83-06.fm

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1 w y wz 8«( 3y 143~153, 005 J. of the Korean Socety for Envronmental nalyss x yá Á Áyk Áy Á wá½ *Á ** y œ, *w x, **w t w Preparaton of Fly sh for Profcency Testng of Doxn nalyss Dongho Moon, Sangwon Lee, hangn Ihm, Taewoong Hwang, Yongyoul Hwang, Jongsang Km*, and Jnchun Woo ** Envronmental Management o. Kyungseo-dong, Seo-gu, Incheon, , Korea *Korea Insttute of onstructon Materals, Seoul , Korea **Korea Research Insttute of Standards and Scence, Daejeon , Korea Fly ash sample collected from muncpal waste ncnerator was prepared for profcency testng of doxn analyss. The collected sample was carred out several steps for homogenzng and then analyzed for evaluatng homogenety and stablty. One way NOV was used for the evaluaton. The uncertanty of each target somer from whole doxn analyss procedure was also evaluated and combned. Next, the uncertantes form repeatng analyss and analytcal procedure were combned. Fnally, the assgned value of the profcency testng sample was suggested. Key words : Doxn, Profcency testng, Uncertanty 1. w y j z j ƒ ³ ƒ w š.,» w» w š. y w» w»» v w sƒƒ v 1. x y w ISO/IE 1705 w x swwš x w ƒwš. ù x w ³ sƒƒ w w y sww p wì ùkü w w. ƒ w x w. ³ sƒwš3,4 EURHEM IT l w 5 Gude w y sƒw x w ƒ w. yr w ƒ w screw conveyor l p w w z w 10 kg w... EP 1613(USEP, 1994 ü d ( y w, 00 w wš SP-331f w HRG/HRMS (VG Ultma, mcromass, UK w. t Wellngton t w, m To whom correspondence should be addressed.

2 144 yá Á Áyk Áy Á wá½ Á w œ m v Kess w. 3. š 3.1. x ³ y ³ y w» w w w. w z z q ƒ yw» 4 yww z 00 mesh(75 um w w. w z w ³ y 00 mesh w w, 00 mesh ƒ wš, ³ sƒ» w 00 mesh w s sƒw. j» 00 mesh j 100 mesh 00 mesh 30 mesh, 35 mesh w. ³ y 3 w s sƒ w w. ƒ w y e w, j»ƒ 4 j»ƒ. 100 mesh e w š w. 30 ³ w w š, ƒ e w., 3 00 mesh wƒ w ùkû, 00 mesh ƒ ƒ 89% q Fg. 1. The result of partcle sze analyss. ³ y 00 mesh w» q. Fg. 1 ùkü. mw l r z matrx ³ w š q 90 w (between-bottle ³ sƒ x 90 5 w w ³ sƒw. ³ sƒ Table 1 ùkü. ³ sƒ t 95% Û4.80 ng-teq/g ³ w s ƒ ü(wthn-bottle ³ sƒ x 90 kw ƒ 3 v, 6 m w ³ sƒw.» m w sƒw. ü ³ sƒ Table ùkü. ü ³ sƒ t 95% Û ng-teq/g Table 1. Homogenety between-bottle (unt : ng-teq/g 3-BB 6-BB F3-BB F6-BB J4-BB,3,7,8-TDF ,,3,7,8-PeDF ,3,4,7,8-PeDF ,,3,4,7,8-HxDF ,,3,6,7,8-HxDF ,3,4,6,7,8-HxDF ,,3,7,8,9-HxDF ,,3,4,6,7,8-HpDF ,,3,4,7,8,9-HpDF ODF ,3,7,8-TDD ,,3,7,8-PeDD ,,3,4,7,8-HxDD ,,3,6,7,8-HxDD ,,3,7,8,9-HxDD ,,3,4,6,7,8-HpDD ODD PDFs PDDs (PDDs+PDFs

