Comparison of Carboxylic Acids and Ions Bound on PM10 During Haze Episode in Chiang Mai Area

Supapan Athirot1, Khajornsak Sopajaree2 and Ying I. Tsai3

1

Department of Environmental Engineering, Chiang Mai University, Chiang Mai 50200, Thailand and Department of Environmental Engineering and Science, Chia Nan University of Pharmacy and Science, Tainan 717, Taiwan
2

Department of Environmental Engineering, Chiang Mai University, Chiang Mai 50200, Thailand

Department of Environmental Engineering and Science, Chia Nan University of Pharmacy and Science, Tainan 717, Taiwan E-mail: s.athirot@yahoo.com Tel. 08-567-1265

Abstract
Aerosol samples were collected between 7 April 1 May 2011 at Chiang Mai University (CMU) and Chiang Mai city hall (CCH) sites in Chiang Mai, Thailand using Quartz Microfiber filters (8x10 in) by PM10 High Volume Air Samplers. The average concentration of PM10 at CCH site (47.2215.71 g m-3) were higher than CMU site (40.709.41 g m-3). Inorganic salts were found at CMU (10.263.41 g m-3) which were site higher than CCH site (9.253.54 g m-3). Sulfate was the most abundant inorganic salts follow by ammonium, calcium and potassium. Carboxylates were found at CCH site (912.70295.17 ng m-3) which were higher than CMU site (903.75223.06 ng m-3). Acetate was the most abundant carboxylates follow by oxalate and malate. Levoglucosan was the most dominant anhydrosugar, that found at CCH site (230.50 61.98 ng m-3) again higher than CMU site (224.4981.79 ng m-3). Mannitol was the most dominant sugar alcohols, which found at CCH site (175.72 60.74 ng m-3) which were higher than CMU site (150.7163.72 ng m-3). Glucose was the most dominant sugars, which found at CMU site (383.49135.16 ng m-3) which were higher than CCH site (316.5596.18 ng m-3). Correlation between oxalate and potassium of this study (r=0.715 at CMU site and r=0.750 at CCH site), indicating source from biomass burning, secondary and conversion from organic acids. The A/F ratio at CMU site (16.29) and CCH site (16.38) more than 1, indicating that a large contribution of primary sources from biomass burning. The M/S ratio at CMU site = 0.69 and CCH site = 0.49, indicating during study period to be primary vehicular emissions. K/Levo in this study at CMU site = 5.27 and CCH site = 5.12. The average ratio of levoglucosan (Levo) and mannosan (Manno) was found at CMU site = 23.07 and CCH site = 17.18, indicating that biomass burning emitted from hardwoods and softwoods. The main sources PM10 in Chiang Mai from biomass burning, crustal matter, traffic emissions, vehicle exhaust and heavy oil burning Keyword: PM10, biomass burning, Carboxylic acids, Anhydrosugars, Chiang Mai

1. Introduction
Particulate matter, also known as particle pollution or PM, is a complex mixture of extremely small particles and liquid droplets. These particles come in many sizes and shapes and can be made up of hundreds of different chemicals. Some particles, known as primary particles are emitted directly from a source, such as construction sites, unpaved roads, fields, smokestacks or fires. Others form in complicated reactions in the atmosphere of chemicals such as sulfur dioxides and nitrogen oxides that are emitted from power plants, industries and automobiles. These particles, known as secondary particles, make up most of the fine particle pollution in the country. The pollution levels have become so severe that areas within four provinces, Chiang Mai, Chiang Rai; Nan and Mae Hong Son have been declared disaster zones due to the almost zero visibility on the 13th March 2007 and high numbers of people seeking medical assistance for respiratory illness. Chiang Mai is the large city in the northern part of Thailand and is about 700 km from Bangkok and is 300 m above sea level, with a population of 1.6 million. Approximate area is 20,107.057 km2, the agriculture area is approcimately 2,936.68 km2 (14.61%). Chotruksa (2010) studied characterization of carboxylic acid and anhydrosugars in PM10 between February and April of dry season 2010 at urban, suburban and mountain sites in Chiang Mai basin, and found concentrations of inorganic and organic species in PM 10 aerosol at urban site are always higher than at suburban and mountain sites. Concentration of carboxylic acids during the PM10 episode was higher than that during non-episodic pollution. Levoglucosan (Levo) and arabitol were the most dominant anhydrosugar and sugar alcohol, the ratio of levoglucosan to PM 10 in forest fire are 0.53-1.59% by PM10 mass. Mass ratio of acetic to formic acids (A/F) > 1, the ratio of malonic to succinic acids (M/S) in the range of 0.81-7.12, the ratio of potassium to levoglucosan (K/Levo) and levoglucosan to mannosan (Levo/Manno) were in the range of 0.70-2.68 and 5.73-69.48, respectively. The most significant contribution to PM 10 in Chiang Mai basin was the photochemical formation of secondary aerosols and primary source from biomass burning contributed by hardwood and softwood of leaves/bark trees. The purpose of this study are to characterize of carboxylic acids, inorganic species, anhydrosugars, sugar alcohols and sugars in aerosol during dry season in Chiang Mai and to explaining differences and identifying the source of pollution in Chiang Mai province.

