anion selfregenerating suppressor, a conductivity detector (CD25), a Spectrasystem automated sampler (AS3500) with 2 mL vials, and a Teflon injection valve using a 1000 L sample loop, in combination with analytical column and Ion Pac AG11-HC, AS-11-HC (4 mm), eluent for the DI water (deionized), 5 mM NaOH, 100 mM NaOH and 100% MeOH gradient elution method to conduct analysis. The flow rate is maintained at 2.0 mL min-1 during the carboxylic acid analyses, which Ion Chromatography Dionex DX-600 gradient elution ratio is shown in Table 3.1. This method allows for the analysis of acetic acid, formic acid, glutaric acid, succinic acid, malonic acid, maleic acid, tartaric acid, malic acid, fumaric acid, oxalic acid and phthalic acid in the aerosol samples.

Additionally, 1000 L of the aqueous extract will be injected into IC Model Dionex ICS-2500 using 9 mM Na2CO3 eluent at a flow rate of 1.4 mL min-1. Concentrations of the separated inorganic species including Cl-, NO3- and SO42-, are determined in analytical column RFICTM Ion Pac AS14A, AG14A (4 mm). Cation system to IC Model Dionex ICS-1000, AS1000, analytical column and Ion Pac CG12A, CS12A (4 mm), injection volume 25 L and an isocratic 20 mM MSA (CH4O3S) eluent at a flow rate of 1.0 mL min-1 will be used for determination of cations, including Na+, NH4+, K+, Mg2+ and Ca2+. Department of anhydrosugars (levoglucosan and mannosan) and sugar alcohols (arabitol, glycerol, erythritol, trehalose dehydrate and mannose) are to IC Model Dionex ICS-2500 (ED50, GP50, AS50), analytical column and Carbo PacTM MA1 (4 mm), flow rate 0.4 mL/min, injection volume 0.2 mL, eluent conducted for the 400 mM NaOH component analysis. Figure 3.3 shows
30

flow chart of MicroVol sampling and analysis. Moreover, Table 3.2 shows chemical structures of carboxylic acids and Table 3.3 showns chemical structure of anhydrosugars and sugar alcohols.

All reagents are of analytical grade, obtained from Merck (Darmstadt, Germany), and are used without further purification. The solutions will be prepared using deionized water from which organic carbon had been removed and the detection limits corresponded to 10-50 ng for the carboxylic acids investigated. Method detection limits (MDLs) of four chemical compound groups measured using IC systems shown in Table 3.4.

Table 3.1
Time(min) 0.0 9.2 12.2 22.0

Ion Chromatography Dionex DX-600 gradient elution ratio

H2O 80% 80 % 0% 0% 5 mM NaOH 4% 4% 84 % 49 % 100 mM NaOH 0% 0% 0% 35 % 100% Methanol 16 % 16 % 16 % 16 %

31

Before weighing Teflon filters were condition at 40 5% RH 24 hr

Sampling PM10 aerosol by Micro Vol 1100

After weighing Teflon filters were condition at 50 5% RH 24 hr

15 mL of centrifuge tube placed and added deionized water 5 mL

Vibration machine 90 minute

Filtered through a 0.2 m ester acetate filter

1000 L filtrated to IC-Dionex DX-600 Analyze: Carboxylic acids

25 L filtrated to IC-Dionex ICS-1000 Analyze: Cation

1000 L filtrated to IC-Dionex ICS-2500 Analyze: Anion

200 L filtrated to IC-Dionex ICS-2500 Analyze: Anhydrosugars and Sugar alcohols

Figure 3.3 Step for MicroVol sampling and analysis flow chart

32

Table 3.2

The names and chemical structures of carboxylic acids

IUPAC name Chemical formula Structural formula

Common name Carboxylic acids Formic acid

methanoic acid

HCOOH

HO

Acetic acid

ethanoic acid

CH3COOH

HO O

Oxalic acid

ethanedioic acid

HOOC-COOH

Malonic acid

propenedioic acid

CH2(COOH)2

Succinic acid

butanedioic acid

C2H4(COOH)2

Glutaric acid

pentanedioic acid

C3H6(COOH)2

Maleic acid

cis-butenedioic acid

C2H2(COOH)2

Fumaric acid

trans-butenedioic acid

C2H2(COOH)2
OH O

Phthalic acid

benzene-1,2dicarboxylic acid

C6H4(COOH)2

HO

Malic acid

monohydroxybutaned ioic acid 2,3dihydroxybutanedioic acid 3-carboxy-3-hydroxy pentanedioic acid

C2H3(OH)(COOH)2

Tartaric acid

C2H2(OH)2(COOH)2 C3H4(OH)(COOH)3

Citric acid

33

Table 3.3

The names and chemical structures of anhydrosugars and sugar alcohols

Common name Anhydrosugars Levoglucosan

IUPAC name

Chemical formula

Structural formula

1,6-anhydro--Dglucopyranose 1,6-anhydro--Dmannopyranose

C6H10O5

Mannosan Sugar alcohols Arabitol

C6H10O5

(2R,4R)-pentane-1,2,3,4,5pentol

C5H7(OH)5

Glycerol

propan-1,2,3-triol

C3H5(OH)3

Erythritol

(2R,3S)-butane-1,2,3,4tetraol

C4H6(OH)4

34

Table 3.4 Method detection limits (MDLs) of four chemical compound groups measured using IC systems

Species

MDL
-3 a

Species

MDL

Inorganic species (g m ) Sulfate 0.011 Nitrate 0.018 Chloride 0.015 Sodium 0.022 Ammonium 0.009 Potassium 0.008 Magnesium 0.018 Calcium 0.007 Sugar Alcohols (ng m-3) Arabitol 5.95 Glycerol 4.16 Erythritol 3.15

Carboxylic Acid (ng m-3) Acetic 12.99 Formic 9.24 Glutaric 3.75 Succinic 6.48 Malic 4.39 Malonic 2.30 Tartaric 7.55 Maleic 0.51 Fumaric 0.79 Oxalic 2.27 Phthalic 1.70 Citric 0.29 Anhydrosugars (ng m-3) Levoglucosan 81.03 Mannosan 15.10

Assumption of sampling volume 6.34 m3

3.4 Other data The charts of the wind rose observed in Figure 3.4 from Thailand Pollution Control Department demonstrate that the difference in prevailing wind direction during intensive observed two periods due to different source of pollutant. During IOP1, wind blows predominately from northwestern to north and second from southeastern, which carries as pollutant from the agriculture burning, forest fire burning and rural areas towards Chiang Mai. As during IOP2, prevailing wind direction from southeastern to south (which would bring pollutant from industrial and agriculture areas) up from other province to Chiang Mai were shown to preferentially occur during dry season. These results show that
35

influence of wind direction due to difference source of pollutant from two intensive periods significantly. Moreover, wind blows at speed of 3.6-5.7 m/s of IOP2 higher than IOP1. a IOP1

b IOP2

Figure 3.4 Wind rose charts during intensive observation period (a) IOP 1and (b) IOP2
36

Chapter 4 Results and discussion

4.1 Meteorological conditions The ambient air quality data were obtained from the Thailand Pollution Control Department (PCD), information was obtained on Air Quality data from February to April 2010 over Chiang Mai province, Thailand. The Air Quality was particularly useful for observing pollutant concentrations. Moreover visibility was obtained from Thai Meteorological Department during sampling.

Site meteorological data shows in Table 4.1 confirm designations of each period of study. In this study to explain two period was the non-episodic pollution period (PM10<120 g m-3) and the PM10 episode (PM10>120 g m-3). During the PM10 episode and non-episodic pollution period, average PM10 concentrations were 156.8838.10 g m-3 and 78.7120.42 g m-3 in IOP1 period versus 105.9316.79 g m-3 in IOP2 period, respectively. The data shows concentrations of pollutant, especially O3, SO2, NO2, NOx, NO and CO, which represents traffic emission, IOP1 period was higher during the PM10 episode. In addition, wind speed during intensive observed nighttime lower than daytime both of period. The results suggest that due to accumulated pollutant in the nighttime and contributed in the daytime. Moreover, higher temperature, lower relative humidity and lower wind speed during the PM10 episode to be high O3 is due to lower visibility, higher PM10 and increase pollutant of these periods. However IOP2 period of this study were high temperature, lower relative humidity, low wind speed and high O3 than IOP1 due to higher SO2, lower visibility, high PM10 can to increase pollutant emission to atmospheric aerosol in Chiang Mai basin.
37

Table 4.1 Meteorological and related air pollution information during the period of study at the suburban site.
During non-episode Parameter
Temperature ( C) Relative humidity (%) Pressure (mmHg) Visibility (km) Prevailing wind direction Wind speed PM10 (g m ) O3 max (ppb)a O3 (ppb) SO2 (ppb) NO2 (ppb) NOx (ppb) NO (ppb) CO (ppm)
a
-3

During the PM episode IOP1 Mean SD

28.49 52.11 731.92 5.80 1.60 156.88 90.86 39.58 1.53 14.69 17.94 3.30 1.11 2.65 7.09 1.38 1.38 0.43 38.10 31.21 24.24 0.46 3.12 2.56 1.11 0.26 2.42 2.42 1.31 0.54 0.66 16.79 26.51 17.93 0.65 2.75 2.72 0.32 0.10

IOP1 Mean SD
25.61 54.07 731.17 8.21 1.68 78.71 49.06 18.72 0.70 14.64 19.78 5.16 0.78 3.38 7.88 1.56 1.24 0.54 20.42 29.42 18.97 0.41 5.34 7.44 2.61 0.19

IOP2 Mean SD
31.83 43.83 729.18 7.13 1.65 105.93 91.00 50.71 1.77 11.62 13.50 1.97 0.91

