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理勞暴露類 CNOS93-04 行 93 年 1 1 93 年 12 31 李亮參行年

勞暴露尿勞暴露來暴露勞尿便理暴露勞尿行量 60 µm polydimethylsiloxane divinylbenzene (PDMS DVB) 尿度 0.01436 µg/ml 2.872 µg/ml 度 11.6 µg/ml 2.320 µg/ml 類度參數尿率 86 ~ 94 率 86% ~ 114% 異數 4.9 % 3.75 % 尿 -20 度令 0.01436 0.0718 0.359 1.436 µg/ml0.0116 0.058 0.290 1.160 ng/ml 度尿 2 率 81.5 %~123.4 % 率 83.63 ~ 110.5 尿 0.43 ng/ml 0.22 ng/ml 尿度尿 Abstract Urinary phenol and cresol is analyzed widely to determine benzene and toluene exposure in human. Most methods utilize direct measurements of phenols and cresols after extraction from urine using gas chromatography or high-performance liquid chromatography. We describe a novel and simple method to measure phenol and cresol from urine exposed to benzene and toluene. A solid phase microextraction and liquid chromatography (SPME-HPLC) system is here applied to the determination of the benzene and toluene exposure biomarker in urine. The PDMS DVB fiber (60 µm) was evaluated. The method was optimized using spiked urine samples in a range from 0.01436 µg/ml to 2.872 µg/ml for pheol and from 0.0116 µg/ml to 2.320 µg/ml for cresol. The effects of equilibration time and ionic strength of samples on the adsorption step were studied. The parameters affecting the desorption process, such as desorption mode, solvent composition and desorption time, were optimized. The method is reproducible and repeatable with recoveries calculated from spiked urine samples, varying from about 86% to 94% for phenol and 86% to 114% for cresol. The coefficients of variation (CV) generated by repeated analyses of urine samples were 4.9 % and 3.75 %, respectively. The stability of sample storage at -20 was assessed and the results were satisfactory. The analytical recovery of urine samples were very good (81.5 %~123.4 % for phenol and 83.63 ~ 110.5 or cresol). The limits of detection for phenol and cresol were 0.43 ng/ml and 0.22 ng/ml respectively. The method enabled the determination of phenol and cresol at low levels in urine samples. Keywords: solid phase microextraction, urine, biological monitoring 勞尿了勞暴露暴露列理列見來識不了更見 (International Agency for Research on Cancer, IARC) 列 group1

Cytochrome P450 2E1 來列 trans,transmuconaldehyde trans,trans-muconic acid(t,t-ma) catechol (CAT) hydroquinone (HQ) 1,2,4-benzenetriol (BT) glutathione S-phenylmercapturic acid (S-PMA) 來 [1-4] 尿 p- 尿 [5] 尿 ph 1 Sep-pak Cl8 濾濾 / / 理離來 S-PMA 來硫 - 硫 - - 2- 硫 HPLC [6-9] 理來論 GC 都理都不 HPLC 不糖硫 [10] 尿量暴露尿理行尿流 GC [11-15] 不更浪漏率不 - 便 - 便了例行量理 (solid- phase microextraction SPME) 了便靈度量 [16-20] 利 SPME 量 µg/l 度 SPME 量 3.1 料 3.1.1 Phenol (99 ) P-cresol(methylphenol 99 ) ChemService NaCl(sodium chloride 99.5 ) GR Merck 晴 99.98 TEDIA99.8 Fluka 3.1.2 HPLC HITACHI L-7100 Pump SH- IMAPDZU SPD-10A UV-VIS DETECTOR SPME SPME-HPLC SUPELCO. SPME-HPLC 六 60 µl 離 ZORBAX Eclipse XDB-C18 LC (Agilent Techn-ologies) 4.6 mm 75 mm 3.5 µm 流 80( ):20( 晴 ):0.02( ) 流 1 L/min 切六 INJECT 來流離行流 3.1.3 SUPELCO Solid Phase Microextraction