3 x 145 Table. Homogenety Wthn-bottle (unt : ng-teq/g I3-1-WB I3--WB I3-3-WB I6-1-WB I6--WB I6-3-WB,3,7,8-TDF ,,3,7,8-PeDF ,3,4,7,8-PeDF ,,3,4,7,8-HxDF ,,3,6,7,8-HxDF ,3,4,6,7,8-HxDF ,,3,7,8,9-HxDF ,,3,4,6,7,8-HpDF ,,3,4,7,8,9-HpDF ODF ,3,7,8-TDD ,,3,7,8-PeDD ,,3,4,7,8-HxDD ,,3,6,7,8-HxDD ,,3,7,8,9-HxDD ,,3,4,6,7,8-HpDD ODD PDFs PDDs (PDDs+PDFs ³ w sƒ (analyss of varance ³ y w ƒ w w e (one way NOV w. ü w p w Fg. w. ü ƒ w d d w ƒ w. 95% Û.01 ng-teq/g Fg.. The result of varance analyss. ³ w sƒ. ƒ w Table 3 ùkü. Table 3. onfdence nterval (unt:ng-teq/g mean SD nterval confdence nterval,3,7,8-tdf Û ,,3,7,8-PeDF Û0.01,3,4,7,8-PeDF Û ,,3,4,7,8-HxDF Û ,,3,6,7,8-HxDF Û0.093,3,4,6,7,8-HxDF Û ,,3,7,8,9-HxDF Û ,,3,4,6,7,8-HpDF Û ,,3,4,7,8,9-HpDF Û0.015 ODF Û0.013,3,7,8-TDD Û0.68 1,,3,7,8-PeDD Û0.45 1,,3,4,7,8-HxDD Û ,,3,6,7,8-HxDD Û ,,3,7,8,9-HxDD Û0.18 1,,3,4,6,7,8-HpDD Û0.311 ODD Û0.119 PDFs Û0.556 PDDs Û1.466 (PDDs+PDFs Û.01

4 146 yá Á Áyk Áy Á wá½ Á Table 3 xw yw y tx ùkü d ƒ y q wš x d y w w txw w. 3.. y sƒ y sƒ GUM(Gude 7 to the Expresson of Uncertanty n Measurement» w EURHEM IT l w Gude. r, d, d y w., y ƒ w ƒ w w., y yw., w y y y w., d w q wš w w, y wš m t y w ƒ y w y wš w y š w y y w y w g w w w z ƒ w w z t ƒw z w HRG/HRMS w. x r. 3 g e z t 8 ng wš w. t z m wš - w we z mw w w. t 1 ng w š y, e f, ù f, y k f e z z z d t wš 0 µl w š w» w w. w Fg. 3 ùkü ùký ƒ ùkú y t w. 17 = d : ƒ k (ng/g : (ng-teq/g : ƒ TEF factor f TEQ f d TEQ d d w = M 1 -- f d : M : (g f : w : (ng d : y (ng/g w = x : w k v j l : ƒ ü t k v j l : ƒ ü t (ng RRF : : ƒ (ng w x l l RRF = l IS Fg. 3. Flow chart for doxn analyss. : ü t mcro

5 x 147 ppette (µl IS : ü t (ng/ml w ( χ f IS f TEQ d = E M x» χ = l RRF 17 ƒƒ wš ƒ y ƒƒ w w w tx. d = M f l RRF x IS f TEQ w x w w. Table 4. The Example of calculatng doxn concentraton value unt calculaton d µl M g f x l RRF IS 100 pg/µl f TEQ x d = M f l RRF IS f TEQ = = pg/g = ng/g 3... y w w y Fg. w. y ƒ y p w š w y w. 1 x y 0 o k ƒ w w vq y w. t ƒw ü t y š w. t ƒw z ü t d w ù kü v w y š w. 3 G/MS d ü t d w ùkü y š w. 4 RRFƒ w y t RRF y w. 5 d y ƒ 1 mg yw e w w e» w d y w. š w w y Table 5 ùkü y y w š w y [u(d] w» w volumetrc flask Fg. 4. Fshborn dagram of the uncertanty factors n doxn analyss.

6 148 yá Á Áyk Áy Á wá½ Á Table 5. Uncertanty factors n doxn analyss step uncertanty factor evaluaton method type sample dvde u(d Standard spke u( l mean RRF u(g volumetrc flask u(f calbraton certfcate B ppet u(p calbraton certfcate B concentraton of standard soluton u( IS certfcate from maker B dsposable mcroppet u( calbraton certfcate B ablty of analyst u(w repetton albraton standard u( VS certfcate from maker B mean rrf u(rrf SD of RRF volumetrc ppette w y d š w w B Type w t y w. v j vr f 1, p 1, f, p w w t y w. ud d ( = up 1 ( uf ( 1 up ( uf ( p 1 f 1 p f z Welch-Satterthwate w. u c y ( ν eff = N [ c ux ( ] ν = ü t w y u( l l = IS ƒƒ y w z w w. ü t w y [u( IS ] q t w y wš, t B x y w. j vr y [u( ] vr y w y š w w j vr v w y w w Bx t y w. x w y x mw x sƒ ww. 3ƒ w w w t y w. u l ( = l u ( IS uv ( mp IS uw ( V W »» w y [u(g]»» ùkù y t y s³ RRF w RRF y ù. t w y u( VS q t w y wš t Bx y wš, RRF y u(rrf 5 t w 5 RRF w z s³ RRF w w RRF t r w t w z y w. ƒ w w w w t y w. 17 w RRF ƒƒ w»» w y ƒƒ w. ug G ( = u ( VS VS w y y y w w y w w d w t y w w. u ( = ud d ( uc l ƒ w t y ƒ w w t y wš» sw w y y wš, w y t w. doxn = 17 ( 95%, k= urrf RRF ( ( l 17 u ± k ug G ( ( ng-teq/g

