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1.1 Introduction
1.2 Purpose
2
(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.
3
Chapter 2 Literature review
4
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.
5
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
Fig.2.2 Surface
Production cycle (land, ocean, snow)
of carboxylic acids in the atmosphere
(Sun and Ariya, 2006)
6
2.3 Sources of carboxylic acids
7
2.3.2 Emissions from biogenic sources
8
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).
9
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).
10
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.
11
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.
12
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.
13
2.6 Anhydrosugars
14
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.
15
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
3.1 Sampling
TOT site
Fig.3.2 Map of Chiang Mai province area identifying the location of air
sampling sites.
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
15 mL of Centrifuge tube
placed and added deionized
water 5 mL
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
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
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