Determination of Size Distribution of Particles in Ground Water Using Flow Field-Flow Fractionation

Transcription

1 w y wz 9«( 4y) 243~249, 2006 J. of the Korean Society for Environmental Analysis z w w j» s x Á Á y w p l, wû w yw Determination of Size Distribution of Particles in Ground Water Using Flow Field-Flow Fractionation Chul Hun Eum, Dong Young Kang, and Seungho Lee Korea Institute of Geoscience and Mineral Resources, Daejeon, , Korea Department of Chemistry, Hannam University, Daejeon , Korea Flow field-flow fractionation(fff) have been used to characterize particles in ground water. The opposed flow sample concentration (OFSC) method is employed, where particles are focused into a narrow band near the inlet of the flow FFF channel by two incoming flow-streams through the inlet and the outlet of the channel. There is no need for stopping the flow for the sample relaxation, which is usually required in conventional Flow FFF operations. The OFSC procedure is optimized for analysis of ground water particulates with respect to various experimental parameters including sample introduction, flow rates, etc. The effectiveness in concentration and characterization of the OFSC-flow FFF was demonstrated with various mixtures of polystyrene latex spheres. Ground water of upto 100mL has been successfully loaded, concentrated, and characterized by OFSC-flow FFF. The OFSC technique makes the application of flow FFF possible for separation and characterization of particles in very low-concentrations. The results show the potential of (OFSC)-Flow FFF. OFSC-flow FFF provides a simplified alternative to existing off-line concentration procedures, and shows high potential for application to analysis of dilute particles in environmental water. Key words : field-flow fractionation, ground water, size distribution, opposed flow sample concentration(ofsc) 1. w y ( w,»,, e, ) w y w w w w. 1,2) p w yw ƒ, ù j»,, š t yw w s ƒ. w t ƒ y û w y j w e. 3) w w y p ü z (Field-Flow Fractionation, FFF) w z wš y š w. FFF 1980 Giddings w» wù. FFF j m v 4) ü š, w j» w ƒ w ƒ x w š. w FFF š w ù l To whom correspondence should be addressed. cheum@kigam.re.kr

2 244 xá Á y l j j» w w. FFF p wù l j», /yw q l w w p w x yw, 5) w,» y 8) 6) š 7) w FFF ƒ y w š. w FFF w v(hydrodynamic volume) w (retention time) ƒ w ƒw w. ƒ y (diffusion coefficient) Stokes w j» ƒ ƒ w, g xk p ƒ š k x w ü g w. w ü w g û ù e w e. w (aggregation) w(shear degradation) z w w ƒ w ƒ š. w j» s y w» w w x (SEM, TEM) kƒ œ k w yw j». j» j m v(size exclusion chromatography) w (, w) w w. 9,10), û w w» w opposed flow sample concentration (OFSC) w FFF w w ü w wš w. 2. x Flow FFF z e FFFractionation (Salt Lake City, UT, U.S.A.) F-1000 Universal Fractionator. 2 v (Plex glass) ù(alumina) œ q(frit) œ q mw ³ w w š, m w Cross stream ³ w œ w. œ q (spacer) q œ q mw (membrane). w z g. ¼ 29.3 cm, s 2.0 cm, (spacer) Ì cm. x w (regenerated cellulose) YM-10(Amicon Inc. MA) š, YM-10 m w (molecular weight cut-off) 10,000. mj e(torque wrench) w 55 Ib/inch ³ w x w. rv YOUNG-LIN M930(Seoul Korea), DMX- 2003T(SMK Inc. Japan) Piston rv GILSON Model M312(Middleton, WI, USA) peristaltic rv w. YOUNG-LIN Scientific M720 (Seoul Korea) w. FFF Data vp FFF.EXE (FFFractionation Inc. Utah, USA) w l w. e(injector) Rheodyne 7725 Injector w. x w needle valve w z (buret) w ƒƒ v d w d w. w w m Ÿ (Gwang-ju city, Korea) š x, x hand suction rv w 1.2 um j» w. m w Flow FFF w normal w š, (aggregation) w š y w y (interaction) yw» w w 1L 1g SDS(sodium dodecyl sulfate) ƒwš, l w 0.2 g NaN 3 (sodium azide) ƒw. w w 4C o þ š w ƒ x w v w j w š š 1 ew ƒ 30 w z x w. Mili-Q e w 0.05% SDS ü l w»

3 z w w j» s 245 w 0.02% NaN 3 sww w. ƒ w ³ w w» w t y yw k z 5 (stirring) e z w, (sintered glass filter) w z w x stop-flow FFF x w» z e rv g x v w w w (injection delay time) (relaxation time) wš yw d w z w w. p v(void volume) d w» w (cross flow) (channel flow) yw d w z 20 ul w vj y w. (channel flowrate) w Ì (thickness) w cm š, p v(void volume) ml. p v w z j» w y w» w 28, 79, 138 nm j» s p l t 3 yww g w. x w 30 ü x w z xw. stop-flow flow FFF w j» j» (retention time) x j» y w z OFSC-Flow FFF w» w stop-flow»» e 3 3-way ew w w w š, ü yw w p peristaltic pump ew. x w stop-flow w 28, 79, 138 nm s p l yw 50 ml 100 ml g x w. ü ù ³ w x w š ü ew frit m w ƒ ùƒ w. sample loading and focusing š w x š (field) (crossflow) ƒw y (stabilization step) e y (diffusion) (field) (crossflow) sx ƒƒ j» d(layer) x w. x d s xk w j» ƒ. OFSC-flow FFF x w (opposed flow) w ü w š ƒƒ 3-way w flow w w x w. OFSC-flow FFF x stop-flow w 28, 79, 138 nm s p l yw 20 ul w 50 ml, 100 ml w š z peristaltic rv w ü œ w. w peristaltic rv x v m rvù Q-rv w ƒ ùkû y w. OFSC needle ew x w cross-flowrate w» w. w x w v j t w wš ü w xw. 3. š 3.1. stop-flow w t stop-flow z e w 3ƒ 28, 79, 138 nm j» s p l yw 30 x ww. (aggregation) wš y (interaction) y w 0.05% SDS 3 w. x w Fig. 1 ùkü š k ƒƒ j» s Fig. 2 ùkü. w s p l (nominal diameter) x mw w (hydrodynamic diameter) wš

