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1 w y wz 10«3y 293~303 ( ) Journal of Korean Society of Urban Environment yw p w Á½ y*á **Á½ y***áy x****á½ * y w»z»»y Á* w y œw Á** w y w ***w HOYA ( )Á**** w m ( , k) A Study on The Chemical Mass Composition of Particle Matter in Seoul Jin-Soo Park ½ Chang-Hwan Kim* ½ Jeong-Joo Lee** ½ Jin-Ho Kim*** Ui-Hyun Hwang**** ½ Shin-Do Kim* Climate and Air Quality Research Department Air Quality Research Division, National Institute of Environmental Research *Department of Environmental Engineering, University of Seoul **Department of Occupational and Environmental Health, Yongin University ***HOYA Electronics Korea Co., LTD. ****Department of Civil Engineering, Gyeongdo Provincial College (Received 25 November 2010 : Accepted 17 December 2010) Abstract Particulate matter is a cause for concern because of its impact on visibility and human health in the world. It is needed to know about construction of particulate matter and to make a policy of reducing particulate matter, to solve the bad effect of particulate matter. In this study, try to define chemical composition of particulate matter of seoul with sampling and chemical analysis. But big portion about 30~40% of gravimetric mass are remained unknown. By way of construction the unknown portion, checking the error of analyzing process and a factor of effect. First, a factor of limit of analysis instrument Second, a factor of uncertainty from estimation of soil materials Third, a factors of uncertainty from estimation of ion fraction Fourth, a factor of conversion organic carbon to organic matter Fifth, a factor of retention of water on conditioned filter. Through checking the five factors as shown as upside, find to way to solve the gaps in gravimetric-measured mass and chemical mass. In this way, result of this study can be more closure to two other Mass. For the reconstruction of PM, concern about five factors show the analytical improve approximately 29%, 19% more chemical mass compared using the chemical analysis. Key Words : particulate matter, chemical composition, gravimetric mass, chemical mass, PM 10, PM 2.5 w jš w ƒ wš. w» w w yw w wš k p q w z w w. d yw mw y w. w yw mw 30~40% yw mw w. w yw w w ƒ y mw yw yw w y w.»» w w, m sƒ y, w sƒ y,»k», w vl w y w. w y w w š mw» yw mw w w ƒ w ƒ w. w 5ƒ w w ƒ w w w w PM 10 PM %, 19%» yw y. :, PM 10, PM 2.5,,, yw Corresponding author sdkim@uos.ac.kr 293

2 294 Á½ yá Á½ yáy xá½ I. w 20»»,» š w ƒ», 50 l»» š, 70 y.» w ƒ š w wš» w w. w ƒ w š l w l w w» w w sƒ w.» yw š, ƒ.» w yw j,, k, w yw w y wš. w w yw,, k yw w ü ³ w» w w wwš.» d y q w» w s yw w ƒ w w 1,2,3). ù ü w ù w» yw yw sƒw»ƒ.,» w,, k w yw ³ w wš yw w wš w. 1. d» II. x w p» w w. d ew w w œ x ww, d w š d w œ ù š ƒ. d l ¾ 4» e Table 1. Period of Sampling Season Period Days Summer ~ Autumn ~ Winter ~ Summer ~ Winter ~ Spring ~ Summer ~ Winter ~ Spring ~ Total 126 w 2z, 3z, ƒ 1z, 3z 126 d w. d» d Table d PM 10 PM 2.5 (Metal), (Ion), k (Carbon) w» w j 47 mm vl w vlq(filter Pack) w s w. PM 10 PM2.5 j w s wš w š, yw» w t lv v lq lv gq j w yw s w. PM 10 PM l/min z ƒ t w, Áz w z k r w» w z w. d yw q w (Dwyer ) (Shinagawa ) w z ƒ 16.7 lpm w 3 w. ƒ w lv vl(teflon Filter) w (Gravitational Mass), d w š, vl(qualtz Filter) w k w. d lv vl s w» 24 w»(25 o C, 35% RH) w conditioningw z j w d d» wš x s w w. s z vl w» 24 w conditioning w z d z