2. Experimental
2.1 Sampling
Aerosol samples were collected between 7 April 1 May 2011, on a 8x10 in Quartz Microfiber filters (Whatman) by using a Staplex PM10 High Volume Air Samplers (The Staplex Company, Inc., Brooklyn, New York, USA), (Figure 1) with flow rates of 1,130 m3 h-1. The collection of PM10 samples was made at two sampling stations located in 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 suburban area, near Suthep mountain, has little traffic and excellent ventilation; and Chiang Mai City Hall (CCH; 2

Located at latitude 18o5013.02 N and longitude 98o5815.01 E) set at ground level, located in the urban area, with heavy traffic highways and has a air quality monitoring station by Pollution Control Department.

Figure 1 Staplex PM10 High Volume Air Samplers

Each sampling collected two sets of aerosol samples were collected daily, one from 7 am to 7 pm (12 h: daytime) every 2 days and another from 7 pm to 7 am (12 h: night time) every 2 days. Figure 2 was shown the geographic locations of air sampling sites.

Figure 2 Location of the sampling sites in Chiang Mai province 2.2 Sampling handing
Before and after sample collection, filters were conditioned at 40 5% RH for 24 hours and subsequently weighed at 503% RH using a Mettler Toledo AT261 analytical balance with a sensitivity of 10 g and a Sartorius CP2P analytical balance 3

with a sensitivity of 1 g. All weight measurements were repeated three or more times and the Shewart control procedures were followed to ensure reliability. Additionally, blank filters were prepared by purging in 99.995% pure nitrogen for 30 seconds and then processed as for sample-containing filters.

2.3 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, 20.0 mL of deionized water (resistivity >18.0 M cm-1 at 25C, Barnstead) will be added and the contents will be shaken (Yihder TS-500 Shaker) in an unlit refrigerator at 4 C for 90 min to prevent the decomposition of the extracted carboxylic acid species. The liquid is then filtered through a 0.2 m ester acetate filter and the aqueous filtrate will be is characterized using IC, following a slightly modified version of the method of Hsieh et al. (2008). 2.3.1 Carboxylic acids Analysis The ion chromatography system (IC) model DX-600, Dionex is equipped with a gradient pump (Model GP50), an ASRSUltra 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 AG11HC, 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. 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. 2.3.2 Ions, anhydrosugars and sugar alcohols analysis Additionally, 1000 L of the aqueous extract will be injected into IC Model Dionex ICS-2500 using 9 mM Na2CO3 eluent at a flow rate of 1.4 mL min-1. Concentrations of the separated inorganic species including 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 CarboPacTM MA1 (4 mm), flow rate 0.4 mL/min, injection volume 0.2 mL, eluent conducted for the 400 mM NaOH component analysis.

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. 2.3.3 Carbon Analysis A W.C. Heraeus CHN-O-Rapid elemental analyzer was used to determine the concentrations of carbon particles on the filter. A thermal conductivity detector (TCD) was applied to detect the CO 2 content in the aerosol sampler after the thermal process, where EC and OC denoted the concentrations of elemental carbon and organic carbon, respectively. Quartz fiber filters were heated prior to use for 4 h at 950C to reduce their carbon blank. Thus, the background concentration of carbonaceous materials in the quartz fiber filter and matrix, which can influence the analyzer results, was minimized (Ohta and Okita, 1990). The filter samples were stored in a freezer to prevent OC loss until they were analyzed for carbon. The operating conditions included oxidation at 950C for a heating time of 1.5 min and reduction at 600C. One-quarter of the filter samples was detected without any pre-treatment. The carbon obtained herein was the total carbon (TC). The other quarter of the samples was put into a 340C oven, and was heated in advance for 10 min to expel the organic carbon fraction (OC). (Cadle and Groblicki, 1982). By applying the same operating conditions used for obtaining TC, described above, the elemental carbon (EC). could be obtained. The value of OC was calculated as the difference between TC and EC. In order to discriminate between EC and OC, and to prevent the pyrolytic conversion of OC to EC arising during the 340C heating process, the precision and accuracy of the analytical process for aerosol carbon were carried out. Acetanilid was employed as the standard for the calibration curve of the carbon analysis. Each calibration curve had at least seven points. The instrument background value was measured after analyzing one standard. One background value and one standard were measured for every five samples. The additional data obtained from the background value was substituted into the calibration curve. The value was compared to the calibration curve to ensure the obtained ratio fell within the 1.000.05 range. The analytical precision of the carbon data was determined by the replicate analysis of 82 standard Acetanilid. The carbon analysis variation coefficient was less than 2% for the carbon samples. The amount of organics was determined to be 1.4 times the organic carbon mass measured (Pinto et al., 1998). The detection limits of TC, EC and OC were 0.01, 0.01 and 0.02 g/m 3, respectively (Cheng and Tsai, 2000). 2.3.4 Heavy metal Analysis Analysis by Agilent 7500a Inductively Coupled Plasma Mass Spectrometer (ICP-MS) using Taiwan EPA NIEA M105.00B analysis methods. An appropriate amount nebulizer was applied to the samples solution after the first spray treatment and then aspirated with the load current transport, will be formed with analysis of elements of the aerosol delivered to solvents. Decomposition, atomic/ion reactions and so on, will be located in the plasma to be analyzed elements in the formation of unit positive ions, and then through the vacuum interface to transfer into the mass spectrometer, then with the mass analyzer to the 5