NW-N

SE-S

NW-N

Average maximum hourly ozone in each sampling sets. Note: Wind speed during IOP1 daytime= 1.890.48 m/s and nighttime = 1.440.47 m/s Wind speed during IOP2 daytime= 2.160.46 m/s and nighttime = 1.140.34 m/s

38

4.2 Mass concentration of PM10 aerosols Figure 4.1 shows the variations of PM10 mass concentration during dry season two periods, firth intensive observation period (IOP1) from 2 Mar. to 2 Apr. in 2010 and second intensive observation period (IOP2) during 9-20 April 2010, comparison intensive observation of two periods between CMU site and TOT site (IOP1) versus CMU site and STM site (IOP2) of this study with PM10 mass concentration from PCD data in Chiang Mai. In this study, show similar pattern with PCD data. The average concentration of PM10 at IOP1-TOT site higher than IOP1-CMU site, IOP2-CMU site and IOP2-STM, respectively, which IOP1 mass concentration of PM10 higher than IOP2 resulted from during collected sampling IOP1 during episode of pollutant, indicating that ambient air pollution in Chiang Mai influenced on the sample sites of this study. Moreover, the PM10 concentration during non episodic pollution and PM10 episode of IOP1-TOT site (77.4425.07 g m-3 versus 142.4617.74 g m-3) higher than IOP1-CMU site (58.0830.85 g m-3 versus 139.5613.97 g m-3) and IOP2CMU site (81.9629.64 g m-3) versus IOP2-STM site (65.1620.05 g m-3) , respectively, during non episodic pollution period shows in Table 4.2, indicating that PM10 was evenly distributed in suburban more than urban and mountain site, which TOT site is located in southern part of Chiang Mai basin and closely industrial area. Therefore, pollutants can be transported from up wind area or due to the emissions from industrial activities.

39

PM10 concentration
PM10 concentration
140 160 180
100 120 140 160 180

100

120

20
20 40 60 80 0

40

60

80

200

220

240

260

0 PM10 conc. of STM site PM10 conc. of PCD data PM10 conc. of CMU site

4/9~4/11, 2010(D)

4/9~4/11, 2010(N)

PM10 conc. of TOT site

PM10 conc. of PCD data

PM10 conc. of CMU site

4/12~4/14, 2010(D)

4/12~4/14, 2010(N)

Date

Figure 4.1 PM10 mass concentration of intensive observation period with

PCD data during period of study

40
IOP2

Date

4/15~4/17, 2010(D)

4/15~4/17, 2010(N)

4/18~4/20, 2010(D)

4/18~4/20, 2010(N)

IOP1

2/2~2/4, 2010(D) 2/2~2/4, 2010(N) 2/5~2/7, 2010(D) 2/5~2/7, 2010(N) 2/8~2/10, 2010(D) 2/8~2/10, 2010(N) 2/11~2/13, 2010(D) 2/11~2/13, 2010(N) 2/14~2/16, 2010(D) 2/14~2/16, 2010(N) 2/17~2/19, 2010(D) 2/17~2/19, 2010(N) 2/20~2/22, 2010(D) 2/20~2/22, 2010(N) 2/23~2/25, 2010(D) 2/23~2/25, 2010(N) 2/26~2/28, 2010(D) 2/26~2/28, 2010(N) 3/1~3/3, 2010(D) 3/1~3/3, 2010(N) 3/4~3/6, 2010(D) 3/4~3/6, 2010(N) 3/7~3/9, 2010(D) 3/7~3/9, 2010(N) 3/10~3/12, 2010(D) 3/10~3/12, 2010(N) 3/13~3/15, 2010(D) 3/13~3/15, 2010(N) 3/16~3/18, 2010(D) 3/16~3/18, 2010(N) 3/19~3/21, 2010(D) 3/19~3/21, 2010(N) 3/22~3/24, 2010(D) 3/22~3/24, 2010(N) 3/25~3/27, 2010(D) 3/25~3/27, 2010(N) 3/28~3/30, 2010(D) 3/28~3/30, 2010(N) 3/31~4/2, 2010(D) 3/31~4/2, 2010(N)

Figure 4.2 shows the relationship between PM10 from PCD data and PM10 from during intensive observed. During IOP1, PM10 concentration from CMU site and TOT has the good relationship with PM10 from PCD data, while during IOP2 the available data is too less for analysis.

250

250

IOP1-CMU site
200

IOP1-TOT site
200

PM10 concentration

PM10 concentration

y = 0.923x - 5.794 r = 0.801

y = 0.632x + 50.23 r = 0.692

150

150

100

100

50

50

0 0 50 100 150 200 250

0 0 50 100 150 200 250

PM10 concentration of PCD data

PM10 concentration of PCD data

140

IOP2-CMU site
120

100

IOP2-STM site

y = 1.044x - 28.67 r = 0.591

PM10 concentration

80

100

y = 0.098x + 54.74 r = 0.077

PM10 concentration

80

60

60

40

40

20

20
0

0 0 50 100 150 200 250

50

100

150

200

250

PM10 concentration of PCD data

PM10 concentration of PCD data

Figure 4.2 Correlation of PM10 concentration from PCD data with PM10 concentration from observed site during period of this study

41

4.3 Aerosol composition of PM10 during non episodic pollution and PM10 episode periods

The concentrations and standard deviations of inorganic salts, carboxylic acids, anhydrosugars, sugar alcohols and ratios of aerosol components during non episodic pollution period and PM10 episode collected at sampling sites of this study are shown in Table 4.2.

The sulfate concentration in PM10 during observation period of this study, IOP2 (7.975.96 g m-3 at CMU site versus 5.472.91 g m-3 at STM site) higher than IOP1, which sulfate increase 3 times. During IOP2 concentration with peak daily maximum high ozone concentration was 91.0026.51 ppb (Table 4.1). These results may be during the ozone increase due to high sulfate, significant photochemical formation processes. It may be increased anthropogenic activity and photochemical reaction, which IOP2 period collected during the Songkran celebrations (Thailand New Years Day) are still in the northern city of Chiang Mai, where most famous for foreigners and many visitor to become a party or may be contributed from biomass burning due to high levoglucosan of this period, also high sulfate in ambient aerosol. Sulfate was the dominant inorganic salts, whereas during non episodic pollution IOP1TOT site nitrate was the dominant species. Particulate nitrate is transformed through the photo-oxidation of NO2 derived from combustion of fossil fuels (Logan, 1983). The major source of nitrate in TOT site may be NOx emission from traffic vehicles. Particulate ammonium mainly originates from ammonia vapor. Ammonium sulfate is the most stable while ammonium chloride is the most volatile, hence ammonia prefers to react with sulfuric acid or sulfate (HO et al., 2003).
42

Table 4.2
Mean (SD) chemical composition of PM10 aerosol during non-episode pollution period and PM10 episode emitted from sampling sites
During non episodic period pollution Species IOP1-CMU (n=19) Mean PM10 (g m ) Inorganic species (g m-3) Sodium Ammonium Potassium Magnesium Calcium Chloride Nitrate Sulfate Carboxylic acids (ng m-3) Acetic acid Formic acid Glutaric acid Succinic acid Malic acid Malonic acid Tartaric acid Maleic acid Fumaric acid Oxalic acid Phthalic acid Citric acid Anhydrosugars (ng m-3) Levoglucosan Mannosan Sugar alcohol (ng m-3) Arabitol Glycerol Erythritol Ratios A/F M/S Oxalic/Sulfate K/Levo Levo/Manno Levo/PM10(%)
-3

During the PM10 episode IOP2-STM (n=8) Mean 65.16 11.34 0.71 1.35 0.75 0.12 0.93 0.62 1.36 5.49 909.48 258.73 57.57 24.06 26.92 35.02 33.02 23.91 35.54 14.28 374.13 6.81 19.48 996.14 967.32 28.82 189.02 129.07 45.31 14.64 4.49 1.23 0.07 0.78 33.56 1.48 SD 20.05 4.63 0.65 0.65 0.28 0.04 0.30 0.21 0.55 2.91 398.47 200.61 44.56 16.17 18.15 22.85 21.03 16.97 26.68 14.41 142.29 4.81 18.14 581.95 582.46 7.47 50.12 31.00 21.90 6.67 IOP1-CMU (n=10) Mean 139.56 15.60 1.19 2.71 2.31 0.73 1.88 0.59 2.34 3.86 1950.83 422.48 115.35 42.73 105.73 136.36 99.54 54.33 92.32 27.38 758.87 54.39 41.34 1258.76 1175.50 83.25 746.90 334.16 346.55 66.19 3.66 0.94 0.20 1.96 14.12 0.84 SD 13.97 4.54 1.04 0.79 0.56 0.28 0.67 0.92 1.95 1.08 547.17 326.74 89.97 24.90 51.68 51.71 32.50 23.80 78.97 13.92 198.82 31.67 34.77 797.26 791.26 20.68 266.15 54.00 194.37 29.43 IOP1-TOT (n=15) Mean 142.46 13.76 0.63 2.04 1.92 0.56 2.09 0.48 2.64 3.41 1605.77 456.33 51.70 34.37 70.05 94.60 77.68 42.93 93.10 15.99 610.56 37.68 20.77 1145.37 1073.13 72.24 573.69 303.59 222.09 48.01 8.83 1.11 0.18 1.79 14.85 0.75 SD 17.74 4.55 0.78 0.72 0.52 0.27 0.85 0.62 2.12 1.09 442.38 313.68 25.42 21.28 32.28 47.42 24.56 24.48 81.35 10.89 162.61 24.24 15.96 645.90 646.88 23.40 242.68 70.48 161.44 30.98