3 yw p w 295 Fig. 1. Seasonal variation of PM 10 and PM 2.5. (gravimetric mass) d w. d ó ù z lv vl ICP/MS IC w e z w. k d w» w, j l w š vl vl(qualtz Filter) w. vl 900 C o 2 w z j qp q v, Ÿ w z, 3 C o þ š w. wv (ICP) w ICP-MS(Thermo Jarrell Ash, Model IRIS-DUO) EPA Method 3051A j q w e(cem microwave digestion system, Model MARS- 5) w e z 20 (Al, Fe, Ca, Mg, Na, K, S, Ti, Mn, Ba, Sr, Zn, V, Cr, Pb, Cu, Ni, Co, Mo, Cd) w w. Ion Chromatography(Dionex 100) w 5 (Na +, NH 4 +, K +, Mg 2+, Ca ) 2+ 3 (Cl, NO 3, SO 2 4 ) ƒƒ w. k Ÿw n (Thermal- Optical Transmission: TOT) NIOSH(National Institute for Occupational Safety and Health) Method 5040 Parameter w OC/EC Analyzer w OC EC w. 1. p III. š Fig. 1 ƒƒ PM 10 PM 2.5 w d» s s ùkü tx m / s³. d» PM 10 PM 2.5 w w Fig. 2. Gravitational Mass Ratio of PM 10 and PM 2.5. ùkü PM 10 ƒ j ùk û, s > >ƒ > ùkû. j» ƒ ƒ û, û PM 10 PM 2.5 p y» w w z (Wash out)» q. Fig. 2 d l w z ùkü. PM 2.5, z PM 10 ùkü v 1:1 z xz [PM 2.5 ]=0.31[PM 10 ] š 2 R 0.52 ùkû.»» ƒ 1 ƒ¾ PM 10 PM 2.5 w. l»» 0.31 PM 2.5 PM 10 s³ 30% wš ù kû. Fig. 3 PM 10 PM 2.5 w s³ ùkü. PM 10 ƒ ƒ ùkü S 1 d» s³ µg/

4 296 Á½ yá Á½ yáy xá½ Fig. 3. Metal Fraction of PM 10 and PM 2.5. Fig. 4. Ion Fraction of PM 10 and PM 2.5. m 3, 2 d» s³ µg/m 3, 3 d» s ³ µg/m 3, 4 d» s³ µg/m 3, 5 d» s³ µg/m 3, 6 d» s³ µg/m 3, 7 d» s³ µg/m 3, 8 d» s³ µg/m 3, 9 d» s³ µg/m ùkû. PM 2.5 S ƒ ùkû. 1 d» s³ µg/m 3, 2 d» s³ µg/m 3, 3 d» s³ µg/m 3, 4 d» s³ µg/m 3, 5 d» s³ µg/m 3, 6 d» s³ µg/m 3, 7 d» s³ µg/m 3, 8 d» s³ µg/m 3, 9 d» s³ µg/m w yw w ùkû. ƒ d» S w r PM 10 Fe, Ca, Al, K, Na, Mg, Zn w š, PM 2.5 w w. Fig. 4 PM 10 PM 2.5 w s³ ùkü. NO 3, SO 4 2 ƒ, NH 4 +ƒ ùkû. s r PM 10 2 PM 2.5 w SO 4 >NO 3 >Cl >Ca 2+ ùkû. w s w w w w w š q. d» PM 10 PM 2.5 y y j y w ƒ š, PM 10 PM 2.5 š wš p PM 2.5 w w q w. Fig. 5 mw ù w, ³x r. PM 10 [Cation] = 0.915[Anion], w wš ùkû. PM 2.5 [Cation] = 0.911[Anion], PM 10 w wš ùkû.»

5 yw p w 297 Fig. 5. Equivalent Ratio of Ion Fraction in PM 10 and PM 2.5. Fig. 6. Carbon fraction and ratio of OC/EC in PM 10 and PM 2.5., ³x ùkù w š (H ) w w» + ƒ» k w ww»» š w ùkù yw š. OC/EC Analyzer w k EC OC Fig. 6 ùkü.» k»» w w w» w w.»k (Elemental Carbon)» w. k PM 10 PM 2.5 w. w, y w q w» w PM 10 PM 2.5»k»k ùkü.»k ù w, m w,»k t y w. PM 10 OC/EC 1.29, PM ùkù PM 10 w w ùkû. 2. yw ICP/MS w w(total Metal), IC w w(total Ion), OC/EC Analyzer w k

6 298 Á½ yá Á½ yáy xá½ Table 2. Chemical Mass of PM 10 Conc (µg/m 3 ) TM (µg/m 3 ) TI (µg/m 3 ) TC (µg/m 3 ) Unknown (µg/m 3 ) 1st nd th th th th th th th Table 3. Chemical Mass of PM 2.5 Conc (µg/m 3 ) TM(µg/m 3 ) TI(µg/m 3 ) TC(µg/m 3 ) Unknown (µg/m 3 ) 1st nd th th th th th th th Fig. 7. Gravitational Mass vs Chemical Mass. w(total Carbon) ww yw (Chemical Mass) wš (Gravitational Mass) y w. Table 2 Table 3 d» PM 10 PM 2.5 yw ùkü, Fig. 7 ƒ w ùkü. PM 10 (Total Metal) w 10%, (Total Ion) 31%, k 18% yw mw w w unknown 41% w. PM 2.5 w 7%, 36%, k 24% 33%ƒ yw w w ùkû.

