Solid Phase Microextraction-GC/MS

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2004, Vol. 48, No. 1

Printed in the Republic of Korea

Solid Phase Microextraction-GC/MS

(DMP, DEP, DBP, BBP, DEHP, DnOP)

^†^‡ *

,

†

‡

(2003. 8. 18 )

Simultaneous Determination of Phthalates(DMP, DEP, DBP, BBP, DEHP, DnOP) by Solid Phase Microextraction-GC/MS

Jae-Hee Lee^†, Jun-Hyun Bae^‡, Jun-Gill Kang*, and Youn-Doo Kim Department of Chemistry, Chungnam National University, Daejeon 305-764, Korea

†Korea Water Resources Corporation, Daejeon 305-730, Korea

‡Department of Environmental Engineering, Anyang University, Kyungki-Do 430-714, Korea (Received August 18, 2003)

. SPME-GC/MS ! "#$% &'() *+,-. /01 23 4%

5 678. 9 :1; &'() *+,% dimethyl phthalate(DMP), diethyl phthalate(DEP), dibutyl phthalate(DBP), benzylbutyl phthalate(BBP), diethylhexyl phthalate(DEHP), di-n-octyl phthalate(DnOP)<=8. >?

T BC$=UV, DBPO DEHPW XY% ZZ 0.192~1.270 ng/ml J 0.077~1.102 ng/ml [\. ]78.

: SPME-GC/MS, &^() *+,, /02

ABSTRACT. A procedure based on solid phase microextraction extraction(SPME)-GC/MS has been developed for the simultaneous analysis of plasticizers. The plasticizers investigated in this study are dimethyl phthalate(DMP), diethyl phthalate(DEP), dibutyl phthalate(DBP), benzylbutyl phthalate(BBP), diethylhexyl phthalate (DEHP), di-n-octyl phthalate(DnOP). The limit of detection(LOD) was 0.163~0.299 with relative standard deciation(RSD) of 5.85~15.80% for these compounds. At water reserviors of Han, Geum, Nakdong and Sumjin rivers, only DBPand DEHP were detected at trace level, 0.192~1.270 ng/ml for DBP and 0.077~1.102 ng/ml for DEHP depending on the river.

Keywords: Solid Phase Microextraction-GC/MS, Plasticizer, Simultaneous Analysis

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Fig. 1. Chemical structures of six phthalates used in this study.

Table 1. Conditioning Temperature and Time for Fibers.

Fiber Film thickness (µm)

Temperature (^oC)

Time (min)

PDMS 100 250 60

PDMS 30 250 60

PDMS 7 320 240

PA 85 300 120

CAR/PDMS 75 280 30

CW/DVB 65 250 30

DVB/CAR/PDMS 50/30 270 240

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; Combi-Pal Autosampler(CTC analytics, Swiss).

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* 30 m, < 0.25 mm<=8. ColumnW 6#Dt 0.25µm

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¹ø³ 9 5 I/G, KLG, HG J GW 0@1 po Ã. ¹78.

&'() *+, >?Ä(50 ng/ml) 20 mlù y zW vial1 N î teflon septa* úû crimp seal Table 2. Injector temperature for SPME fiber

Temperature(^oC) Fiber(µm)

260 PDMS(100, 30), CW/DVB(65) DVB/CAR/PDMS(50/30)

300 PDMS(7), PA(85), CAR/PDMS(75) Table 3. Injector split ratio programming on time

Time(min) Split state Split ratio

0.01 Off Off

10.0 On 20.1

40.0 On 20.1

Table 4. GC oven temperature programming for phthalates Temp(^oC) Rate (^oC/min) Hold

Time(min)

Total Time(min)

100 - 2.00 2.00

150 8.0 0.00 8.25

240 4.0 0.00 30.75

275 10.0 5.75 40.00

Carrier gas: He(99.999%), Column flow: 1.2 ml/min(con- stant flow)

Table 5. Mass spectrometer operation parameters

Parameter Value

Ionization Mode Temperature Emission Current Scan Rate Filament Delay

Threshold Background Mass Mass Range

Data Aquisition Time

Ion Preparation Maximum Ionization Time Target TIC

E.I(70 eV) Auto Gain Control

220^oC for manifold, 240^oC for transfer line 20 µA

0.66 scane/sec 6 min 10 count

45 amu 45-450 amu 40 min None 25,000 µs sec

20,000 count

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p!; alkyl < phthalate Ö; ·, DEHP>

DnOP>DBP>BBP>DEPDMP <=8. SPME1 W 0@ ^ t 3±! :$%, % Fig. 2. Inter-relation of response with time and temperature of DMP and DEP.