IOP1-TOT (n=14) Mean 77.44 7.85 0.61 0.93 0.83 0.26 1.26 0.49 2.08 1.39 1125.85 486.07 51.73 9.19 24.16 45.65 41.65 33.25 121.26 6.77 243.52 25.04 37.57 466.69 413.01 53.68 271.84 192.71 61.10 18.03 9.40 1.72 0.18 2.02 7.69 0.53 SD 25.07 4.04 0.81 0.65 0.45 0.10 0.46 0.60 1.53 0.87 580.35 386.85 34.95 6.95 13.80 22.66 15.67 34.89 67.29 5.78 127.58 19.09 33.43 258.22 253.56 22.43 84.70 61.36 55.00 5.83

IOP2-CMU (n=8) Mean 81.96 13.90 0.63 1.21 0.78 0.11 1.26 0.63 1.30 7.97 1347.66 385.02 66.94 51.84 61.05 67.05 61.63 48.48 44.28 38.28 477.50 6.92 38.68 1016.01 988.69 27.32 175.29 134.01 26.92 14.37 5.75 1.01 0.06 0.79 36.19 1.21 SD 29.64 6.81 0.25 0.42 0.37 0.03 0.43 0.26 0.38 5.96 428.71 227.48 40.19 38.18 38.64 37.05 29.89 28.65 22.58 30.52 73.49 2.94 28.08 567.11 567.78 3.16 32.80 15.48 13.36 7.21

5.72 1.30 0.14 2.68 5.73 0.57

SD 30.85 3.92 0.49 0.89 0.57 0.30 0.61 0.18 0.62 1.46 517.76 266.09 37.57 10.27 36.50 46.08 27.43 30.38 66.47 7.33 207.48 23.46 29.87 189.11 174.43 19.83 102.24 80.73 41.20 7.30

58.08 7.30 0.48 1.23 0.89 0.31 0.92 0.25 1.22 1.99 1037.97 332.47 58.16 11.76 37.61 59.10 48.76 31.90 86.20 9.59 284.32 29.59 48.52 391.32 333.18 58.14 291.77 214.86 59.47 17.45

43

In addition ammonium and sulfate are photochemical end-products (Hsieh et al., 2007, 2008). In this study, ammonium and potassium higher during the PM10 episode at CMU site, while source of particulate potassium are biomass combustion, indicating that urban area is significant source from the secondary photochemical product from traffic emission or biomass burning. High calcium concentration observed at TOT site. Calcium is a constituent in coal fly ash also biomass smoke and, dependent on regional geology, a constituent of mineral dust (Salam et al., 2003). Crustal matter originates from soil and road side were observed among the crustal elements (magnesium and calcium) (Ho et al., 2003), noted that at suburban area might be contributor mineral dust from industrial or biomass burning.

The water soluble organic acids were monocarboxylic acids (acetic acid and formic acid), dicarboxylic acids and tricarboxylic acids. Carboxylic acid concentration during the PM10 episode is higher than that during non-episodic period. Acetic acid was the most abundant monocarboxylic acids follow by formic acid. Oxalic acid was the dominant dicarboxylic acids both periods. During non episodic pollution period, IOP1, oxalic acid was significantly higher during the IOP2 than during the IOP1. The most pronounced period difference was shown by maleic acid, which had high concentrations in during IOP1 but was only detected during IOP2 low concentrations demonstrates that the molecular composition of these acids during two intensive observation period was also different. During the PM10 episode, oxalic acid was the most abundant species of the detected dicarboxylic acids, followed by malic acid, which the maximum concentration peak occurred at CMU site for oxalic acid high value at CMU site during dry season indicating that secondary photochemical end product be a major source of oxalic acids in urban site. Its might come from the secondary formation of traffic emission (Wang et al., 2007b; Hsieh et al., 2008,
44

2009). In contrast, IOP1 during non episodic, oxalic acid was most abundant species follow by maleic and malic acid. It is interesting to notice that during IOP1 the unsaturated dicarboxylic acids, maleic acid. These results may be source of maleic acid contributed from coal burning or wood burning during firth intensive period.

Anhydrosugars (levoglucosan and mannosan) were identified in aerosol sample, found in maximum concentrations at CMU site of 1258.76797.26 ng m-3 during the PM10 episode. Levoglucosan concentration was the dominant anhydrosugars, follow by mannosan during both periods. During non episodic pollution period IOP2, levoglucosan was higher than IOP1. As a result, it may be biomass burning largely contributed to atmospheric aerosols from levoglucosan emitted.

On the other hand, concentrations of levoglucosan observed in atmospheric particulate matter, the annually averaged of range from 0.12-0.48 g m-3 in wood smoke (Caseiro et al., 2009). Bergauff et al. (2009) showed levoglucosan from wood stove was an overall decrease of 50% from 3036344 ng m-3 to 1537117 ng m-3, but little change between the last years of the program (2006/2007 and 2007/2008). Santos et al. (2002) reported that concentration of levoglucosan range from 0.15-1.65, 0.36-6.83 ng m-3 and 0.1928.42 ng m-3 at the downtown Corpo de Bombeiros, suburban and countryside site, and from 10.55-35.06 ng m-3 and 2.7 ng m-3 in the smoke samples from the burnt leaves and bagasse, respectively. Ward et al. (2006) observed levoglucosan concentration in the range 900-6000 ng m-3 from the Missoula smoke sample during wildfire season. In this study, indicating that levoglucosan

45

was found to be the most useful marker for biomass burning generated from natural forest fire event in the mountain around Chiang Mai basin.

Moreover, levoglucosan was the most abundant anhydrosugars. Compared to wood combustion smoke the levoglucosan emissions relative to PM trend to be a little lower in the forest fire smoke samples. In a recent study concentrations of 4-15% levoglucosan in smoke PM of common midEuropeanwood types (Schmidl et al., 2008a, b) were reported. Zhang et al. (2008) found that the levoglucosan/PM percentage ratio was, on average 4.5% (2.9-6.5%) contribution from biomass burning. The ratios of levoglucosan to PM in fireplace emission are 0.8-26% (Fine et al., 2002, 2004). In this study, levoglucosan constituted 0.53-1.48% of PM10, indicating that biomass burning source emission was major types of forest fire in Chiang Mai basin. Another anhydrosugar, mannosan emitted during pyrolyses of hemicelluloses material, was found to be a useful compound for distinguishing between soft- and hardwood combustion. Mannosan concentration was in range 27.32-83.25 ng m-3 of this study, higher during the episode PM10 at CMU site. Caseiro et al. (2009) reported that mannosan concentration were lower than levoglucosan ones, the average for cold season range from 35-68, 69-212 and 46-69 ng m-3 in the Vienna, Graz and Salzburg regions, respectively.

Concentration of sugar alcohols was found during the PM10 episode higher level than during non episodic pollution period, which maximum at CMU site. Pio et al. (2008) reported Total sugar alcohol and monosugar concentrations ranged from about 40 to 100 ng m-3, with the maximum level found in a sample less affected by the smoke plumes. In general, sugar alcohols were found to be most prevalent in the coarse fraction. Arabitol was the dominant sugar alcohols follow by glycerol and erythritol. Sugar alcohols often found on the bark of
46

trees, braches and leaves (Mederios et al., 2006), indicating that during dry season, biomass burning contributed sugar alcohols emitted from bark of trees and leaves.

4.4 Concentration of chemical species in daytime and nighttime during non episodic pollution period and PM10 episode

The daytime and nighttime average concentration during non episodic pollution and PM10 episode at two sites was shown in Figure 4.3. Sulfate was the most abundant inorganic salts follow by ammonium, nitrate, calcium and potassium. During non episodic pollution, sulfate, nitrate and ammonium were higher in nighttime but low at STM site, indicating that during non episodic pollution, the nighttime was low mixing layer that limited dispersion of aerosol species due to accumulate during nighttime, while STM site height above ground level around 1400 m due to photochemical product during daytime. During the PM10 episode, Nitrate contributed during daytime than nighttime. Additionally, NOx from traffic emissions are photochemicallly converted to an intermediate production NO2 to PM2.5 is higher during the daytime, is rapidly converted into NO2 and then NO3 aerosol (Hsieh et al., 2008b), indicating that during the PM10 episode nitrate increased photochemical reaction of daytime. Moreover, crustal calcium higher during daytime showed that soil and roadside dust contributed during daytime. However, at TOT site, mostly contributed inorganic species in the nighttime during non episodic pollution, while during the PM10 episode mostly contributed in the daytime, indicating source of suburban site during non episodic pollution accumulate source in the nighttime and contribute transport to during the PM10 episode.
-

47

6.0 5.5 5.0

6.0

IOP1-CMU site
Daytime (PM10 mass conc.= 59.94 +/- 30.26 g m )
-3

5.5 5.0

IOP1-TOTsite
Daytime (PM10 mass conc.= 86.56 +/- 30.54 g m-3) Nighttime (PM10 mass conc.= 70.60 +/- 19.41 g m )
-3

Concentration (g m-3)

4.0 3.5 3.0 2.5 2.0 1.5 1.0 .5 0.0

e ium ium ium nesium alcium hlorid Sod mon Potass C C Am Mag ate Nitr ate Sulf

Concentration (g m-3)

4.5

Nighttime (PM10 mass conc.= 59.35 +/- 33.29 g m-3)

4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 .5 0.0

e ium ium ium nesium alcium hlorid Sod mon Potass C C Am Mag

ate Nitr

ate Sulf

Chemical species

Chemical species

16.0 15.0 14.0 13.0 12.0 11.0 10.0 9.0 8.0 7.0 2.0 1.8 1.6 1.4 1.2 1.0 .8 .6 .4 .2 0.0

IOP2-CMU site
Daytime (PM10 mass conc.= 70.85 +/- 21.03 g m-3) Nighttime (PM10 mass conc.=93.07 +/- 35.76 g m-3)

16.0 15.0 14.0 13.0 12.0 11.0 10.0 9.0 8.0 7.0 6.0 5.0 3.0 2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 1.0 .8 .6 .4 .2 0.0

IOP2-STM site
Daytime (PM10 mass conc.= 70.47 +/- 18.08 g m-3) Nighttime (PM10 mass conc.= 59.85 +/-23.16 g m-3)