7 yw p w 299 Table 4. Internal and external Concentration of Si and Al in PM 10 Area PM 10 (µg/m 3 ) Si (µg/m 3 ) Al (µg/m 3 ) Si/Al Burbank (87/09) Down town LA Hawthorne Long Beach Anaheim Rubidoux san Nicolas Azusa Riverside Phoenix frensno Corcoran CA Mexicali CA Table 5. Internal and external Concentration of Si and Al in PM 2.5 Area PM 2.5 (µg/m 3 ) Si (µg/m 3 ) Al (µg/m 3 ) Si/Al Bakersfield (95/12) Frensno Burbank (87/6) Rubidoux Long beach Anaheim Cheongju (95~96) Seoul (01~02) Autumn Winter Spring Summer Spring Summer Autumn Winter yw w »» w (Lost Metal)»» ICP/MS w m w. w m sƒw l w w w ƒ. m w w Siƒ ICP/MS w y» 3). Si SiO 2ù AlSi xk w, p Al ƒ. ü d (PM 10, PM 2.5 ) w Si w. Table 4, Table 5, ü d Si Al w. d ù»

8 300 Á½ yá Á½ yáy xá½ Fig. 8. Correlation of Si and Al in PM 10 and PM 2.5. ùkü ù Si/Al w š 2.1~2.9 ü w ùkü š. Al Si w, Fig. 8 ùkü w, j w ùkü š w ùkü. w d Al w Si w. PM 10, Al Si y ql(conversion Factor Al to Si in PM 10 ) Fig w š, PM 2.5 Al Si y ql w. Si = Al (PM 10 ) Si = Al (PM 2.5 ) m sƒ y (Soil Metal) m sƒw ƒ y w(sum of the oxides method) w 2). y w w w ƒ y xk š ƒ wš w x k w. m y x k wš y w š, m y w. mw m Si, Al, Fe, Mg, Ca, Na, K w y w (Sum of the oxides method) w. y w w m SiO 2, Al 2 O 3, Fe 2 O 3, MgO, CaO, Na 2 O, K 2 O w ƒ wš ƒ w wì w. w ƒ w ƒ w. ƒ s³ e 0.86 ù w. Soil = (2.14Si +1.89Al +1.43Fe +1.66Mg +1.4Ca Na +1.20K) / sƒ y SO 4 2 xk H 2 SO 4, NH 4 HSO 4, (NH 4 ) 3 (SO 4, (NH 4 SO 4 ƒ xk ù (NH 4 SO 4 wxk w yw SO 4 2 (NH 4 SO 4 w, NO 3 yw mw NH 4 NO 3 w» w w. 2NH 4 (g)+so 4 2 (g) (NH 4 SO 4 NH 4 (g)+no 3 (g) NH 4 NO 3 d Sulfate Ammonium Sulfate w» w S (Moler Ratio) yql w, Nitrate w Ammonium Nitrateƒ Ammonium Nitrate w ƒ w S w 1.29 yql w w. (NH 4 SO 4 = SO 4 2 ~ is Molar Ratio (NH 4 NO 3 =1.29 NO 3 ~ 1.29 is Molar Ratio w vl (Particle bound water) Ammonium Sulfate Ammonium Nitrate», d Sulfate Nitrate Mass