4 246 xá Á y Table 1. Nominal and measured diameters of polystyrene standards. Nominal diameter (nm) Diameter determined by Flow FFF (nm) Peak max. Error (%) First moment Error (%) w j» x j» w y w Table 1 ù kü. Fig. 1, 2 ùkù 3ƒ j» t š, j» s w y w. 3ƒ 28, 79, 138 nm j» ƒ t w j» x mw j» 0.01% 6% ùkù e xeƒ j x mw y w š w x»» w y w. stop-flow flow FFF xwš j» x y w š, y w x mw j» w ew r. OFSC-flow FFF w w (application) ƒ r OFSC-Flow FFF w t stop-flow Flow FFF w 3ƒ 28, 79, 138 nm j» s p l t yw 20 ul 50 ml g ü w stop-flow z w y wš e y wš j» s y wš ƒ j» vj r. x Fig. 3 ùkü. 3ƒ 28, 79, 138 nm j» t yw 50 ml k z x w, p stop-flow e y w. e w stop-flow z e OFSC w x w j»ƒ e w. Fig. 1. Fractogram of polystyrene latex standards. Flow conditions are Vc=0.8 ml/min and Vout=2.0 ml/ min. Carrier solution is contained 0.05% SDS with 0.02% NaN 3. Fig. 2. Size distribution of polystyrene latex standards. Flow conditions are Vc=0.8 ml/min and Vout=2.0 ml/min. Carrier solution is contained 0.05% SDS with 0.02% NaN 3.

5 z w w j» s 247 x Fig. 5 ùkü. x x y w» w 2 x ƒ e w y w š OFSC-flow FFF ƒ w ƒ ƒ y w w m w OFSC - z x w œ ƒ» w E-4 S-12 2ƒ Fig. 3. Fractogram of polystyrene latex standards obtained by OFSC-Flow FFF run. 50 ml containing 20 ul diluted sample was introduced into channel. The focusing flow rate is 1:15 with flow rates at the normal and opposed inflow inlets of 0.2 and 3.0 ml/min. The focusing time is 60 min. During the separation, Vc=0.8 ml/min,vout=2.0 ml/min Fig. 3 mw OFSC ƒ y w z stop-flow OFSC ƒ ew y w» w w Fig. 4 ù kü. stop-flow w ¼ focusing ƒ w j Fig. 4 mw y w. 3ƒ t yw 20 ul 100 ml k z ü w xw Fig. 5. Fractograms of polystyrene latex standards obtained by OFSC-Flow FFF run. 100 ml containing 20 ul diluted sample was introduced into channel. The focusing flow rate is 1:15 with flow rates at the normal and opposed inflow inlets of 0.2 and 3.0 ml/min. The focusing time is 60 min. During the separation, Vc=0.8 ml/min, Vout=2.0 ml/min. Fig. 4. Overlaid fractograms of polystyrene latex standards obtained by Stop-flow mode and OFSC mode Flow FFF runs. Fig. 6. Fractograms of ground water named S-12 sample obtained by OFSC-Flow FFF run. The focusing flow rate is 1:15 with flow rates at the normal and opposed inflow inlets of 0.2 and 3.0 ml/min. The focusing times are a) 30, b) 100, c) 150 min. Injection volumes are a) 10, b) 50, c) 100 ml. During the separation, Vc=0.5 ml/min, Vout=1.0 ml/min.

6 248 xá Á y Fig. 7. Overlaid of size distributions of ground water named E-4 and S-12sample obtained by OFSC-Flow FFF run. The focusing flow rate is 1:15 with flow rates at the normal and opposed inflow inlets of 0.2 and 3.0 ml/min. The focusing times is 100 min. Injection volumes is 50 ml. During the separation, Vc=0.5 ml/min, Vout=1.0 ml/min. ƒ. w E-4 S-12 OFSC-Flow FFF Fig. 6 ùkü. OFSC flow FFF w ü w ƒ p ƒ» fractogram y w š, E-4 S-12 j» s y w Fig. 7 ùkü. Fig. 7 mw ƒ j» s y w mw ƒ j» sƒ y w w E-4 S-12» w. ƒƒ w wš w OFSC-Flow FFF w w w. 4. flow FFF w w ƒ wš yw š OFSC-Flow FFF w xwš š w. ƒ š w x w wš y w ww. mw ƒ w., 28, 79, 138 nm j» ƒ s p l t w OFSC- Flow FFF l p w ƒ y w. w FFF l w xw ƒ j» s y w ü w j» s y wš ƒ ƒ ƒ pw j» s y ƒ. w, OFSC-Flow FFF w» x wš ww yw w ƒ f w. FFF w ww w w yw w ƒ. w» y w. š x 1. Rudin, A and Johnston, H.K. Polym. Lett., 1970, 9, Giddings, J. C, J. Chem. Educ., 1973, 50, Bekett, R, Bigelow, J.C, Zhang, J and Giddings, J. C,

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