Concentration (g m-3)

So d

ium ium ium nesium alcium hloride mon Potass C C Am Mag

Concentration (g m-3)

ate Nitr

ate Sulf

So d

ium ium ium nesium alcium hloride mon Potass C C Am Mag

ate Nitr

ate Sulf

Chemical species

Chemical species

6.0 5.5 5.0

6.0

IOP1-CMU site
Daytime (PM10 mass conc.= 145.27 +/- 17.19 g m-3) Nighttime (PM10 mass conc.=133.86 +/- 7.88 g m-3)

5.5 5.0

IOP1-TOT site
Daytime (PM10 mass conc.= 146.38 +/- 15.46 g m )
-3

Concentration (g m-3)

-3 Concentration (g m )

4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 .5 0.0

e ium ium ium nesium alcium hlorid Sod mon Potass C C Am Mag ate Nitr ate Sulf

4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 .5 0.0

Nighttime (PM10 mass conc.= 139.02 +/- 19.89 g m-3)

ium ium nesium alcium hloride ium Sod mon Potass C C Am Mag

Nitr

ate

Sulf

ate

Chemical species

Chemical species

Figure 4.3 Mean of inorganic species concentration in daytime and nighttime (a) during non episodic pollution period and (b) during the PM10 episode emitted from sampling sites

48

During non episodic pollution period during the IOP1 and IOP2 at CMU site the average concentration of PM10 in daytime varied of (56.9430.26 g m-3 versus 70.85 21.03 g m-3) lower than the nighttime (59.3533.29 g m-3 versus 93.0735.76 g m-3), respectively, shows in Figure 4.3, while at IOP1TOT and IO2-STM PM10 concentration at the daytime higher than nighttime showed that during non episodic pollution period, pollutant emitted from anthropogenic or traffic emission contributed in nighttime was significant source due to particle at urban site. During the PM10 episode at IOP1-CMU and TOT site PM10 concentration in daytime (145.2717.19 g m-3 versus 146.3815.46 g m-3) higher than the nighttime (133.867.88 g m-3 versus 139.0219.89 g m-3), respectively, indicating that anthropogenic emission or biomass burning due to particles was significant source in urban site contributed in the daytime during the PM10 episode. Moreover the both of period, showed that at suburban site pollutant contributed during the daytime.

The abundance of the individual carboxylic acids during daytime and nighttime are presented in Figure 4.4. Average concentrations of carboxylic acids were abundant in daytime than in the nighttime. This fact may be attributed to the carboxylic acids formed by photochemical reaction and emitted directly by fossil fuels and biomass combustion processes which occur with more frequency at daytime. Moreover, in the nighttime, removal mechanisms could lead to a decrease in carboxylic levels (Souza et al., 1999). Acetic acid was abundant monocarboxylic acid follow by formic acid. In addition, oxalic was the dominant dicarboxylic acid during both daytime and nighttime followed by maleic or malic acid.

49

a During non episodic pollution period

1400 1300 1200 1100 1000 900 800 700 600 500 400 300 180 160 140 120 100 80 60 40 20 0
ic ic ic ic lic lic lic tic ric ric ric ric Ace FormGluta Succin Ma MalonTarta MaleFuma Oxa Phtha Cit

IOP1-CMU site
Daytime (PM10 mass conc.= 56.94 +/- 30.26 g m-3) Nighttime (PM10 mass conc.= 59.35 +/- 33.29 g m-3)

Concentration (ng m-3)

Concentration (ng m-3)

1400 1300 1200 1100 1000 900 800 700 600 500 400 300 200 100 50 40 30 20 10 0

IOP1-TOT site
Daytime (PM10 mass conc.= 86.56 +/- 30.54 g m-3) Nighttime (PM10 mass conc.= 70.60 +/- 19.41 g m-3)

ic ic ic ic lic lic lic tic ric ric ric ric Ace FormGluta Succin Ma MalonTarta MaleFuma Oxa Phtha Cit

Carboxylic acids

Carboxylic acids

Concentration (ng m-3)

180 160 140 120 100 80 60 40 20 0

ic ic ic ic lic lic lic tic ric ric ric ric Ace FormGluta Succin Ma MalonTarta MaleFuma Oxa Phtha Cit

Concentration (ng m-3)

1400 1300 1200 1100 1000 900 800 700 600 500 400 300

IOP2-CMU site
Daytime (PM10 mass conc.= 70.85 +/-21.03 g m )
-3

Nighttime (PM10 mass conc.= 93.07 +/- 35.76 g m )

-3

1400 1300 1200 1100 1000 900 800 700 600 500 400 300 200 100 70 60 50 40 30 20 10 0

IOP2-STM site
Daytime (PM10 mass conc.= 70.47 +/- 18.08 g m-3) Nighttime (PM10 mass conc.= 59.85 +/- 23.16 g m-3)

ic ic ic ic lic lic lic tic ric ric ric ric Ace FormGluta Succin Ma MalonTarta MaleFuma Oxa Phtha Cit

Carboxylic acids

Carboxylic acids

b During the PM10 episode

1400 1300 1200 1100 1000

IOP1-CMU site
Daytime (PM10 mass conc.= 145.27 +/- 17.19 g m )
-3

Nighttime (PM10 mass conc.= 133.86 +/- 7.88 g m )

-3

Concentration (ng m-3)

900 800 700 600 450 400 350 300 250 200 150 100 50 0
ic ic ic ic lic lic lic tic ric ric ric ric Ace FormGluta Succin Ma MalonTarta MaleFuma Oxa Phtha Cit

Concentration (ng m-3)

1400 1300 1200 1100 1000 900 800 700 600 500 300 250 200 150 100 50 0

IOP1-TOT site
Daytime (PM10 mass conc.= 146.38 +/- 15.46 g m )
-3

Nighttime (PM10 mass conc.= 139.02 +/- 19.89 g m )

-3

ic ic ic ic lic lic lic tic ric ric ric ric Ace FormGluta Succin Ma MalonTarta MaleFuma Oxa Phtha Cit

Carboxylic acids

Carboxylic acids

Figure 4.4 Mean of carboxylic acids concentration in daytime and nighttime (a) during non episodic pollution period and (b) during the PM10 episode emitted from sampling sites

50

During non episodic pollution, Oxalic, acetic and formic acid were found in daytime but at IOP1-CMU site higher in the nighttime. Its might be more source of carboxylic in nighttime at CMU site in this period, while other period due to photochemical reaction from biomass burning are significant source of these acids emitted in daytime. During the PM10 episode, average concentration of carboxylic acids was higher during daytime. But maleic and tartaric acids were significantly in nighttime higher than daytime, indicating that during the PM10 episode, daytime photochemical reaction decompose the atmospheric to maleic and tartaric acid.

The mean of anhydrosugars and sugar alcohols concentration in daytime and nighttime during non episodic pollution and PM10 episode was shown in Figure 4.5. During non episodic pollution period, levoglucosan concentration showed in the nighttime higher than the daytime, but at STM site higher in the daytime. This may be associated with a development of inversion layer where pollutants accumulate. Moreover, mannosan and arabitol were higher in daytime, which the hardwood or softwood burning of biomass burning usually occurs in the daytime, resulting in enhanced daytime smoke tracer concentrations, which was clearly evident in the mannosan and arabitol concentration patterns during the active burning period of this study. During the PM10 episode, levoglucosan was found higher concentration in nighttime, which levoglucosan is a byproduct of cellulose pyrolysis. These results suggest that smoke concentrations may increase at nighttime during the PM10 episode.

51

a During non episodic pollution period

2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 200 140 120 100 80 60 40 20 0
Lev c oglu osan n nosa Man l bito Ara l cero Gly Ery ol thrit

IOP1-CMU site
Daytime (PM10 mass conc.= 56.94+/- 30.26 g m )
-3

Nighttime (PM10 mass conc.= 59.35 +/- 33.29 g m )

-3

2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 280 260 240 220 200 180 160 140 120 100 80 60 40 20 0
og Lev san luco

IOP1-TOT site
Daytime (PM10 mass conc.= 86.56+/- 30.54 g m )
-3

Nighttime (PM10 mass conc.= 70.60+/- 19.41 g m )

-3

-3 Concentration (ng m )

-3 Concentration (ng m )

n nosa Man

Ara

l bito

l cero Gly

Ery

thrit

ol

Anhydrosugars and Sugar alcohol species

Anhydrosugars and Sugar alcohol species

2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 180 160 140 120 100 80 60 40 20 0
og Lev san luco

IOP2-CMU site
Daytime (PM10 mass conc.= 70.85+/- 21.03 g m )
-3

Nighttime (PM10 mass conc.= 93.07 +/- 35.76 g m )

-3

2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 200 180 160 140 120 100 80 60 40 20 0
Lev n cosa oglu

IOP2-STM site
Daytime (PM10 mass conc.= 70.47+/-18.08 g m )
-3

Nighttime (PM10 mass conc.= 59.85+/- 23.16 g m-3)

Concentration (ng m-3)

-3 Concentration (ng m )

an nos Man

l bito Ara

ce Gly

rol

Ery

ol thrit

n nosa Man

Ara

l bito

l cero Gly

Ery

ol thrit

Anhydrosugars and Sugar alcohol species

Anhydrosugars and Sugar alcohol species

b During the PM10 episode

2400 2200 2000 1800 1600 1400 1200 1000 700 600 500 400 300 200 100 0
Lev c oglu osan n nosa Man l bito Ara l cero Gly Ery ol thrit

2400

IOP1-CMU site
Daytime (PM10 mass conc.= 145.27 +/- 17.19 g m-3) Nighttime (PM10 mass conc.= 133.86 +/- 7.88 g m )
-3

