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理料易行年年類了料料易理不理率異數量率料量 ~ ~ ~ 料量 1

料年陸不料年來類量年類量類量類量量不量不量不蘭量不年令量類量量年來力量降量料類年來類料量量了立類量料量率率度留率率度理不例行立了易量料量行立易量例行 2

料料料 (distilled spirit) 21 (non-distilled spirit)24 54 (ethyl carbamate, EC) (guaiacol) 1,3- (1,3-butanediol) 1,5- (1,5-pentanediol) 3- -1,5- (3-methyl-1,5-pentanediol) 2- - (2-methyl pentanoic acid) 1,6- (1,6-hexanediol) ( 度 98 ) SCI ( ) 0.4g 2- - (2-methyl-n-pentanoic acid) 100mL 量量 ( ) 2- - (relative response factor RRF) 0.4% (w/v) 0.4% (w/v) 2- - 不例 (ethyl carbamate /2-methyl-pentanoic acid=2/1 1/1 1/2) 兩 2- - RRF = (A S /W S ) (A IS /W IS ) (1) A S = ethyl carbamate GC A IS = 2-methyl-pentanoic acid GC W S = ethyl carbamate 量 (ug) W IS = 2-methyl-pentanoic acid 量 (ug) ( ) 量 * 料易理 (1) ( 不理 ) (Method I) (2) ( 5-10 ) (Method II) 3

(3) EC (v/v=1/2) (Method III) 0.1 L GC 量 (2) Ethyl carbamate (ug/ml) = (A S /A IS ) (W IS /RRF) 1/V (2) V = (ml) Method : 類 1 ml 7 ml vial 200 µg/50 µl (IS = 2-Methyl-n-Pentannoic Acid) 0.1 µl EC 量 4

Method : 類 25 ml 250 ml 400 µg/100 µl (IS = 2-Methyl-n-Pentannoic Acid) 2-5 ml 0.1 µl EC 量 Method : 類 25mL 100 ml 量 200 µg/50 µl (IS = 2-Methyl-n-Pentannoic Acid) 50 ml 2-3 0.2-0.5 ml 0.1 µl EC 量 5

( ) 量 (200 g /ml) 2.5 1.0 0.5 0.25 0.1 g/ml 1 ml 50 g (2-methyl-pentanoic acid) GC 量度 ( ) 5 g 1 ml, 25 ml 25mL 200, 400 200 g Method I, Method II Method III 量率 ( 六 ) GC Hitachi G-3000 FID H 2 flow rate=30 ml/min air flow rate=300 ml/min 度 =280 o C 度 =240 o C He flow rate = 4 ml/min 離 CP-Wax (30 m 0.53 mm 1 m) (Chrompack, Netherlands) 度 100 o C 2 3 o C 率 135 o C 5 o C 率 155 o C 50 o C 率 300 o C 量 0.1 L direct injection mode 論理量 ( ) 連 GC 量理李 19 1 ml ph 2.0 6

10 連 1 ml GC 量 split mode 30~40min 糖率 90% 20 5 ml ph 2.0 NaCl 6 heptanoic acid GC 量 splitless direct injection mode 20min 糖率 92~98% 兩糖便糖量 90% 率 Sheu et. al., 1996, 率不度靈度年 GC (injector) insert 塞 1~2m guard column 離降 22-24 tailing GC 度 GC 離 megapore column 24 GC GC 離留留 insert 不 100 insert 便 insert 10 injector 理料 ( ) 不理量 (Methood I) ( ) GC(Method II)( ) GC(Method III) 離立便料量離 (EC) CP-Wax 行度 100 o C 2 min 8 o C 220 o C 50 o C 率 250 o C 度 290 o C 度 250 o C 料 EC GC 留 12.73min 20 min 料量 guaiacol, 1,3-butanidiol, 2-methyl-n-pentanoic acid, 1,5-pentanediol 7

3-methyl-1,5-pentanediol 1,6-hexanediol 六 GC 1,5-pentanediol 3-methyl-1,5-pentanediol 1,6-hexanediol 留 11.41, 14.32, 14.68, 17.24, 18.57 19.08min GC 2-methyl-n-pentanoic acid 不 EC 量 GC Method I, Method II Methood III 類 20 ~ 2-methyl-n-pentanoic acid 量類 EC 量 EC 2-methyl-n-pentanoic acid ( ) (RRF) EC 量 (2) EC GC (Y ) 度 (X ) 數 R 2 =0.99 EC 0.42 量類不理 GC (Method I) ) GC (Method II) GC (Method III) FID FID=1 attenuation=1 EC 量 0.5, 0.1 0.1 g/ml 六 5 g 六類料 ( ) Method I Method II Method III : Method I 率 95~119% 異數 (cv%) 9.2% Method II 率 96~112% 異數 (cv%) 8.9% Method III 率 96~107% 異數 (cv%) 7.3% 料量 8