Fig. 3. Inter-relation of response with time and temperature of DBP and BBP.

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9 æè Ë SPME fiber% PA85 fiber, ºm Y% 500 rpm, ÜY% 50^oC, 0Ít 70 ^ ½ Fig. 4. Inter-relation of response with time and temperature of DEHP and DnOP.

Fig. 5. The influence of fiber to detector response.

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Phthalate% benzene 6^W ortho\1 RzW carboxyll* e46 « 1 alkyl % aryl «<

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1 W “ortho-effect”W U! ØéØÈ ³8.⁹< Fig. 6. General fragmentation of phthalate.

Fig. 7. E.I. Mass spectrum of six phthalate compounds.

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W <×1 W o³ m/z 223 Æ¨ «^6 butyl «

Fig. 10. Fragmentation of Benzylbutyl phthalate.

Fig. 11. Fragmentation of Diethylhexyl phthalate.

Fig. 9. Fragmentation of Diethyl phthalate.

Fig. 8. Fragmentation of dimethyl phthalate.

Fig. 12. Chromatogram of six phthalate compounds. (a) total ion count (TIC) chromatogram of phthalate, (b) extracted ion chromatogram m/z 163 for dimethyl phthalate and (c) extracted ion chromatogram m/z 149 for other phthalate.

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W <×1 W o³ m/z 251 Æ¨. ¹3 4=8.

, DEHP1;% Fig. 11 < ØW ethylhexyl

«< <× o³ m/z 279 Æ¨O R z* <×

o³ m/z 167 Æ¨* Éþ$=8.

6fW &'() *+, +pÄ 9 51 ¸'

^ A% Fig. 121; ]% O 8. Chromatogram b 1;% DMPW ¢o <Ü m/z 163, c 1;%

Ø phthalateW ¢o <Ü m/z 149 P "C

nó <È 78.

&'() *+, >?Ä 2, 4, 6, 8, 10, 12, 14 ng/ml ù N 50^oC1; 500 rpmU! ºµ; 70

/ PA85 fiber!; X0, î, Bª³ GC J MS

t Fig. 13~151; ]% O 8. »ºU!, >?

W Ç2#1; ²% Õ¹#o 68µ x o BTât -t âo Øé.86 3 48.

, 1 ppb 1 /$% 0@Ä DU! 9 5

 50 º1æè78. « A. Table 61 ÚÛ78.

Table 61 ÚÛ³ O <, DMP% *À t >?

EF(0.054 ng/ml)O BC(0.163 ng/ml)., DnOP

% *À ®t >?EF(0.100 ng/ml) J BC(0.299 ng/ml). Øé=8.

0@% I/G, KLG, HG, G s 4 GW # Fig. 13. Calibration curves of DMP and DEP.

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À1; ó! 3~5 ã 2 lù M î 23 k^41 5¥ 4^oCW 67+1 ]É6, <

` 0@ 1 Ák³ &'() *+,. 9 51 ¸ ' 278. « A. Table 71 ÚÛ78.

Table 71 Øé" A. ]µ, DBPO DEHP% 4

G QR1; BC$=UØ 8ô phthalate-% BC$

88. I/GW DBPO DEHPW &9ñ t 0.48 0.08 ng/ml<=6 KLGW 1 :ë

% DBPO DEHPW &9ñt 0.60O 0.42 ng/ml<=

8. «^6, GW 1 :ë% DBPO DEHPW

&9ñt 1.27O 1.10 ng/ml<6, HGW _% DBP O DEHPW &9ñ< 0.19O 0.61 ng/ml. ]78.

Solid phase microextraction(SPME)1 W phthalate -W ^ 0, 50^oC, 500 rpm1; 70 /1 PA 85 fiber1 W phthalate -* 90% <D vÎ$=8.

Fig. 14. Calibration curves of DBP and BBP.

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Mass spectrum Ë ¹ A, Z ó fragmentation ionW m/zt 8¿ 8: DMP; 163, DEP;

149, 177, 223, DBP; 149. 223, BBP; 91, 149, 223, 251, DEHP; 149, 167, 279, DnOP; 149, 279. Z ó B T;ât â * 0.934~0.972! âo < Øé

6 4UV, D>?EF(RSD)% 5.4~9.5%<6 BC

(LOD)% 0.163~0.299 ng/ml!; <`W /02

< *Þ78.

