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Chapter 1 Introduction

1.1 Introduction

Particulate matter is the major air pollutant of atmospheric aerosolsand can be the predominant constituent of find atmospheric particles, are

important organics 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). Carboxylic acids in

the particle phase accounted for a small fraction of the organic carbon.

Results indicated that photochemical processes and anthropogenic

emissions such as automobile exhaust are major sources of atmospheric

carboxylic acids (Khwaja, 1995). 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

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 andmarine atmosphere. Oxalic acid was found as the most abundant species,

followed by succinic and malonic (Khawaja, 1995; Chebbi and Carlier,

1996; Ho et al., 2006; Hsieh et al., 2008; Tsai et al., 2008; Hsieh et al.,

2009).

Average (SD) concentrations (ng/m3) of PM10-bound ions in each

season. Both anions (SO42- , NO3

-, and Cl-) and cations (NH4+, Na+, K+,

Mg2+ and Ca2

+) were significantly higher in dry period (Dec-Mar) and

transition period I (Oct-Nov) than those in other season. The dominant

anion and cation were SO42- and NH4+, respectively. There was a strongcorrelation between NH4

+ and SO42- (r = 0.953), followed by Na+ and

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SO42- (r = 0.651) and K+ and Cl- (r = 0.606). It suggested that the main

acidity of dry deposition in this region was due to H2SO4, which was

neutralized by NH4+. Concentrations of elements and metals were high in

dry season. High toxic metals including lead (Pb), mercury (Hg),

cadmium (Cd) and arsenic (As), were detected. This is probably due tolocal activities such as open burning of biomass, etc. and traffic density in

the area. It can be concluded that temporal variation plays more important

roll than spatial variation(Chuersuwan et al., 2004, Chantara and

Chunsuk, 2008, Chantara 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 vegetationsubjected 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. manosan, 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.

1.2 Purpose

In northern of Thailand, few studies describe atmospheric

measurements of particulate matter during the dry season (December toMarch), 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 200300 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 (Chantara and Chunsuk, 2008). The average pH of rainwater in

Chiang Mai was 5.5, indicating the rainwater tended toward the neutral

property. Means of log-transformed bulk deposition were 14% (Na+

andK+), 13% (Mg2+), 7% (Ca2+), 4% (NO3

-), 3% (SO42- and Cl-) and 2%

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(NH4+) higher than that of wet-only deposition. This can be implied that a

comparison of carboxylic acids and anhydrosugars in PM aerosol has not

been reported in the literature.

The purpose of this study is to characterize of carboxylic acids(acetic acid, formic acid, glutaric acid, succinic acid, malonic acid,

tartaric acid, malic acid, maleic acid, phthalic acid, fumaric acid and

oxalic acid) and anhydrosugars (levoglucosan, mannosan and galactosan)

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 province. In addition, ions OC/EC, and heavy metal bound

on PM10 will be determined.

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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 wind blown dust. Secondary aerosol are

often produced by atmospheric gases reacting and condensing, or by

cooling vapour condensation (gas to particle conversion). Figure 2.1

shows some of these processes, along with the three size 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)

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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 PM10component. 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. Acombination 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

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 thistime (Hsieh et al., 2008).

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By the Fig. 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 changethe 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

Chemical

Transformation

Gas/Particle

Partition

Cloud

Fine

Aerosols

Coarse

AerosolsOrganic aerosols

IN

C

Organic and inorganic

Mixed aerosols

Transportation

Volatile

Compounds

EmissionDry

Emission Emission

Wet

Deposition

Fig.2.2 Production cycle of carboxylic acids in the atmosphere

(Sun and Ariya, 2006)

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2.3 Sources of carboxylic acids

2.3.1 Direct emissions from anthropogenic sources

The observed amounts of dicarboxylic acids in the particle phaseaccounted 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. Anthropogenic sources are important for the precursors of succinic,

maleic and fumaric acids (Rhrl and Lammel, 2002). All of these

sources are of local importance and their global contribution seems to beminor. Moreover, only the anthropogenic sources which have an

important contribution to atmospheric concentrations of carboxylic acids.

2.3.1.1 Biomass combustion

Biomass combustion including wood burning stoves, forest fires,

and agricultural 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.

2.3.1.2 Motor exhaust emissions

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 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).

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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 thananthropogenic 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 bothdirect anthropogenic emissions (benzene, toluene, nitrogen dioxide and

acetone) and compounds formed during long-range transport of

anthropogenic hydrocarbons (formaldehyde and acetaldehyde).

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 bythe 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).