2200 2000 1800 1600 1400 1200 1000 800 600 500 400 300 200 100 0
Lev n cosa oglu

IOP1-TOT site
Daytime (PM10 mass conc.= 146.38+/- 15.46g m )
-3

Nighttime (PM10 mass conc.= 139.02 +/- 19.89 g m )

-3

-3 Concentration (ng m )

-3 Concentration (ng m )

no Man

san

Ara

l bito

l cero Gly

Ery

ol thrit

Anhydrosugars and Sugar alcohol species

Anhydrosugars and Sugar alcohol species

Figure 4.5 Mean of anhydrosugar and sugar alcohols concentration in daytime and nighttime (a) during non episodic pollution period and (b) during the PM10 episode emitted from sampling sites

52

4.5 Contribution of chemical species Figure 4.6 shows that of identified species each site of sampling during observes period, inorganic salts to the PM10 most abundant species follow by carboxylic acid, anhydrosugars and sugar alcohols, respectively, while others species the biggest contribution to PM10 were not to found in this study may be some source contributed to aerosols. However, IOP2 percentage to contribution inorganic salts, carboxylic acid and anhydrosugars higher than IOP1. The results during IOP2 period maximum average ozone increase due to high sulfate, significant photochemical formation processes, which inorganic salt to contributed 16.90% at CMU site and 17.41% at STM site, respectively. Moreover, high ozone during IOP2 due to contribute anhydrosugars higher than IOP2, indicating that inorganic salts, carboxylic acids and anhydrosugars increased with an increase in atmospheric ozone concentrations, to be related to secondary photochemical processes in the atmosphere rather than primary emissions from traffic or biomass burning.

53

Inorganic 11.79% Carboxylic 1.57% Anhydrosugars 0.80% Sugar alcohols 0.52%

Inorganic 9.82% Carboxylic 1.24% Anhydrosugars 0.74% Sugar alcohols 0.39%

Others 85.32%

Others 87.82%

IOP1-CMU site (PM10 = 86.18 g m-3)

IOP1-TOT site (PM10 = 111.07 g m-3)

Inorganic 16.96% Carboxylic 1.64% Anhydrosugars 1.24% Sugar alcohols 0.21%

Inorganic 17.41% Carboxylic 1.40% Anhydrosugars 1.53% Sugar alcohols 0.29%

Others 79.94%

Others 79.38%

IOP2-CMU site (PM10 = 81.96 g m-3)

IOP2-STM site (PM10 = 65.16 g m-3)

Figure 4.6 Contribution of individual species to total composition in PM10 during intensive observation period of each sites

Inorganic species were found to comprise 11.79%, 9.82%, 16.96% and 17.41% of PM10 mass concentration 86.1847.20 g m-3, 111.0739.27 g m-3, 81.9629.64 g m-3 and 65.1620.05 g m-3. Sulfate is a major constituent of inorganic salts in PM10 during observation site shown in Figure 4.7, comprising 29.93%, 22.33%, 57.33% and 48.42% during IOP1 at CMU and TOT sites versus during IOP2 at CMU and STM sites, respectively. During IOP2 higher sulfate than IOP1, which high percent of sulfate at CMU site, indicating that during the ozone increases due to high sulfate, significant photochemical formation from anthropogenic activity and photochemical reaction in urban area. Nitrate (21.73% of inorganic salts), calcium (15.48% of inorganic salts) were high percentage to contributed at TOT site, indicating that
54

significant source in suburban area was emitted from photochemical product or soil and roadside dust from industrial area. Ammonium and potassium were high percentage of inorganic salt at CMU site during IOP1, showed that source of urban area emitted from traffic emission or biomass burning. At STM site sulfate was dominate inorganic species follow by nitrated, ammonium, calcium and potassium, respectively, which during IOP2 at STM site, where most famous visitor travel in Bhubing Palace due to high concentration of these species. The results that photochemical product is significant source in mountain site during observe period.

Magnesium 4.52% Sodium 7.14%

Chloride 3.63% Sulfate 25.93%

Magnesium 3.80% Sodium 5.67%

Chloride 4.41%

Sulfate 22.33%

Calcium 12.32%

Calcium 15.48%

Ammonium 13.79%
Potassium 13.59% Ammonium 17.09%

Potassium 12.80% Nitrate 21.73%

Nitrate 15.78%

Magnesium Chloride Sodium 0.80% 4.54% 4.56% Calcium 9.06%

Magnesium 1.09% Sodium 6.30% Calcium 8.24%

Chloride 5.48%

Potassium 5.64% Sulfate 57.33%

Potassium 6.64%

Sulfate 48.42%

Nitrate 9.37%

Nitrate 11.96%

Ammonium 8.69%

Ammonium 11.88%

Figure 4.7 Contribution of individual species to total amount of inorganic species in PM10 during intensive observation period of each sites

55

Carboxylic acids were found to comprise 1.57%, 1.24%, 1.64% and 1.40% of PM10 mass concentration 86.1847.20 g m-3, 111.0739.27 g m-3, 81.9629.64 g m-3 and 65.1620.05 g m-3 at IOP1-CMU, TOT site and IOP2CMU, STM site, respectively. Figure 4.8 shows the percentage contributions of individual carboxylic acids to the total for each sites of sampling. Carboxylic acids in the particle phase accounted for a small fraction of the organic carbon, which source of carboxylic acid include direct release into the atmosphere via anthropogenic and/or biogenic activities, and photochemical oxidation of precursor organic species (Khwaja, 1995). Acetic acid was the most abundant monocarboxylic acids follow by formic acid. Acetic acid may be mostly from primary emission of vegetation and soil (Wang et al., 2007b). Direct emissions of formic acid from biogenic and anthropogenic source are probably negligible at this time of year (Glasius et al., 2000). Since the samples used here were collected in dry season, the harvest season in Chiang Mai, biomass burning of forest fire or wood burning was prominent in the field of suburban areas. The higher acetic level at TOT site (34.25% of carboxylic acids) might be related to the biomass processes indicating that source of suburban site emitted from biomass burning. Oxalic acid was dominated dicarboxylic acids, accounting for 41.14% of carboxylic acids IOP2-STM site, 35.43% of carboxylic acids IOP2CMU site, 33.11% of carboxylic acids IOP1-CMU site and 31.54% of carboxylic acids IOP1-TOT site follow by maleic or malic acid. Oxlic acid is the final product of photochemical decomposition of other dicarboxylic acids in atmospheric aerosol. Moreover, it is the most abundant dicarboxylic acids in atmospheric aerosol (Glasius et al., 2000; Salam et al., 2003; Ho et al., 2006; Tsai et al., 2010).

56

Tartaric acid 2.93% Succinic acid 4.52% Malonic acid 4.90% Citric acid 3.40% Formic acid 5.76%

Phthalic acid Glutaric acid 2.82% 1.66% Fumaric acid 1.16%

Succinic acid 3.49%

Oxalic acid 33.11%

Tartaric acid 2.78%

Phthalic acid 2.30%

Glutaric acid 1.62% Fumaric acid 0.84%

Malonic acid 4.39% Citric acid 2.10% Formic acid 3.76% Malic acid 5.16% Maleic acid 7.76%

Oxalic acid 31.54%

Malic acid 6.34% Maleic acid 6.53%

Acetic acid 26.87%

Acetic acid 34.25%

IOP1-CMU site (Carboxylic acid = 1352.75 680.85 ng m-3)

Tartaric acid 3.60% Succinic acid 4.53% Malonic acid 4.57% Citric acid 2.87% Formic acid 4.97% Malic acid 4.98% Maleic acid 3.29% Acetic acid 28.57% Phthalic acid 0.51% Glutaric acid 3.85% Fumaric acid 2.84%

IOP1-TOT site (Carboxylic acid = 1374.08 560.17 ng m-3)

Tartaric acid Phthalic acid Glutaric acid 0.75% 2.63% 2.65% Fumaric acid Succinic acid 2.96% 1.57% Malonic acid 3.63% Citric acid 2.14% Formic acid 6.33% Malic acid 3.85% Maleic acid 3.91%

Oxalic acid 35.43%

Oxalic acid 41.14%

Acetic acid 28.45%

IOP2-CMU site (Carboxylic acid = 1430.66 428.71 ng m-3)

IOP2-STM site (Carboxylic acid = 969.64 430.95 ng m-3)

Figure 4.8 Contribution of individual species to total amount of carboxylic acids in PM10 during intensive observation period of each sites

On the other hand, oxalic acid may be good tracer of biomass burning (Jaffrezo et al., 1998). Interestingly, good correlation was observed between oxalic acid and potassium shown in Figure 4.9. Oxalic acid presents the best relationship with potassium during IOP1 (r = 0.895 at CMU site and r = 0.936 at TOT site), while during IOP2 the available data is too less for analysis or difference period due to different source. These sources might include biomass burning, secondary and conversion from larger organic acids.