specific mass-to-charge ratio of the ions to be resolved then be detected with electron multiplier, many elements of the future conduct qualitative and quantitative work. 2.4 Meteorological data Ambient air quality data were obtained from the Thailand Pollution Control Department (PCD), information was obtained on air quality data from 7 April to 1 May 2011 over Chiang Mai province, Thailand. The air quality was particularly useful for observing pollutant concentrations

3. Results and Discussion

The variation of PM10 mass concentration during dry season, that collect from 7 April to 1 May, 2011 shown in Figure 3, comparison intensive observation period between CMU site and CCH site with PM10 mass concentration from PCD data in Chiang Mai were in similar pattern. The average concentration of PM10 at CCH site (47.2215.71 g m-3) were higher than CMU site (40.709.41 g m-3).

Figure 3 PM10 mass concentration of intensive observation period with PCD data during period of study
In addition, the correlation of PM10 concentration between PM10 data from PCD and this study are plotted as shown in Figure 4. The correlation between PM10 from PCD data and PM10 during period of study for both sampling sites show a good correlation which present the correlation coefficients of 0.791 and 0.840 for CMU and CCH sites, respectively. This correlation verify the mass concentration that determined by gravimetric method is equivalent to the TEOM method. Thus, collected filters were furthers analyzed for the chemical compositions.

Figure 4 Correlation of PM10 concentration from PCD data with PM10 concentration from observed site during period of this study
The concentrations and standard deviations of inorganic salts, carboxylic acids, anhydrosugars, sugar alcohols, sugars and ratios of aerosol components are shown in Table 1. From Table 1 inorganic salts were found at CMU (10.26 3.41 g m-3) site were higher than CCH site (9.253.54 g m-3). Sulfate was the most abundant inorganic salts follow by ammonium, calcium and potassium. Carboxylates were found at CCH site (912.70295.17 ng m-3) were higher than CMU site (903.75223.06 ng m-3). Acetate was the most abundant carboxylate follow by oxalate and malate. Levoglucosan was the most dominant anhydrosugar, that found at CCH site (230.50 61.98 ng m-3) were higher than CMU sits (224.4981.79 ng m-3). Mannitol was the most dominant sugar alcohols, which found at CCH site (175.7260.74 ng m-3) were higher than CMU sit (150.7163.72 ng m-3). Glucose was the most dominant sugars, which found at CMU site (383.49135.16 ng m-3) were higher than CCH site (316.5596.18 ng m-3). Oxalate may be good tracer of biomass burning (Jaffrezo et al. 1998). Figure 5 shown good correlation between oxalate and potassium. Oxalate presents good relationship with potassium during period of this study (r=0.715 at CMU site and r=0.750 at CCH site), indicating source from biomass burning, secondary and conversion from organic acids.

Figure 5 Correlation of potassium concentration with oxalate concentration of each site sampling
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Primary emissions and photochemical transformations were suggested as the sources of carboxylic acid (Yu, 2000). Acetic acid was mainly from primary emissions, while formic acid was largely from secondary transformations. The acetae/ formate (A/F) mass ratio was used to distinguigh the primary (A/F>1) and secondary (A/F>1) sources (Villanueva-Fierro et al., 2004; Wang et al., 2007). Table 1 shown A/F ratio at CMU site (16.29) and CCH site (16.38), indicating that a large contribution of primary sources from biomass burning.