2.4 Ions, OC/EC, and heavy metals in atmospheric aerosols

Add some information on the formation of OC/EC

Atmospheric aerosols were sampled and analyzed for H+, NH4+,

Ca2+

, Mg2+

, Na+

, K+

, SO42-

, Cl-

, and NO3-

. Gaseous ammonia was alsomeasured. The analyses demonstrated that these ions are these main

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constituents of the particulate water-soluble fraction of the aerosols

sampled. Ion balance studies showed that the main compounds present

were (NH4)2SO4, NH4NO3, and NH4Cl in polluted aerosols and NaCl and

MgCl2 in maritime aerosols. Backward air mass trajectories for collected

samples indicated that NH4Cl is primarily produced locally, NH4NO3 hasa local to medium-distance origin, and (NH4)2SO4 has been transported

over long distances (Roy and Casimiro 1983).

The levels of Suspended Particulate Matter (SPM) and heavy

metals viz. Pb, Cd, Cr, Ni and Fe were measured. Metal concentration

was determined by Atomic Absorption Spectrometry. The atmospheric

aerosol samples were highly enriched with elements viz. Pb and Cd,

which originate from various human activities like transportation and

industrial processes. Principal Component Analysis (PCA) showedvehicular traffic and industrial emission as the major contributors of

metals (Khillare et al., 2004).

2.5 Source of ions, OC/EC and heavy metal in PM10

2.5.1 Direct emissions from anthropogenic sources

In particular, K+, NO3, SO4

2 and Ca2+ are considerably enriched

indicating the seasonal influence of the biomass burning. Fog and rain

with comparable chemical contents in mineral elements indicate a

generalized contamination of the boundary layer by marine (Na+, Cl),

terrigenous (Ca2+) and above all by biomass burning (K+, NO3, SO4

2)

sources (Lacaux et al.1992).

An accurate and complete emission inventory for atmospheric trace

metals on a global scale is needed for both modeler community and

policy makers to assess the current level of environmental contamination

by these pollutants, major emission sources and source regions, and the

contribution of the atmospheric pathway to the contamination ofterrestrial and aquatic environments. Major progress has been made in

assessing emissions of trace metals in various countries and even regions.

These improved national and regional emission inventories have been

used in this work to assess the global trace metal emissions from

anthropogenic sources in the mid-1990s. The results of this work

conclude that stationary fossil fuel combustion continues to be the major

source of Cr, Hg, Mn, Sb, Se, Sn, and Tl with respect to the coal

combustion and the major source of Ni and V with respect to oil

combustion. Combustion of leaded, low-leaded, and unleaded gasolinecontinues to be the major source of atmospheric Pb emissions. The third

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major source of trace metals is non-ferrous metal production, which is the

largest source of atmospheric As, Cd, Cu, In, and Zn (Pacyna and Pacyna,

2001).

2.5.2 Emissions from biogenic sources

Fog and rain with comparable chemical contents in mineral

elements indicate a generalized contamination of the boundary layer by

marine (Na+, Cl), terrigenous (Ca2+) and above all by biomass burning

(K+, NO3, SO4

2) sources. The organic content (HCOO, CH3COO)

higher for the fogs than for rains, unexplainable by the dilution effect, has

its source at a local level in the forest ecosystem. The estimation, from

the organic content of fog and rain, of the gaseous concentrations of

formic and acetic acids confirm the production of carboxylic acidsmeasured (Lacaux et al.1992).

A proper inventory of atmospheric emissions from natural sources

is basic to our understanding of the atmospheric cycle of the trace metals

(and metalloids), and is also needed for assessing the extent of regional

and global pollution by toxic metals. It is generally presumed that the

principal natural sources of trace metals in the atmosphere are wind-borne

soil particles, volcanoes, seasalt spray and wild forest fires. Recent

studies have shown, however, that particulate organic matter is thedominant component of atmospheric aerosols in non-urban areas and that

over 60% of the airborne trace metals in forested regions can be attributed

to aerosols of biogenic origin. Here I estimate that biogenic sources can

account for 3050% of the global baseline emissions of trace metals. For

most of the toxic metals, the natural fluxes are small compared with

emissions from industrial activities, implying that mankind has become

the key agent in the global atmospheric cycle of trace metals and

metalloids.

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 duringafternoon hours, followed by a decrease in the late afternoon. These

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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). The low formic/acetic acid ratio(0.23-2.4) in the

present this study is reflective of the influence of anthropogenic source

rich in acetic acid. Formaldehyde concentrations varied from 0.63 to 3.7ppbv 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 thephotooxidation 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

chemical transformations of precursors production photochemical which

the precise mechanisms of production of carboxylic acid by the ozonereactions 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.