7 x y y w y [u(d] 100 w» w» 10 ml volumetrc flask wš 1 ml ppette w w v j v j ƒƒ f 1, f š wš vr ƒƒ p 1, p š w w d. d f 1 f = p 1 p y 100 w 1/10 w w. v j, vr y w B Type w t y w. - 1 ml volumetrc ppette y u(p 1 w vr ³ ml. ƒ k= w t y w. up 1 ( = = p 1-10ml volumetrc flask y u(f 1 10 ml volumetrc flask w ³ ml š k=, t y, uf ( = = f 10 - vr 1/10 y u(p, ³ vr w, up ( = = p - v j y u(f, ³ v j w, uf ( = = f 10 3 y q w w t y ud d ( = = up 1 ( uf ( 1 up ( uf ( p 1 f 1 p f [ 0.005] + [ 0.001] + [ 0.005] +[ 0.001] = z ν eff Welch-Satterthwate w ù» Bx sƒ ƒƒ y w m w š z w j ƒ z w ü t w y u(l (5 w l = IS ƒƒ y w z w w. -ü t w y [u( IS ] ü t q t w y w. t t š Bx y w. t ³ 100 ng/ml ± 5% ƒx s ƒ w u ( IS = = IS 3 š w. - j vr y [u( ] vr w y vr y w y š w. j v r v w y w w 10Û0.3 µl k= Bx t y w uv ( mp = = w. x w y w (10 µl 10z w w z x sƒ w. j vr d w Table 6 ùkü. u(w = š t y u(w/v W ƒ w w

8 150 yá Á Áyk Áy Á wá½ Á Table 6. The result of analyst ablty u l ( = l = 1st 9.9 nd rd 10. 4th th th 9.7 7th 9.7 8th th th 9.9 mean 9.95 SD standard uncertanty degree of freedom 9 u ( IS uv ( mp IS uw ( V W [ ] + [ 0.015] +[ ] = z ν eff Welch-Satterthwate l w »» w y [u(g]»» ùkù y t y s³ RRF w RRF y ù - t w y u( VS t q t w y w. t t š Bx y w. t ³ y 5% t wš ƒx s ƒ w u ( VS = = VS 3 š w. -RRF y u(rrf 5 t w 5 RRF w z s³ RRF w w RRF t r w t w z y w. RRF 1 RRF RRF 3 RRF 4 RRF s³ RRF : 0.986(»» t r : 0.04(»» t : = u(rrf = t r / 5 : 4 ƒ s³ y u(rrf/rrf = » RRF ƒ ƒƒ w w. ƒ w w ug G ( = = u ( VS VS urrf RRF ( [ ] + [ ] = z Welch-Satterthwate w 55ƒ. w w y Table 7 w. Table 7. The result of uncertanty factors for doxn analyss step sample dvde u(d Standard spke u( l mean RRF u(g uncertanty factor evaluaton method type Relatve standard uncertanty volumetrc flask u(f calbraton certfcate B ppet u(p calbraton certfcate B concentraton of standard soluton u( IS certfcate from maker B dsposable mcro ppet u( calbraton certfcate B ablty of analyst u(w repetton albraton standard u( VS certfcate from maker B mean rrf u(rrf SD of RRF ombnded standard uncertanty degree of freedom nfnte

9 x 151 Table 8. The uncertanty of nstrument analyss for Doxn u(d u( l / l u(g/g u(/ Furan Doxn,3,7,8-TDF ,,3,7,8-PeDF ,3,4,7,8-PeDF ,,3,4,7,8-HxDF ,,3,6,7,8-HxDF ,3,4,6,7,8-HxDF ,,3,7,8,9-HxDF ,,3,4,6,7,8-HpDF ,,3,4,7,8,9-HpDF ODF ,3,7,8-TDD ,,3,7,8-PeDD ,,3,4,7,8-HxDD ,,3,6,7,8-HxDD ,,3,7,8,9-HxDD ,,3,4,6,7,8-HpDD ODD w y y y w w y w w d w t y w w Table 8 ùkü. u ( = ud d ( u l ƒ w t y ƒ w w t y wš» w y y wš, w y t w doxn = 17 ( 95%, k= ( l 17 u ± k ug G ( ( ng-teq/g, d Table 9 w t w. = (30.567Û ng-teq/g( 95%, k= 3.3. x y tx x w d w y w w x p w sƒ» sƒ w o ƒƒ z w š w 7 30 ƒƒ z w. Table 11 1 ùkþ. s³ ng-teq/g, ng-teq/g w wù q wš», ü» w sƒw. Table 13 ùkü. p y. 4. w x w. ³ y w z,, ü ³ sƒ w w p w» w y q wš w. x p ³ w sƒ w w w š w.