9 yw p w 301 sw. sƒw» w w w (Particle Bound Water-PBW) sƒƒ v w. d Aerosol Inorganic Model (AIM) 4) w sƒw.» ammonium sulfate sodium chloride w» w.» š w. nitric acid ammonia e { w ƒ k wš. w yw š,» k y z» lifetime d w š,, w». AIM w» l sx k H + NH 4 + Na + SO4 2 NO 3 Cl H2 O w ƒ yw w w w wš ù Wexler w w mw w 5). [Water] = ( ) + ( *NH 4 +)+( *NO 3 )+( *SO 2 4 )+( * + (NH 4 )+( *NO 3 *NH 4 +) + ( * (NO 3 ) + ( *SO 2 4 *NH 4 +) + ( * SO 2 4 *NO 3 )+( *(SO 2 4 ) NH 4 + = amount associated with nitrate and sulfate, NO 3 = amount associated with ammonium 3.3. k »»k y (OC to OM) k y» 2 Ÿyw xk š,»k» w w» x w. w» p w yw sƒ w», Ÿw mw yw»/» k sƒw. ù,»k (organic carbon) ù, ww xk w» w»k» sƒw sƒ.,»k» w» w w š. White Robert CHON» w ƒ w k k 1.3~1.39 ƒ» w 6), Grosjean Friedlander k s³ w 1.4 ql w 7). z Van Cauwenberghe 8), Countess 9), Japar 10), Turpin 11) w» w» w ƒ. Turpin w» w k w urban»k» y q l 1.6 ± 2, Non-urban 2.1 ± 0.2 w 11), ƒ y k p w» yql 1.6 w» y w. OM =1.6 OC 4. yw yw (Chemical Mass) (Gravitational Mass) Unknown w w» w w w sƒ y w w w š, d w w. ICP/MS mw ³ (Si) Al w w š m xk y w w y w w. sulfate, Nitrate, Ammonium w Ammonia w š e wwš ( w ) w mw w w.»k»» k» ƒ w y w y wš w»k w dw» w. Fig. 9 yw ùkü, mw PM 10 41% yw ƒ w w» ww yw ƒ š w yw 88%ƒ w ƒ w y w. PM 2.5 yw mw 67% w š 33%ƒ y û ƒ w 86%ƒ w ƒ w.

10 302 Á½ yá Á½ yáy xá½ Fig. 9. Reconstruction Chemical Mass. IV. y wš ƒwš w w w» w p v wš wš ³ v w. w d yw ww ù w û. w» w yw ³ w. w d yw mw,, k w w. w PM 10 41% PM %» w yw mw w. w m mw y w,, k w ƒ w w. w 5ƒ w w ƒ w w w w PM 10 88%, PM %» yw y. mw ƒ l w yw yw w ƒ w, z w w z d k ƒ w. wz k,, k w mw yw yw p w ƒ w w. References 1. J. C. Chow, J. G. Watson, L. C. Pritchett, W. R. Pierson, C. A. Frazier, and R. G. Purcell, 1993, The DRI thermal/optical reflectance carbon analysis system: Description, evaluation and applications in U.S. air quality studies, Atmospheric Environment, 27A(8), E. Andrews, P. Saxena, S. Musarra, L. M. Hildemann, P. Koutrakis, P. H. McMurry, I. Olmez, and W. H. White, 2000, Concentration and composition of atmospheric aerosols from the 1995 SEAVS experiment and a review of the closure between chemical and gravimetric measurements, J. Air Waste Manage., 50, S. L. Rees, A. L. Robinson, A. Khlystov, C. O. Stanier, and S. N. Pandis, 2004, Mass balance closure and the Federal Reference Method for PM2.5 in Pittsburgh, Pennsylvania, Atmospheric Environment, 38, S. L. Clegg, P. Brimblecombe, and A. S. Wexler, 1998n, A thermodynamic model of the system H+- NH4+ Na+ SO42 NO3 Cl H2O at K, J. of Phys. Chem., 102A, A. S. Wexler and Z. Ge, 1998, Hydrophobic particles can activate at lower relative humidity than slightly hygroscopic ones: a Kohler theory incorporating surface fixed charge, J. Geophy. Res., 103, W. H. White and P. T. Roberts, 1977, On the nature and origins of visibility-reducing aerosols in the Los

11 yw p w 303 Angeles air basin, Atmospheric Environment, 11, D. Grosjean and S. K. Friedlander, 1975, Gasparticle distribution factors for organic and other pollutants in the Los Angeles atmosphere, J. Air Pollution Control Assoc., 25, L. Van Vaeck, and K. Van Cauwenberghe, 1978, Cascade impactor measurements of the size distribution of the major classes of organic pollutants in atmospheric particulate matter, Atmospheric Environment, 12, R. J. Countess, G. T. Wolff and S. H. Cadle, 1980, The Denver winter aerosol: A comprehensive chemical characterization, J. Air Pollution Control Assoc., 30, S. M. Japar, A. C. Szkarlat, R. A. Gorse, Jr. E. K. Heyerdahl, R. L. Johnson, J. A. Rau and J. J. Huntzicker, 1984, Comparison of solvent extraction and thermal optical carbon analysis methods: Application to diesel vehicle exhaust aerosol, Environ. Sci. Techonol., 18, Turpin, J. Barbara and H. J. Lim, 2001, Species Contributions to PM2.5 Mass Concentrations: Revisiting Common Assumptions for Estimating Organic Mass, Aerosol Science and Technology, 35,