21 24 45 Method I Method II Method III 量量 Method I : 21 EC 量 0-2.74 g/ml 24 EC 量 0-1.01 g/ml, 45 EC 率 22% Method II : 21 EC 量 0-2.28 g/ml 24 EC 量 0-1.12 g/ml, 45 EC 率 72% Method III : 21 EC 量 0-2.57 g/ml 24 EC 量 0-1.35 g/ml, 45 EC 率 77% Method II Method III EC 率 Method I, Method I 度 0.5 g/ml( ), EC 量若 0.5 g/ml 便 Method I 便論料易理, : ( ) (1 ml) (2-methyl-n-pentanoic acid, IS) GC (Method I) ; ( ) 類 (25 ml), 5-10, GC (Method II) ; ( ) 類 (25 ml) (v/v=1/2) 2-3, 0.5 ml, GC (Method III) Oven temperature 100 o C 2 3 o C 率 135 o C, 5 o C 率 155 o C 50 o C 率 300 o C 量料 20-30 來 45 量率 22 72 77% Method I Method II Method III 45 類, 45 料量 0~ 2.74 0~2.28 0~2.57 g/ml 9

參 10

55. Drexler-W; Schmid-ER.1989. A gas chromatographic method for the determination of ethyl carbamate in spirits. Ernaehrung-; 13 (10) 591-594. 56. Kiyoshi-Y; Kojiro-T. 1989. Simplified method for determination of ethyl carbamate in sake. Journal-of-the-Brewing-Society-of-Japan,84 (3) 192-194. 14

Table 1. Gas chromatographic retention time of some standard candidates Compound Retention time (min) a Guaiacol 11.41 1,3-Butanediol 14.32 2-Methyl-n-pentanoic acid 14.68 3-Methyl-1,5-pentanediol 17.24 1,5-Pentanediol 18.57 1,6-Hexanediol 19.08 a CP-Wax column (0.53mm 30m, DF=1.5µm) was used. Oven condition 100 (1min)@ 3 /min 135 @5 /min 155 /min@ 50 /min 300. Table 2. Relative response factor (RRF) and GC retention time (RT) of 2-methyl-n-pentanoic acid to ethyl carbamate Compound RRF a RT b Ethyl carbamate (EC) 0.42 12.73 2-Methyl-n-pentanoic acid (MePA) c 1.00 14.68 a RRF of 2-methyl-n-pentanoic acid to ethyl carbamate. b CP-Wax column (0.53mm 30m, DF=1.5µm) was used. c Internal standard. Oven condition 100 (1min)@ 3 /min 135 @5 /min 155 /min@ 50 /min 300. 18

Table 3. Lowest quantitatively determinable concentration of ethyl carbamate by gas chromatography with FID detector Sample preparation* Concentration (µg/ml) Detectability a Recovery b RSD c 2.5 Yes 102.4 5.8 1.0 Yes 104.9 6.6 0.5 Yes 108.1 9.5 0.25 No -- -- 0.1 No -- -- 2.5 Yes 99.1 4.9 1.0 Yes 102.8 5.1 0.5 yes 96.7 7.3 0.25 yes 107.5 8.9 0.1 Yes 118.4 12.7 0.05 No -- -- 2.5 yes 97.7 5.7 1.0 yes 102.3 6.3 0.5 yes 94.8 7.4 0.25 Yes 105.6 8.4 0.1 yes 117.3 13.9 0.05 no -- -- * = by direct injection method; =25mL sample was concentrated to 2-5mL, before injection; =25mL sample was extracted with ethyl acetate, and concentrated to 0.5-1 ml,before injection. a FID range 1, Attenuation 1. b Average of three analyses. c Coefficient of variation cv. 19