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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 andformic and acetic acids in the gas phase are these reported.

Approximately 98% of the total acetic and formic acids were in the gas-

phase 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 ratio1). These acid ratios fell in the 0.94-

1.85 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 carboxylicacid 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 most abundant acid followed by acetic, pyruvic, hydroxyl-butyric

and glycolic. Among the organic acids studied, oxalic acid was the most

abundant. In addition, correlation between oxalic and pyruvic 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 C4dicarboxylic 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 415, 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 firsttime in ambient air. The results indicate that in particular anthropogenic

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sources are important for the precursors of succinic, maleic and fumaric

acids. Biogenic sources seem to influence the occurrence of malic acid

significantly.

Yao et al. (2002) reported that the C3/C4 mass ratios from asuburban 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 2025m above the

ground level and not close to the heavy traffic, which may explain the

lower contribution of primary vehicular emissions to dicarboxylic acidsthan when measured at the ground level close to the heavy traffic.

Hsieh et al. (2008) studied speciation and temporal characterization

of dicarboxylic acids in PM2.5 during a PM episode and a period of non-

episodic 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 biomassburning in paddy fields may contribute to oxalic acid content in PM

episode aerosol in the study area, especially during nighttime.

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2.6 Anhydrosugars

Anhydrosugars, such as levoglucosan, mannosan and galactosan,

are formed in pyrolysis process of cellulose and hemicellulosescontaining materials, and thus are important tracers for biomass burning

emission (e.g. wood, rice straw, leaves, 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). 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 (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). Thelevoglucosan 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. 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). 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

used as specific tracers show in Table 2.1 provides a list of important

saccharides found in atmospheric aerosols.

Jordan et al. (2006) describes levoglucosan major constituent of

woodsmoke in ambient air collected in Launceston, Australia during the

winter months (May-September) of 2002-2003 were analyzed for organiccompounds. The proportion of radiocarbon (14C) in aerosols used to

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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

sample 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. There was good correlation betweenlevoglucosan and OC (0.89 of PM2.5 and 0.87 of PM10). This suggests that

biomass burning is a significant source of aerosol organic carbon.

Moreover, the most probable source for the high levoglucosan

concentrations and levoglucosan to OC ratios is the burning of fallen

leaves at that time of the year. 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.

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Table 2.1Saccharides commonly found in atmospheric aerosol and

their sources (Caseiro et al., 2007)Compound

Primary sugars (mono- and disaccharides)

ArabinoseFructose

Galactose

Glucose

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--D-mannopyranose)

1,6-Anhydrogluco-furanose

LichensLichens

Soil biota

Soil biota

Fungi

Lichens

Soil biota

Wood burning

Soil biota

Soil biota

Soil biota

PlantsSoil biota

Yeast

Bacteria, fungi

Soil biota

Fungi, Lichens

Lichens

Soil biota

Soil biota

Soil biota

Fungal sporesFungi

Lichens

Soil biota

Bacteria

Lichens

Soil biota

Fruits, berries,

hardwood

Soil biota

Wood burning

Wood burning

Wood burning

Wood burning

Better add some information on ions, OC/EC, and Metals ( papers

from thais researchers)


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Chapter 3 Experimental

3.1 Sampling

Aerosol samples were collected on a 47-mm Teflon filters(Zefluor,Pall) using a Ecotech MicroVol 1100 Particulate Sampler (Fig.3.1) with

a total flow rate of 3 L min-1, between 2 February-2 April 2010, at two

sites: Faculty of Architecture Chiang Mai University (CMU; Located at

latitude 18o4754.90 N and longitude 98o5655.75 E), set at a height of

12 m above ground, located in the urban area, has little traffic, near

Suthep mountain and excellent ventilation; TOT Public Company

Limited (TOT; Located at latitude 18o 41 40.04 N and longitude 99o 2'

59.45 E), set at ground level, with heavy traffic highways and close to

the industrial zone. Each sampling collected two sets of aerosol sampleswere 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.

The geographic locations of air samplings are shown in Fig. 3.2.

Fig. 3.1 Ecotech MicroVol 1100 Particulate Sampler

Add :High Volume air sampler including filter types, concentrationanalysis.


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Fig.3.2 Map of Chiang Mai province area identifying the location of air

sampling sites.

3.2 Sampling handing

Before and after sample collection, filters were conditioned at

40 5% RH for 24 hours and subsequently weighed at 50 3% 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 andthen 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, especially carboxylic acids and ammonium

nitrate. For analyzing carboxylic acid, cations and anions, 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

CMU site

TOT site


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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).