Table 1 Mean (SD) chemical composition of PM10 aerosol from observed site during period of this study
CMU (n=26) Mean SD PM10 (g m-3) 40.70 9.41 Inorganic species (g 10.26 m-3) 3.41 Sodium 0.37 0.23 Ammonium 1.50 0.56 Potassium 1.01 0.32 Magnesium 0.49 0.32 Calcium 1.48 0.94 Chloride 0.28 0.15 Nitrate 0.45 0.18 Sulfate 4.64 1.65 Species Carboxylates (ng m-3) 903.75 Acetate 500.42 Formate 30.71 Pyruvate 31.46 Glutarate 3.08 Succinate 12.50 Malate 101.84 Malonate 8.64 Tartarate 7.45 Maleate 6.41 Fumarate 13.49 Oxalate 156.28 Phthalate 4.61 Citrate 26.84 223.06 209.04 26.11 14.76 1.34 8.93 49.32 4.26 3.47 2.77 11.49 54.34 1.62 12.51 CCH (n=24) Mean SD 47.22 15.71 9.25 3.54 0.24 0.10 1.45 0.59 1.03 0.34 0.36 0.22 1.15 0.55 0.20 0.13 0.57 0.29 4.24 1.89 912.70 505.57 30.86 25.64 3.09 11.15 101.38 5.46 7.89 6.02 9.83 173.15 3.47 29.18 295.17 209.00 32.17 32.17 1.30 8.06 50.38 1.87 7.23 2.53 6.21 104.02 1.46 8.76 CMU (n=26) CCH (n=24) Mean SD Mean SD Anhydrosugars (ng 224.49 m-3) 81.79 230.50 61.98 Levoglucosan 192.16 78.81 201.00 55.99 Mannosan 8.33 5.17 11.70 4.76 Galactosan 8.30 4.18 17.80 3.99 Species Sugars (ng m-3) Mannose Glucose Galactose 416.06 18.40 383.49 14.18 132.02 336.35 98.23 7.27 7.80 4.02 135.16 316.55 96.18 5.29 12.00 4.90 82.55 264.92 68.29 18.84 23.18 18.49 33.30 25.19 10.71 10.80 34.41 14.03 63.72 175.72 60.74 1.92 6.42 3.25 16.38 0.49 0.04 5.12 17.18 0.43

Sugar alcohols (ng m-3) 256.71 Erythritol 26.79 Glycerol 48.15 Inositol 26.72 Mannitol 150.71 Xylitol 4.35 Ratios A/F M/S Oxalate/SO4 K/Levo Levo/Manno Levo/PM10*100

16.29 0.69 0.03 5.27 23.07 0.47

The malonate/succinate (M/S) mass ratio was a useful indicator to differentiate primary (vehicular) source from secondary sources. Kawamura and Kaplan (1987) reported the M/S ratio to be 0.3-0.5 from vehicular emissions. M/S ratio in Table 1 shown ratio at CMU site = 0.69 and CCH site = 0.49, indicating during study period to be primary vehicular emissions. Potassium (K) a commonly used tracer for biomass burning. Tsai et al. (2010) reported K/Levo ratio of 0.288 for hardwood (fresh sandal wood), higher than the 0.229 in hardwood (aged sandal wood), while Chotruksa et al. (2010) reported K/Levo ratio in the range 0.78-2.68 in hardwood. K/Levo in this study at CMU site = 5.27 and CCH site = 5.12. The average ratio of levoglucosan (Levo) and mannosan (Manno) was found at CMU site = 23.07 and CCH site = 17.18, indicating that biomass burning emitted from hardwoods and softwoods. 8

4. Conclusion
This study observed 2 sampling sites. Sulfate was the most abundant inorganic salts follow by ammonium, calcium and potassium. The most abundant carboxylic acids: acitic acid> oxalic acid > malaic acid. The A/F raio > 1, indicating that source from primary source by wood burning or vehicular emission. The M/S ratio < 1 reported source from primary vehicle exhaust. The K/Levo ratio 5.12-5.27 and the Levo/Manno ratio 17.18-23.07 biomass burning emitted from hardwoods. Levoglucosan was abundant anhydrosugars species followed by mannosan. Glucose and mannitol were dominant sugars and sugar alcohols species, respectively. The results in this study were shown the main sources PM 10 in Chiang Mai from biomass burning, crustal matter, traffic emissions, vehicle exhaust and heavy oil burning.

5. Reference
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Villanueva-Fierro, I., Popp, C.J., and Martin, R.S., 2004. Biogenic emissions and ambient concentrations of hydrocarbons, carbonyl compounds and organic acids from ponderosa pine and cottonwood trees at rural and forested sites in Central New Mexico. Atmospheric Environment 38 : 249-260. Wang, Y., Zhuang, G., Chen, S., An, Z., Zheng, A., 2007. Characteristics and sources of formic, acetic and oxalic acids in PM2.5 and PM10 aerosols in Beijing, China. Atmospheric Research 84 : 169-181. Yu, S.C., 2000. Role of organic acids formic, acetic, pyruvic and oxalic in the formation of cloud condensation nuclei (CCN): a review. Atmospheric Research 53 : 185217.

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