Table 4. Recoveries of the spiked ethyl carbamate from various alcoholic liquor or beverages by spitless direct injection GC method (method Sample Blank a (µg) (A) Amount added (µg)(b) Amount found (µg) b (C) Recovery ( ) c CV ( ) d Whisky 1 ND 5.12 5.79 113.09 7.62 Kaoliang 1 ND 5.12 5.61 109.60 4.38 Medecine wine ND 5.12 6.14 119.92 9.17 Red wine 1 ND 5.12 5.07 99.02 7.39 Grape wine 1* 3.37 5.12 9.29 109.42 8.27 Plum wine ND 5.12 4.87 95.12 7.69 a Ethyl carbamate in 1 ml whisky. b Average of triplicate analyses. c Recovery C A / B 100. d Coefficient of variation cv. 20

Table 5. Recoveries of the spiked ethyl carbamate from various alcoholic liquor or beverages by concentration-direct injection GC method (method Sample Blank a (µg) (A) Amount added (µg)(b) Amount found (µg) b (C) Recovery ( ) c CV ( ) d Whisky 1 1.25 5.12 6.23 97.80 3.47 Kaoliang 1 1.71 5.12 7.17 104.97 5.81 Medecine wine ND 5.12 4.91 95.90 7.38 Red wine 1 0.38 5.12 6.18 112.36 8.92 Grape wine 1* 4.49 5.12 9.33 97.09 5.67 Plum wine 1.39 5.12 6.71 103.07 2.19 a Ethyl carbamate in 25 ml whisky. b Average of triplicate analyses. c Recovery C A / B 100. d Coefficient of variation cv. 21

Table 6. Recoveries of the spiked ethyl carbamate from various alcoholic liquor or beverages by solvent extraction-spitless direct injection GC method (method Sample Blank a (µg) (A) Amount added (µg)(b) Amount found (µg) b (C) Recovery ( ) c CV ( ) d Whisky 1 1.32 5.12 6.86 106.52 3.89 Kaoliang 1 1.36 5.12 6.25 96.45 5.64 Medecine wine ND 5.12 5.48 107.03 7.28 Red wine 1 ND 5.12 4.98 97.27 6.89 Grape wine 1* 4.58 5.12 15.02 103.29 7.34 Plum wine 1.12 5.12 6.37 102.08 5.43 a Ethyl carbamate in 25 ml whisky. b Average of three analyses. c Recovery C A / B 100. d Coefficient of variation cv. 22

Table 7. Ethyl carbamate levels found in some alcoholic beverage Sample EC content µg/ml Method Method Method Distilled spirit Whisky 1 1.02 1.25 1.32 Whisky 2 ND 0.78 0.85 White liquor 1 ND ND ND Kao liang 1 1.34 1.71 1.25 Kao liang 2 0.93 0.83 0.79 Kirin whisky ND 0.26 0.31 XO-1 ND 0.20 0.18 XO-2(J) ND ND 0.14 VSOP-A ND 0.32 0.41 VSOP-B ND 0.24 0.31 Drambule-B 2.74 2.28 2.91 Kliporiff-c ND 0.56 0.62 Drambule-d 2.43 1.82 2.57 Martell-e ND ND ND Pushkin-f ND ND ND Smirnoff-g ND ND ND Cocorico-h 1.46 1.72 1.28 J&B-I 2.01 1.23 1.59 Rice wine 1 ND 0.21 0.15 Rine wine 2 ND 0.20 0.13 Rine wine heads ND 0.18 0.14 Non-distilled spirit Plum wine 1 ND 0.59 0.72 Plum wine 2 ND 0.43 0.35 Plum wine 3 ND 0.23 0.37 Red wine 1 ND ND 0.12 Red wine 2 ND ND ND Red wine 3 ND ND 0.13 Red rose 1 ND ND ND Red rose 2 ND ND 0.13 Red rose 3 ND ND 0.11 White wine 1 ND ND 0.14 White wine 2 ND ND 0.11 White wine 3 ND ND 0.17 Yellow wine 1 ND 0.62 0.84 Yellow wine 2 ND 0.54 0.73 Shao-Hsing wine 1 0.88 1.12 1.35 Shao-Hsing wine 2 0.74 0.69 0.85 Taiwan beer 1 ND 0.28 0.34 Taiwan beer 2 ND 0.37 0.41 Beer 3 ND 0.22 0.37 Beer 4 ND 0.38 0.42 Medecine wine 1 ND ND ND Medecine wine 2 1.01 0.82 0.75 Medecine wine 3 ND 0.15 0.19 Medecine wine 4 ND ND 0.11 Detectability (%) 22.22% 71.79% 76.92% a Average of two analyses. 23