10 15 yá Á Áyk Áy Á wá½ Á Table 9. Expresson of fly-ash concentratons wth uncertanty Furan Doxn concentraton (ng-teq/g u(/ standard uncertanty u( expanded uncertanty k=,3,7,8-tdf ,,3,7,8-PeDF ,3,4,7,8-PeDF ,,3,4,7,8-HxDF ,,3,6,7,8-HxDF ,3,4,6,7,8-HxDF ,,3,7,8,9-HxDF ,,3,4,6,7,8-HpDF ,,3,4,7,8,9-HpDF ODF ,3,7,8-TDD ,,3,7,8-PeDD ,,3,4,7,8-HxDD ,,3,6,7,8-HxDD ,,3,7,8,9-HxDD ,,3,4,6,7,8-HpDD ODD PDFs PDDs (PDDs+PDFs Table 10. The concentraton of profcency testng sample wth uncertanty expresson (ng-teq/g relatve standard uncertanty by repetton relatve standard uncertanty by evaluaton combned relatve standard uncertanty standard uncertanty expresson wth uncertanty (k=,3,7,8-tdf Û ,,3,7,8-PeDF Û0.019,3,4,7,8-PeDF Û0.91 1,,3,4,7,8-HxDF Û ,,3,6,7,8-HxDF Û0.170,3,4,6,7,8-HxDF Û0.55 1,,3,7,8,9-HxDF Û ,,3,4,6,7,8-HpDF Û0.11 1,,3,4,7,8,9-HpDF Û0.04 ODF Û0.0,3,7,8-TDD Û ,,3,7,8-PeDD Û ,,3,4,7,8-HxDD Û ,,3,6,7,8-HxDD Û0.45 1,,3,7,8,9-HxDD Û0.69 1,,3,4,6,7,8-HpDD Û0.490 ODD Û0.156 PDFs Û0.445 PDDs Û1.010 w (PDDs+PDFs Û1.104

11 x 153 Table 11. The evaluaton of stablty after 7 s Table 1. The evaluaton of stablty after 30 s B7-7 B-7 E-7 E7-7 B7-7 H7-30 K-30 K7-30,3,7,8-TDF ,,3,7,8-PeDF ,3,4,7,8-PeDF ,,3,4,7,8-HxDF ,,3,6,7,8-HxDF ,3,4,6,7,8-HxDF ,,3,7,8,9-HxDF ,,3,4,6,7,8-HpDF ,,3,4,7,8,9-HpDF ODF ,3,7,8-TDD ,,3,7,8-PeDD ,,3,4,7,8-HxDD ,,3,6,7,8-HxDD ,,3,7,8,9-HxDD ,,3,4,6,7,8-HpDD ODD PDFs PDDs w (PDDs+PDFs ,3,7,8-TDF ,,3,7,8-PeDF ,3,4,7,8-PeDF ,,3,4,7,8-HxDF ,,3,6,7,8-HxDF ,3,4,6,7,8-HxDF ,,3,7,8,9-HxDF ,,3,4,6,7,8-HpDF ,,3,4,7,8,9-HpDF ODF ,3,7,8-TDD ,,3,7,8-PeDD ,,3,4,7,8-HxDD ,,3,6,7,8-HxDD ,,3,7,8,9-HxDD ,,3,4,6,7,8-HpDD ODD PDFs PDDs w (PDDs+PDFs Table 13. The result of NOV for stablty evaluaton n mean SD SS MS F-value p-value reference sample total y yw» w y jš w sww. y s ƒ w m, w sww w. ù y q w ƒ w w. sƒ y %(y y 4% sƒ. ù sƒ yƒ g z sww y ƒw q. z 98% sƒw y 3% ƒw.» t w. š x 1. Yosho Ida, Hroyuk Ifak, etc., The japan Socety for nalytcal hemstry, 001, 50, x», 004. w x» 3. Xuel ao, Xaoba Xu, Wenxuan u, Zhqun X, Fresenus J nal hem., 001, 370, R.Van leuvenbereen, G.N. Kramer, E.. Maer, hemosphere, 1998, 37, S. L. R. Ellson, M. Roslen,. Wllams, Quantfyng Uncertanty n nalytcal Measurement nd ed., 000, EURHEM/IT workng group 6. Katsunor Motohash, k, 003, 30, , d y tx e, 1998, w t w