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Chapter 1 Introduction

1.1 Introduction

Particulate matter is the major air pollutant of atmospheric aerosols


and 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 and
marine 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 strong
correlation 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 to
local 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-β-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. 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 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 µg 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+ and
K+), 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 109.0±54.1 µg 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 µg m-3. By contrast, concentrations of SO42-, NO3-,
and NH4+ in PM10 were lower, averaging 10.2, 6.6, and 6.0 µg 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
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).

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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 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 CCN
Gas/Particle
Transportation Partition
Fine IN
Aerosols
Volatile
Compounds
Coarse Organic aerosols
Aerosols

Organic and inorganic


Mixed aerosols
Dry Wet
Emission Emission Deposition Emission
Deposition

Fig.2.2 Surface
Production cycle (land, ocean, snow)
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 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. Anthropogenic sources are important for the precursors of succinic,
maleic and fumaric acids (Röhrl and Lammel, 2002). 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

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 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
(Röhrl 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).
Nevertheless, formic acid still had a predominantly (89±5%) 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).

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 also
measured. 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 has
a 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) showed
vehicular 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−, SO42− 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−, SO42−)
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 of
terrestrial 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 gasoline
continues 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−, SO42−) 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 acids
measured (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 the
dominant 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 30–50% 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 during
afternoon 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 3.7
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 µm 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
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.

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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 São Paulo City, Brazil. Ambient
level measurements of formic, acetic, α-hydroxy-acetic (glycolic),
β-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 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 ratio<1 and in situ formation by
photochemical processed; high ratio>1). 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 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 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.

Röhrl 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

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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 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.

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 biomass
burning 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 hemicelluloses
containing 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-β -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). 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. 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 organic
compounds. 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 140±55 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 between
levoglucosan 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 2.1 Saccharides commonly found in atmospheric aerosol and
their sources (Caseiro et al., 2007)
Compound
Primary sugars (mono- and disaccharides)
Arabinose Lichens
Fructose Lichens
Soil biota
Galactose Soil biota
Glucose Fungi
Lichens
Soil biota
Wood burning
Mannose Soil biota
Xylose Soil biota
Maltose (monohydrated) Soil biota
Sucrose Plants
Soil biota
Mycose (Trehalose) Yeast
Bacteria, fungi
Soil biota
Sugar alcohols
Arabitol Fungi, Lichens
Erythritol Lichens
Soil biota
Glycerol Soil biota
Inositol Soil biota
Mannitol Fungal spores
Fungi
Lichens
Soil biota
Sorbitol Bacteria
Lichens
Soil biota
Xylitol Fruits, berries,
hardwood
Soil biota
Anhydrosugars
Galactosan Wood burning
(1,6-anhydro-β-D-galactopyranose)
Levoglucosan (1,6-anhydro-β-D-glucose, Wood burning
1,6-anhydro-β-D-glucopyranose)
Mannosan (1,6-anhydro-β-D-mannopyranose) Wood burning
1,6-Anhydrogluco-furanose Wood burning

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


from thais researchers)
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 18o47’54.90’’ N and longitude 98o56’55.75’’ 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 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.
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, concentration


analysis.
CMU site

TOT site

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 μg and
a Sartorius CP2P analytical balance with a sensitivity of 1 μg. 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 -18°C 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 MΩ cm-1 at 25°C, 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 μm 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 μL 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 and phthalic acid in the aerosol samples.

Additionally, 1000 μL 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
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 µL 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.
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

5 mM 100 mM 100 %
Time(min) H2O
NaOH NaOH 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
單位:ppb
Before weighing Teflon
filters were condition at
40±5% RH 24 hr

Sampling PM2.5-10 aerosol


by MicroVol 1100

After weighing Teflon


filters were condition at
40±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 µm


ester acetate filter

1000 μL filtrated to 25 µL filtrated to 1000 μL filtrated 200 µL filtrated


IC-Dionex DX-600 IC-Dionex to IC-Dionex to IC-Dionex
Analyze : ICS-1000 ICS-2500 ICS-2500
carboxylic acids Analyze : Cation Analyze : Anion Analyze :
and oxalic acid anhydrosugars

Fig. 3.3 Step for MicroVol sampling and analysis flow chart
Table 3.2 The names and chemical structures of carboxylic acids and
anhydrosugars
Table 3.2 The names and chemical structures of carboxylic acids and
anhydrosugars (continue)
Common
Common IUPAC
IUPAC Chemical
Chemical Structural
Structuralformula
formula
name
name name
name formula
formula
OH
Phthalic acid
Formic methanoic acid
benzene-1,2- C6HCOOH
O

acid H4(COOH) HOHO O


dicarboxylic acid 2

O
Acetic acid
Oxalic ethanoic acidacid
ethanedioic CHC3COOH
2H2O4 HO O
acid OH
HO O
O
Glutaric
Levoglucosan pentanedioic acid
1,6-anhydro-β-D- C5H8O4 O O
O x a lic a c id
acid glucopyranose C6H10O5
HO OH
O
Mannosan
Succinic 1,6-anhydro-β-D- C6H10O5 HO
butanedioic acid
mannopyranose C4H6O4 OH
acid
O
O
1,6-anhydro-β-D- C6H10O5 Succinic acid
Malic monohydroxybutanedioic
Galactosan galactopyranose OH
C4H6O5 HO
acid acid
OH O
O acid
Malic O
Malonic
propenedioic acid C3H4O4
acid HO OH
O H acid
Malonic O
2,3-
Tartaric HO
dihydroxybutanedioic C4H6O6 OH
acid
acid O OH
OH
T ar ta O a cid
ric
Maleic O OH
cis-butenedioic acid C4H4O4
acid
O
Maleic acid
Fumaric HO
trans-butenedioic acid C4H4O4 OH
acid
O
Fumaric acid

3.4 Other data


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 pollutant
concentrations.
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