57

3.5

3.5

IOP1-CMU site
3.0

IOP1-TOT site
3.0

2.5

2.5

Potassium

Potassium
0 100 200 300 400 500 600 700 800 900 1000 1100 1200

2.0

2.0

1.5

1.5

1.0

1.0

.5

.5

0.0

0.0 0 100 200 300 400 500 600 700 800 900 1000

Oxalic acid

Oxalic acid

1.6 1.4 1.2

1.4

IOP2-CMU site
1.2

IOP2-STM site

1.0
1.0

Potassium

Potassium
0 100 200 300 400 500 600

.8

.8 .6 .4 .2 0.0

.6

.4

.2

0.0 0 100 200 300 400 500 600 700

Oxalic acid

Oxalic acid

Figure 4.9 Correlation of potassium concentration with oxalic acid concentration of each site sampling

Wang and Shooter (2004) noted that maleic acid was the second most abundant species of the detected DCAs in the winter with intensive wood and coal burning. Moreover, maleic acid was the dominant source from wood burning in atmospheric aerosols (Tsai et al., 2010). In this study, the contribution of maleic acid to identified carboxylic acid emission was 6.53%, 7.76%, 3.29% and 3.91% of the total emissions at IOP1-CMU, TOT site and IOP2-CMU, STM site. These results may suggest that maleic acid most abundant source emitted from coal combustion. The contribution of malic acid was significantly biogenic source emission (Rhrl and Lammel, 2002).
58

Anhydrosugars were found to comprise 0.80%, 0.74%, 1.24% and 1.53% of PM10 mass concentration 86.1847.20 g m-3, 111.0739.27 g m-3, 81.9629.64 g m-3 and 65.1620.05 g m-3 at IOP1-CMU site, TOT and IOP2CMU, STM site, respectively. Figure 4.10 shows the percentage contributions of individual anhydrosugars to the total for each sites of sampling. Levoglucosan clearly dominated both of species, accounting for 90.33%, 92.26%, 97.31% and 97.11% of anhydrosugars from IOP1-CMU site, TOT and IOP2-CMU, STM site, respectively. Levoglucosan and the related degradation products from the thermal degradation of cellulose and hemicelluloses and are commonly use as tracers for wood smoke in the atmosphere (Simoneit et al., 1999; Jordan et al., 2006; Lee et al., 2008; Schmidl et al., 2008a; Fabbri et al., 2009). Levoglucosan a molecular marker for biomass burning (Medeiros et al., 2006; Ward et al., 2006; Zhang et al., 2008) in general, in clouding softwood, hard wood, grasses and other foliar fuels (Fine et al., 2002, 2004; Engling et al., 2006b), Moreover, during IOP2 percentage of levoglucosan contributed higher than IOP1 indicating that levoglucosan emitted from biomass burning significantly second intensive observation period of this study. Second species contribution anhydrosugars of mannosan was in range 2.69-9.67% of this study. In the same study, mannosan, a pyrolysis product from hemicelluloses, it the second most abundant anhydrosugar in the wood smoke samples (Schmidl et al., 2008a). Mannosan, another anhydrosugar emitted during pyrolyses of cellulose material was found to be a useful compound for distinguishing between softwood and hardwood combustion (Schmidl et al., 2008b).

59

Mannosan 9.67%

Mannosan 7.74%

Levoglucosan 90.33%

Levoglucosan 92.26%

Mannosan 2.69%

Mannosan 2.89%

Levoglucosan 97.31%

Levoglucosan 97.11%

Figure 4.10 Contribution of individual species to total amount of anhydrosugars in PM10 during intensive observation period of each sites

Figure 4.11 shows the relationship between levoglucosan and potassium. Levoglucosan presents the good relationship with potassium during IOP1 r = 0.790 at CMU, r = 0.752 at TOT site versus IOP2, r = 0.899 at CMU site and r = 0.791 at STM site. This suggests that biomass burning is significant source of aerosol organic carbon in Chiang Mai basin.

60

3200 3000 2800 2600 2400 2200

2600

IOP1-CMU site

2400 2200 2000 1800

IOP1-TOT site

y = 557.3x - 145.8 r = 0.790

Levoglucosan

y = 607.7x - 94.20 r = 0.752

Levoglucosan

2000 1800 1600 1400 1200 1000 800 600 400 200 0 0.0 .5 1.0 1.5 2.0 2.5 3.0 3.5

1600 1400 1200 1000 800 600 400 200 0 0.0 .5 1.0 1.5 2.0 2.5 3.0 3.5

Potassium

Potassium

2000 1800 1600 1400

2400

IOP2-CMU site

2200 2000 1800 1600

IOP2-STM site

y = 1370.x - 86.15 r = 0.899

Levoglucosan

y = 1621.x - 252.9 r = 0.791

Levoglucosan

1200 1000 800 600 400 200 0 0.0 .2 .4 .6 .8 1.0 1.2 1.4 1.6

1400 1200 1000 800 600 400 200 0 0.0 .2 .4 .6 .8 1.0 1.2 1.4

Potassium

Potassium

Figure 4.11 Correlation of levoglucosan concentration with potassium concentration of each site sampling

Sugar alcohols were found to comprise 0.52%, 0.39%, 0.21% and 0.29% of PM10 mass concentration 86.1847.20 g m-3, 111.0739.27 g m-3, 81.9629.64 g m-3 and 65.1620.05 g m-3 at IOP1-CMU site, TOT and IOP2CMU, STM site, respectively. Figure 4.12 shows the percentage contributions of individual sugar alcohols to the total for each sites of sampling. Arabitol was the most abundant species, accounting for 57.05%, 58.43%, 76.45% and 68.28% of sugar alcohols from IOP1-CMU site, TOT and IOP2-CMU, STM site, respectively, higher during IOP2 at CMU site, follow by glycerol and erythritol. The sugar alcohols arabitol were found in the leaf combustion is much higher than in log combustion (Schmidl et al., 2008b), excellent marker
61

for fungal spores (Caseiro et al., 2007; Bauer et al., 2008). Tsai et al. (2010) found that sugar alcohol could be used as a diagnostic marker of saccharide polyols for identifying the contribution of incense smoke. These studies, sugar alcohol typical for biomass burning were found significant concentration in the leaf smoke in ambient PM10 samples.

Erythritol 7.63%

Erythritol 7.84%

Glycerol 35.31%

Glycerol 33.73%

Arabitol 57.05%

Arabitol 58.43%

Erythritol 8.20% Glycerol 15.36%

Erythritol 7.75%

Glycerol 23.97%

Arabitol 76.45%

Arabitol 68.28%

Figure 4.12 Contribution of individual species to total amount of sugar alcohols in PM10 during intensive observation period of each sites

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4.6 Composition of mass ratios with other studies

4.6.1 Carboxylic acids

The acetic acid/ formic acid (A/F) mass ratio was used to distinguish the primary (A/F>1) and the secondary (A/F<1) sources (Villanueva-Fierro et al., 2004; Wang et al., 2007b). Acetic was mainly from primary emissions, while formic acid was largely from secondary transformations, A/F values were collected from major primary emission source including vehicular emission, biomass burning, and soil and vegetation emissions, and from secondary source were reported A/F values in Table 4.3. The A/F mass ratios in PM10 of Chiang Mai, during non episodic pollution, ratios in range 4.49-9.40. During the PM10 episode, A/F ratios was in range 3.66-8.83, indicating that a large contribution of primary sources from biomass burning at Chiang Mai basin both period of this study. The malonic acid/succinic acid (M/S) mass ratio in atmospheric particle is a useful indicator to differentiate primary (vehicular) source from secondary sources. The M/S ratio has been reported to be 0.3-0.5 from vehicular emissions (Kawamura and Kaplan, 1987), whereas, Kawamura and Ikushima (1993) reported a maximum mass ratio of 3 from secondary atmospheric particle in the summer in Tokyo, which these ratio have been reported in the literature shown in Table 4.3. In this study, as shown in the Table 4.2, during the non-episodic pollution have significantly higher M/S mass ratios than the PM10 episode. During non episodic pollution, the samples collected had an average M/S ratio in range 1.01-1.72, indicating that during non episodic pollution more potential to be secondary source was the principal source of dicarboxylic acid. During the
63

PM10 episode, the average M/S ratio was 0.94 and 1.11 at CMU ad TOT site, respectively. At CMU site ratio were lower than TOT site ratio, suggesting that more potential to be primary source is dominant source of dicarboxylic acid in urban site during the PM10 episode.

Table 4.3 Summary presentation of research findings related to acetic/formic and malonic/succinic ratios in aerosol
Source Primary source Secondary source Biomass burning Vehicular emissions Biomass burning Wood burning (rural) Wood burning (forested) Vehicular emission Primary vehicle exhaust Secondary formation Secondary source A/F >1 <1 2-10 1.75-2.38 0.71 3.86 2.83 M/S Reference Wang et al. (2007b) Talbot et al. (1988)

0.3-0.5 0.5-0.6 1.5-2.7 >3

Wang et al. (2007b) Villanueva-Fierro et al. (2004) Kawamura and Kaplan (1987) Yao et al. (2004) Kawamura and Ikushima (1993) Hsieh et al. (2008)

Primary vehicle exhaust (nighttime) 0.76 Secondary source (daytime) 1.15 Primary source of biomass burning 3.66-9.40 This study More potential to be secondary source 1.01-1.72 This study (non-episodic pollution) More potential to be primary source 0.94 This study (PM10 episode)

The mass ratio of oxalic to sulfate are present as the end products of organic and inorganic species, the oxalic acid/sulfate mass ratio is informative for determining the formation of dicarboxylic acids from inorganic salts. The ratio for ambient aerosol was higher during PM episode in range 0.504-0.603, while during non-episodic period in range 0.405-0.486 (Hsieh et al., 2008). The oxalic/sulfate ratio has been reported 0.80-0.83 from incense emissions (Tsai et
64

al., 2010). The oxalic/sulfate ratio (Table 4.2) was higher during PM10 episode than non episodic pollution period demonstrates that higher potential formation strength for sulfate during PM10 episode.