The ion chromatography system (IC) model DX-600, Dionex is

equipped with a gradient pump (Model GP50), an ASRS-Ultra anion self-

regenerating 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% MeOHgradient 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 and phthalic acid in the aerosol samples.

Additionally, 1000 L of the aqueous extract will be injected intoIC 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

F-, Cl-, NO2-, Br-, NO3

- and SO42-, and oxalic acid, 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, mannosan and galactosan)

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. Fig. 3.3 shows flow chart of MicroVol sampling and analysis.

Moreover, Table 3.2 shows chemical structures of carboxylic acids and

anhydrosugars.


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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.

Table 3.1 Ion Chromatography Dionex DX-600 gradient elution ratio

Time(min) H2O5 mM

NaOH

100 mM

NaOH

100 %

Methanol

0.0 80% 4 % 0 % 16 %

9.2 80 % 4 % 0 % 16 %

12.2 0 % 84 % 0 % 16 %

22.0 0 % 49 % 35 % 16 %

Table 3.2 Method detection limits (MDLs) of four chemical compound groups

measured using IC systems

Species MDL Species MDL

Inorganic Salts Carboxylic Acid

Sulfate 4.79 Acetic acid 8.42

Nitrate 7.81 Formic acid 5.99

Nitrite 6.70 Glutaric acid 2.43

Chloride 6.98 Succinic acid 4.20

Sodium 10.32 Malonic acid 1.49

Ammonium 4.21 Tartaric acid 4.89

Potassium 7.91 Maleic acid 1.58

Magnesium 18.38 Fumaric acid 2.45

Calcium 7.37 Phthalic acid 5.28

Anhyderosugars Oxalic acid 7.06

Levoglucosan 6.97 Sugar Alcohols

Mannosan 4.76 myo-Inositol 7.48

Galactosan 12.59 Glycerol 11.84

Glucose 12.59 Xylitol 18.78

ppb


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Fig. 3.3 Step for MicroVol sampling and analysis flow chart

Before weighing Teflon

filters were condition at

405% RH 24 hr

Sampling PM2.5-10

aerosol

by MicroVol 1100

After weighing Teflon

filters were condition at

405% RH 24 hr

Filtered through a 0.2 m

ester acetate filter

Vibration machine 90 minute

15 mL of Centrifuge tube

placed and added deionized

water 5 mL

1000 L filtrated toIC-Dionex DX-600

Analyze :

carboxylic acids

25 L filtrated toIC-Dionex

ICS-1000

Analyze : Cation

1000 L filtratedto IC-Dionex

ICS-2500

Analyze : Anion

and oxalic acid

200 L filtratedto IC-Dionex

ICS-2500

Analyze :

anhydrosugars


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Table 3.2 The names and chemical structures of carboxylic acids and

anhydrosugars


23/29

Table 3.2 The names and chemical structures of carboxylic acids and

anhydrosugars (continue)

3.4 Other data

Common

name

IUPAC

name

Chemical

formula

Structural formula

Formic

acid

methanoic acidHCOOH

OHO

Acetic

acid

ethanoic acid CH3COOH

O

HO

Glutaricacid

pentanedioic acid C 5H8O4 O

OH

O

HO

Succinic

acidbutanedioic acid C 4H6O4

O

OH

O

HO

Malic

acid

monohydroxybutanedioic

acid C4H6O5

OH

O

HOO

OH

Malonic

acidpropenedioic acid C 3H4O4

O

OH

O

HO

Tartaric

acid

2,3-

dihydroxybutanedioic

acid

C4H6O6

OH

OHO

HO

O

OH

Maleic

acidcis-butenedioic acid C4H4O4

O

OHO

OH

Fumaric

acidtrans-butenedioic acid C4H4O4

O

OH

O

HO

Common

name

IUPAC

name

Chemical

formula

Structural formula

Phthalic acid

benzene-1,2-

dicarboxylic acidC6H4(COOH)2

O

HO

O

OH

Oxalic acid ethanedioic acid C2H2O4 O

O H

O

H O

Levoglucosan 1,6-anhydro--D-

glucopyranose C6H10O5

Mannosan 1,6-anhydro--D-

mannopyranose

C6H10O5

Galactosan

1,6-anhydro--D-

galactopyranose

C6H10O5


24/29

Ambient air quality data were obtained from the Thailand Pollution

Control Department (PCD), information was obtained on Air Quality data

from 2 February to 2 April 2010 over Chiang Mai province, Thailand.

The Air Quality was particularly useful for observing pollutantconcentrations.


25/29

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Check References Citation

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