I/G, KLG, G J HGW =>æ!. ]µ,

DBPO DEHP% 4G QR1; BC$=UØ 8ô phthalate-% BC$ 88. DBPO DEHP QR G1; (1.27 ng/ml J 1.10 ng/ml)! BC$=U V, DEP% HG1; +(0.19 ng/ml)! «^6 DEHP

% I/G1; +(0.08 ng/ml)! BC$=8. ¢£, DEHPW _ WHOW ¿ ? ñ 8 ng/mlO

µ, @ëW ó =>ñt S+ <'6 A

P, 4G QR1; BC$6 4¿ Bµ, m

½O B0* ÷Ú8.

Fig. 15. Calibration curves of DEHP and DnOP.

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9 25t Cmo< 4e DU! 8 1

;W 21 ¨È w ¡U! @³8.

1. Eichelberger, J. W.; Behymer, T. D.; Budde, W. L.

Determination of organic compounds in drinking water by LSE and capillary column GC/MS, Revision 2.2- EPA EMSL-Ci, May 1991.

2. Munch, J. W. Determination of organic compounds in drinking water by liquid solid extraction and capillary column GC/MS, National Exposure Research Labora- tory Office of Research and Development U.S. Envi- ronmental Protection Agency, 1995.

3. Jara, S.; Lysebo, C.; Creibrokk, T.; Lundances, E. Analy.

Chim. Acta, 2000, 407, 165.

4. Kambia, K.; Dine, T.; Gressier, B.; Germe, A. F.; Luy- ckx, M.; Brunet, C.; Michaud, L.; Gottrand, F. J. Chro- matogra. B 2001, 755, 297.

5. Brossa, L.; Marce, R. M.; Borrull, F.; Pocurull, E. J.

Chromatogra. A 2002, 963, 287.

6. Koch, H. M.; Gonzalez-Reche, L. M.; Angerer, J. J.

Chromatogra. B 2003, 784, 169.

7. Prokpkova, G.; Holadova, K.; Poustka, J.; Hajalova, J.

Analy. Chim. Acta 2002, 457, 211.

8. Petrovic, M.; Eljarrat, E.; de Alda, M. J. L.; Barcelo, D.

J. Chromatogra. A 2002, 974, 23.

9. McLafferty, F. W.; Turecek, F. Interpretation of mass spectra. fourth edition, University Science Books, 1993.

Table 6. Standard Deviation and Detection Limit for Phthalates.

Phthalates Measurement No. Mean

ng/ml

SD ng/ml

LOD ng/ml

1 2 3 4 5

DMP DEP DBP BBP DEHP DnOP

0.951 0.972 0.937 1.092 1.195 1.152

1.004 0.938 0.964 0.981 1.113 1.124

1.074 1.034 0.950 0.917 0.987 1.029

1.019 0.979 0.974 0.904 0.963 1.079

0.941 1.115 1.105 1.006 1.094 0.899

0.998 1.008 0.986 0.980 1.070 1.057

0.054 0.069 0.068 0.076 0.095 0.100

0.163 0.208 0.204 0.227 0.286 0.299 average Mean = 1.017 ng/ml, SD = 0.077 ng/ml, LOD = 0.231 ng/ml

Table 7. Analysis of Phthalates in Water Samples of Han, Geum, Nakdong and Sumjin Rivers Water

System Site No.

ng/ml DMP, DEP

BBP, DnOP Water System

Site No.

ng/ml DMP, DEP

BBP, DnOP

DBP DEHP DBP DEHP

Nakdong River

N-1 0.66(±0.05) ND ND

Han River

H-1 1.31(±0.07) 1.26(±0.12) ND

N-2 0.33(±0.03) ND ND H-2 1.62(±0.14) 0.91(±0.07) ND

N-3 0.28(±0.03) ND ND H-3 1.16(±0.08) 0.99(±0.06) ND

N-4 0.42(±0.04) ND ND H-4 1.15(±0.12) 1.32(±0.08) ND

N-5 0.72(±0.05) 0.38(±0.05) ND H-5 1.11(±0.08) 1.04(±0.09) ND

Sumjin River

S-1 1.13(±0.07) ND ND

Gum River

G-1 0.26(±0.04) 0.39(±0.05) ND

S-2 0.83(±0.05) 0.62(±0.06) ND G-2 ND 0.34(±0.03) ND

S-3 0.29(±0.04) ND ND G-3 0.32(±0.03) 1.09(±0.06) ND

S-4 0.42(±0.04) 0.72(±0.08) ND S-5 0.33(±0.03) 0.76(±0.05) ND

Solid Phase Microextraction-GC/MS  