4.6.2 Anhydrosugars

Potassium (K), a commonly used tracer species for biomass burning, also was found to correlation with levoglucosan (Levo), a mass ratio in range 0.782.68 (see in Table 4.4). Tsai et al. (2010) reported K/Levo ratio of 0.288 for hardwood (fresh sandal wood), higher than the 0.229 in hardwood (aged sandal wood), while Caseiro et al. (2009) reported K/Levo ratio in the range 0.8-2.1 in softwood. Moreover, Ward et al. (2006) studies wood type in forest fire smoke the ratio K/Levo in the range 0.045-2.6. In US studies burning American wood type in fireplaces (e.g. Fine et al., 2002, 2004) K/Levo ratios were in the range 0.017-0.230. Recent studies have shown, a significant variation in K/Levo ratio in wood burning emission, indicating that during more complete combustive processes, potassium is possibly a more reasonable biomass burning tracer in this study. The average ratio of levoglucosan (Levo) to mannosan (Manno) was found lower ratio in range 5.73-7.69 during non episode IOP1, while high this ratio in range 14.12-36.19. During IOP2 site was higher ratio than IOP1. These ratio might change the during period or sites due to different emission patterns of anhydrosugars from different type of combustion occurring in different site, indicating that more detail the sites variation of those compound. Table 4.4 shows the recent, other studies found this ratio for investigate biomass burning and forest fire the difference between hardwood and softwood type (Find et al., 2004; Engling et al., 2006; Ward et al., 2006; Caseiro et al., 2009). Moreover, Tsai et al. (2010) found that the ratio Levo/Manno of 12.5 and 13.5 in incense
65

burning from fresh sandal wood and aged sandal wood, repectively. The ratio Levo/Manno in the particulate emission from burning woods commonly used in Austria (softwoods: spruce and larch, hardwoods; oak and beech was found to be high for hard woods (typically 14-15) and lower for softwoods (3.6-3.9). Briquettes from softwoods had a ratio of 2.5 (Schmidl et al., 2008a), suggesting that during dry season in Chiang Mai high biomass burning is a significant emitted from hardwood and softwood.

Table 4.4 Comparison of ratios for various wood burning and atmosphere aerosols (reported in the literature)
Aerosol type Incense burning, Taiwan Sample type Hardwoods (fresh sandal wood) Hardwoods (aged sandal wood) Hardwood Softwood Hardwood Softwood Hardwood Softwood Hardwood Forest fire smoke Softwood Hardwood Softwood K/Levo 0.288 0.229 Levo/Manno Reference 12.5 Tsai et al. (2010) 13.5 14.4 3.6-3.9 13.8-32.3 2.6-5.0 0.017-0.230 0.119-0.138 0.036-0.122 0.045-2.6 0.8-2.1 0.78-2.68 Schmidl et al. (2008a) Engling et al. (2006) Fine et al., (2002) Fine et al., (2004) Ward et al., (2006) Caseiro et al., (2009) This study

Wood stove, mid European Alpine regions Chamber burns Fireplace, NE US Fireplace, Midwest and W US Northern America, Wildfires period Wood burning, Austrian regions Dry season, Chiang Mai, Thailand

13-24 4.8-5.6 4.1-6.4 14.12-36.19 5.73-7.69

66

4.7 Relationships among chemical species in daily PM10 and gaseous pollutants Principal component analysis (PCA) has been conducted to identify the factors influencing the variance of the measured chemical species, air pollutant and wind speed during intensive observation period in CMU site. The rotated factor loading matrix from PCA is shown in Table 4.5. Seven factors with eigenvalues>1.0 were found to explain 74.46% of the total variance. The first factor (PC1) accounting for 40.03% of total variance was loaded with PM10, crustal elements (magnesium and calcium), ammonium, potassium, photochemical products of dicarboxylic acids (succinic, malonic and oxalic acid), biogenic source of malic acid, biomass marker levoglucosan, mannosan, sugar alcohols (arabitol, glycerol and erythritol) and CO. Sugar alcohols often found on the bark of trees, branches and leaves (Medeiros et al., 2006). This factor could be interpreted as one representing photochemical product from traffic emission and biomass burning of leaves and bark of trees. The second factor (PC2) accounting for 10.60% was strong negative loading associated with sulfate, O3 and SO2. This could be interpreted to result from photochemical oxidation of SO2 produced oxidants to form sulfate. The third factor (PC3) accounting for 7.70% of the total was mainly associated with sea salts (sodium and chloride), which Chiang Mai is more than 700 km inland of shore. Therefore, a considerable local contribution at Chiang Mai can be assumed. The fourth factor (PC4) accounting for 6.19% of the total variance was negative correlated primary with tartaric acid and NOx, which could be interpreted as representing the effects of traffic emission source. Fifth factor (PC5) accounting for 5.09% of the total variance was negative correlated wind speed, indicating wind blows strong due to dispersion pollution. From these results, it can be concluded that the composition of atmospheric aerosols in Chiang Mai Basin

67

during intensive period was mainly affected by biomass burning of leaves/bark trees and photochemical process from traffic emission.
Table 4.5 Varimax-rotated principal component loadings of daily PM10 chemical species and gaseous pollutants during intensive observation period of this study (n=74) PC1 PC2 PC3 PC4 PC5 Variable PM10 Sodium Ammonium Potassium Magesium Calcium Chloride Nitrate Sulfate Acetic Formic Succinic Malic Malonic Tartaric Maleic Oxalic Levoglucosan Mannosan Arabitol Glycerol Erythritol CO O3 SO2 NOx Wind Speed 0.85a 0.36 0.85 0.93 0.77 0.78 0.25 0.50 0.28 0.40 0.46 0.79 0.75 0.85 0.38 0.05 0.91 0.63 0.63 0.79 0.73 0.82 0.63 0.44 0.47 -0.27 -0.07 0.03 -0.17 0.07 0.14 0.37 0.14 -0.26 0.20 -0.70 0.10 -0.21 -0.15 -0.01 -0.03 -0.10 0.46 -0.12 -0.41 0.50 0.42 0.25 0.21 -0.18 -0.60 -0.66 0.47 0.04 -0.08 0.74 0.03 0.03 0.01 -0.12 0.66 -0.16 -0.07 0.40 0.31 -0.07 0.26 -0.14 -0.20 0.39 -0.12 -0.09 0.19 -0.03 -0.16 -0.11 -0.41 0.17 -0.26 -0.28 0.26 0.01 -0.26 0.11 -0.04 0.10 0.21 -0.10 0.07 0.09 0.33 -0.33 -0.21 -0.21 -0.22 -0.60 -0.33 0.16 -0.31 0.14 0.17 0.05 0.07 0.00 0.18 0.04 -0.63 0.29 0.06 0.24 0.16 0.10 0.06 0.05 0.39 0.11 0.20 -0.19 -0.29 -0.21 -0.12 -0.24 -0.31 0.11 -0.04 0.10 -0.05 0.05 0.03 0.02 0.22 -0.42 0.09 -0.08 -0.68

PC6 -0.07 -0.01 0.05 -0.14 0.05 0.46 0.15 0.70 0.16 0.36 -0.15 -0.06 -0.24 0.05 0.34 0.10 -0.12 -0.01 -0.13 -0.17 -0.17 -0.13 -0.21 0.02 0.08 0.14 0.04

Eigenvalue 10.81 2.86 2.08 1.67 1.37 1.31 Cumul. eigenvalue 10.81 13.67 15.75 17.42 18.80 20.10 % Total variance 40.03 10.60 7.70 6.19 5.09 4.85 Cumul. % variance 40.03 50.63 58.33 64.52 69.61 74.46 a Bold marked component loadings were |0.60|, indicating a significant component loading. 68

4.8 Comparison with literature data The finding that some chemical species (inorganic salts, carboxylic acids, anhydrosugars and sugar alcohols) had significantly higher during dry season concentration in Chiang Mai Basin in PM10 for the literature. Concentrations of chemical species in different size were used for comparison. The data listed in Table 4.6-4.8 include a literature overview of the selected compounds, determined at other sites.

Inorganic salts in PM10 for comparison with other literature in recent years of atmospheric aerosol shown in Table 4.6. In general, the reported urban concentrations are higher than those at the remote (such as summer time in Aveiro, Portugal). Similar chain length distributions of inorganic salts, with a predominance of sulfate, have been reported in all the sites. Sulfate is slightly lower to those reported in other site like, Aveiro but other sites are high sulfate. Interestingly, potassium in this study was higher than other reported. This result suggesting that biomass burning is significant source in Chiang Mai basin.

Table 4.7 shows comparison carboxylic acids with other literature in recent years of atmospheric aerosol. Mostly, the reported urban concentrations or during episode are higher carboxylic acids. There are some differences between the relative abundances of the carboxylic acids found in this study and those in most other regions in the world were oxalic, malonic and succinic acids were often the three most abundant species. The mean concentration of glutaric, tartaric, maleic and fumaric acids were higher than the recent reported. Chiang Mai during dry season has more carboxylic acids. It is therefore strongly suggested that coal combustion or biomass burning in Chiang Mai has
69

contributed significantly to the production of some particulate carboxylic acids in dry season.

Table 4.8 shows comparison anhydrosugars and sugar alcohols from forest (wildfire) in this study with anhydrosugars and sugar alcohols emissions from combustion of other types of biomass (reported in the literature). Ambient anhydrosugars and sugar alcohols concentrations measured during biomass burning studies at various other sites in different countries have been lower in many cases than those observed during this study. Mostly, anhydrosugars and sugar alcohols were found in coarse particulate size. Levoglucosan was abundant species. Smoke emissions from forest burning have often been associated with relatively low ambient anhydrosugar concentrations as well, except for some observation of higher tracer concentrations in Launceston, Australia from woodsmoke, Montana, U.S.A. from Forest, Beijing, China from biomass burning and Douliou, Taiwan from rice straw during burning peak with ambient levoglucosan values up to microgram (Jordan et al., 2006; Ward et al., 2006; Zhang et al., 2008; Lee et al., 2008). Interestingly, sugar alcohols have a few studies, which in this report shown high concentration of sugar alcohols. Usually, sugar alcohols are found to be very small, mostly under the limit of detection.

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Table 4.6 Inorganic salt concentrations (g m-3) measured at various sampling sites around the world in recent years
Location Sampling period Size Sulfate Nitrate Chloride Sodium Ammonium Potassium Magnesium Calcium

Nanjing China/Urban a Hong Kong, China/Urban

b c

Feb.-May., 2001 Nov. 2000-Feb., 2001 (Winter) PM episode (Nov., 2004) non episodic (Sep.Oct., 2004) PM episode (Nov., 2004) non episodic (Sep.Oct., 2004)
g d

PM2.5 PM10 PM10 PM10 PM2.5 PM2.5 Four mode Four mode TSP PM2.5-10 PM10 PM10 PM10

19.07 15.90 15.77 14.23 15.38 11.28 15.82 11.49 11.3 0.885 1.99-7.97 1.39-3.41 5.49

5.72 5.29 4.92 4.45 12.62 6.14 12.90 6.33 3.63 0.706 1.22-2.34 2.08-2.64 1.36

1.36 1.46 8.64 3.15 1.84 3.62 2.53 2.03 0.885 0.25-0.63 0.48-0.49 0.62

2.58 3.37 7.85 1.92 1.42 3.45 1.96 1.27 0.502 0.48-1.19 0.61-0.63 0.71

3.31 3.05 3.06 8.06 6.08 8.19 6.12 1.86 0.0064 1.23-2.71 0.93-2.04 1.35

1.51 1.33 0.72 1.70 1.51 1.22 1.07 1.55 0.022 0.89-2.31 0.83-1.92 0.75

0.34 0.39 0.82 0.15 0.17 0.44 0.28 0.41 0.083 0.31-0.73 0.26-0.56 0.12

2.17 2.00 1.57 0.48 0.71 1.04 0.95 6.83 0.181 0.92-1.88 1.26-2.09 0.93

Hong Kong, China/Industrial area Hong Kong, China/Background Tainan, Taiwan/Suburban e

Tainan, Taiwan/Suburban f

Dhaka, Bangladesh /Urban Aveiro, Portugal/Rural

h

Mar.-Apr., 2001 Summer, 2003

i j

Chiang Mai, Thailand/Urban

Dry season (Feb.Apr., 2010)

k

Chiang Mai, Thailand/Suburban Chiang Mai, Thailand/mountain

a

Wang et al. (2002). Ho et al. (2003). Hsieh et al. (2008). Hsieh et al. (2009).

b,c,d e f g h

Salam et al. (2003). Pio et al. (2008). i,j,k This study.

71

Table 4.7 Carboxylic acids concentrations (ng m-3) measured at various sampling sites around the world in recent years
Location
Christchurch, New Zealand Hong Kong, China/Urban b Tainan, Southern/Suburban c Tainan, Taiwan/Suburban d
a

Sampling period
Winter Summer Winter Summer Autumn and Summer PM episode (Nov., 2004) non episodic (Sep.-Oct., 2004) PM episode (Nov., 2004) non episodic (Sep.-Oct., 2004) August and September Winter Summer Winter 1996 2002-2003 October, 1995 Summer, 2003 Dry season (Feb.-Apr., 2010)

Size
PM10 PM10 PM2.5 PM2.5 PM2.5 PM2.5 PM2.5 Four mode Four mode PM2.5 PM2.5 PM2.5 PM2.5 PM2.5 PM10 TSP PM2.5-10 PM10 PM10 PM10

Acetic
430 78 84 87-328 332.5-422.5 456.3-486.1 258.7

Formic
480 110 154 89-245 58.2-115.4 51.7-51.73 57.6

Glutaric
20.0 7.0 0.9 11.8-51.8 9.2-34.4 24.1

Succinic
31 23 50 7 29.6 61.2 77.4 67.3 80.0 52.86 71.9 33.0 55-167 2.7 37.6-105.7 24.2-70.0 26.9

Malic
53.0 41.7 36.3 29.5 35.9 14.75 6.54 2.51 1.9 59.1-136.4 45.6-94.6 35.0

Malonic
6.6 5.1 20 13 20.8 50.7 64.7 61.6 71.3 23.25 89.1 47.6 43-107 8.4 48.8-99.5 41.6-77.7 33.0

Tartaric
11.6 4.7 4.0 4.38 3.85 7.51 0.2 31.9-54.3 33.2-42.9 23.9

Maleic
74 1 45.5 25.8 13.2 26.3 8.01 14.76 19.9 12.4 44.3-92.3 93.1-121.3 35.5

Fumaric
3.15 3.38 9.6-27.4 6.8-16.0 14.3

Oxalic
85 39 350 90 449.3 795.1 460.4 986 676 147.1 478 268 1140 353 377 58-360 17.3 284.3-758.9 243.5-610.6 374.1

Phthalic
78.0 89.9 6.92-54.4 25.0-37.7 6.8

Citric
38.7-48.5 20.8-37.6 19.5

Tainan, Taiwan/Suburban

Ali Mountain, Taiwan/Background f Hong Kong, China/Urban g So Paulo, Brazil h Beijing, China i New York, USA j Aveiro, Portugal k Chiang Mai, Thailand /Urban l Chiang Mai, Thailand/Suurban m Chiang Mai, Thailand/Mountain n
a

Wang and Shooter (2004). Yao et al. (2004). c Hsieh et al. (2007). d Hsieh et al. (2008). e Hsieh et al. (2009). f Tsai et al. (2008). g Ho et al. (2006). h Souza et al. (1999). i Wang et al. (2007b). j Khwaja (1995). k Pio et al. (2008). l, m, n This study
b

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Table 4.8 Anhydrosugars and sugar alcohols concentrations (ng m-3) measured at various sampling sites around the world in recent years
Type/Location Forest fire/Aveiro, Portugal a Rice straw/Douliou, Taiwan
b

Sampling period Summer, 2003 Burning peak Burning season

c

Size PM2.5-10 PM2.5-10 PM2.5-10 PM2.5 PM2.5 PM10 Bulk aerosols PM10 PM10 PM10

Levoglucosan 17-105 370-1104 199-378 120-950 1726-6091 55.1-1962 1-55.1 1410-16000 120-480 333.18-1175.50

Mannosan 332.8-1086.8 1.8-10.4 18-114 27.32-83.25

Arabitol 5.2 0.7-6.6 129.07-334.16

Glycerol 26.92-346.55

Erythritol 14.37-66.19

Agricultural waste/Hong Kong, China Forest (wildfire)/Montana, U.S.A. Biomass burning/Beijing, China Forest (wildfire)/Maine, U.S.A. Woodburning/Austria
h f g e d

Winter Aug.-Sep., 2003 July, 2002-July, 2003 May-Oct., 2002 Winter One year, 2004
i

Woodsmoke/Launceston, Australia

Forest (wildfite)/Chiang Mai, Thailand

a b c d e f g h i

Dry season

Pio et al. (2008). Lee et al. (2008). Wang et al. (2007a). Ward et al. (2006). Zhang et al. (2008). Medeiros et al. (2006). Jordan et al. (2006). Caseiro et al. (2009). This study.

73

Chapter 5 Conclusion

5.1 Conclusions

This study has investigated the inorganic salts, water-soluble carboxylic acids, anhydrosugars and sugar alcohols in PM10 aerosols were observed two periods during non episodic pollution and PM10 episode in Chiang Mai basin. Some principal conclusions were presented as follows:

(1) Water-soluble carboxylic acids, anhydrosugars and sugar alcohols in PM10 aerosols concentration were found during the PM10 episode higher level than during non episodic pollution period. But during second observation period, the sulfate concentration in PM10 was increase 3 times because ozone increases due to high sulfate, significant photochemical formation processes emitted from anthropogenic activity. (2) High calcium concentration observed at TOT site, indicating that suburban area might be contributor mineral dust from industrial or biomass burning. (3) Acetic acid was the most abundant monocarboxylic acids follow by formic acid. Oxalic acid was the dominant dicarboxylic acids both periods. (4) During PM10 episode concentration of species higher than during non episodic pollution period, which CMU site concentrations are higher than other site, indicating that more source from biomass burning or traffic emission were transport to urban area. (5) During the PM10 episode, carboxylic acids higher during daytime
74

indicating that carboxylic formed by photochemical reaction and/or emitted directly by biomass burning processes more frequency at daytime. (6) During non episode IOP1, the most pronounced in during IOP1 but was only detected during IOP2 low concentration demonstrates that the molecular composition of these acids during two intensive observation periods was also different. Moreover, maleic acid was the second dominant species of dicarboxylic acid during IOP1, suggests that coal burning was significant source contribution maleic acid during firth intensive period. (7) Levoglucosan concentration was the dominant anhydrosugars, follow by mannosan, which levoglucosan was found to be the most useful marker for biomass burning generated from natural forest fire event in the mountain around Chiang Mai basin. Moreover, the ratios of levoglucosan to PM10 in forest fire are 0.53-1.48%. (8) Levoglucosan concentration showed in the nighttime higher than the daytime both of period, which levoglucosan is a byproduct of cellulose pyrolysis. These results suggest that activity from biomass burning emitted during the nighttime. (9) The sugar alcohols arabitol were found in the leaf combustion was the most abundant species higher in daytime. (10)The ratio of acetic to formic acids (A/F) > 1 was often used to demonstrate the primary source by wood burning or vehicular emission, and it indicated that the contribution of primary sources from biomass burning. (11)The ratio of malonic to succinic acids (M/S) were within the values reported for more potential to be primary source (PM10 episode) and more potential to be secondary source (non-episodic pollution).
75

(12)The ratio of K/Levo and Levo/Manno were used to for investigate biomass burning, which during dry season in Chiang Mai high biomass burning is a significant emitted from hardwood and softwood. (13)The composition of atmospheric aerosols in Chiang Mai Basin during intensive period was mainly affected by biomass burning of leaves/bark trees and traffic emission.

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5.2 Suggestions for the future work Characterize of inorganic salts, carboxylic acids, anhydrosugars and sugar alcohols of particulate matter during dry season at Chiang Mai basin showed promising results. Recommendations for further study for explain differences and identifying the source of pollutant in Chiang Mai aerosols include:

1. Measure emission others species such as OC and EC should be studied to investigate. 2. The size distributions of water-soluble organic species in atmospheric should be found.

77

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