Holder 57331 連 SUPELCO Solid Phase Microextraction Fiber 1250 r- pm 度 30 5 1 3.2 行 condition fiber fiber 15 切 Inject 流 15 離留行行切 Inject 流行論 4.1 4.1.1 類 SPME 率類 CW-TPR 60 µm PDMS DVB 行量率 CW-TPR 量 PDMS DVB 4.1.2. 了立力率數尿 ph 2 2mL 4 ml PDMS DVB 尿 5 15 30 40 60 min 行 1 30 min 狀 fiber 30 min Area response 8e+5 6e+5 4e+5 2e+5 0 1 0 10 20 30 40 50 60 70 Absorption time (min) Phenol Cresol 尿 4.1.3 SPME-HPLC 了來兩了立 HCl ph 2 ~ 3 不例 / 晴 / 行 / 晴 / (80/20/0.02%) 1 3 5 7 行 5 5 92 ~ 94 6 ~8 留 HCl ph 2 ~ 3 行 5 行不 1 3 5

不 1 4.1.4 2 不類尿留離流 5 兩留若不留省留留 4.1.5 類類留 (%) 留 (%) 6.49-2.97 1.57 流 2.13 1.41 4.03-2.68 0.30 流 0.52 0 類離度度降 Na 2 SO 4 NaCl KCl NH 4 Cl 類行類不類度不類 2 Na 2 SO 4 NaCl KCl NH 4 Cl 類 Na 2 SO 4 離度 NaCl 來 NaCl 來類 Area resopnse 5e+5 4e+5 3e+5 2e+5 1e+5 Na 2 SO 4 NaCl Kcl NH 4 Cl No salt 4.1.6 ph 類 ph 不離度異 ph ph 2 3 4 7 行 60 µm P-DMS/DVB 30 SPME-HPLC 5 1 ph=2 量不 ph 度異不度 ph 2 ~ 3 3 Area resopnse 4e+5 3e+5 2e+5 1e+5 0 Phenol Cresol ph 尿 3.2 留列 3.2.1 量立不度尿行度量度 0.01436 ~ 1.436 µg/ml 0.0116 ~ 1.16 µg/ml 量度度 0.01436 ~ 7.18ug/mL 度量 ph ph 2 ph 3 ph 4 ph 7 0 Phenol Cresol Salt

R 2 0.995 度 0.0116 ~ 5.8 ug/ml 度量 R 2 0.995 4.2.2 了尿 matrix effect 尿離離尿 1 1 度 0.01436 ~ 1.436 µg/ml 0.0116 ~ 1.16 µg/ml 量不量率若尿離量不度率不量率 90 論立量率異不不 4.2.3 率勞尿 430.8 ng/ml 348ng/mL 離量率率 86 ~ 114 異數 1 ~ 8 尿不立量度 (µg/ml) R 2 y=1.4 10 5 x+8.9 10 3 0.9974 0.01436 ~ 1.436 尿 y=1.4 10 5 x +8.1 10 3 0.9985 : 尿 (1:1) y=1.4 10 5 x +7.8 10 3 0.9986 y=2.7 10 5 x +9.3 10 3 0.9993 0.0116 ~ 1.16 尿 y=2.7 10 5 x +7.2 10 3 1.000 : 尿 (1:1) y=2.8 10 5 x +5.1 10 3 0.9988. 不量 ( 尿 : =1:1) 尿率量尿量度率 (%)±(n=3) 率 (%)±(n=3) (µg/ml) ( 尿 : 尿 ( 尿 : =1:1) =1:1) 0.1436 103.7±2.8 106.3±1.8 110.0±6.6 110.8±1.8 0.2872 103.2±0.41 102.2±0.77 108.8±2.4 104.8±0.78 0.4308 103.2±3.6 105.5±5.3 106.6±1.4 107.4±5.3 0.7180 99.1±1.7 103.2±3.0 105.6±4.5 104.6±3.1 1.436 98.2±2.1 100.5±2.5 99.3±2.0 101.5±2.5 0.116 90.8±0.65 91.6±5.7 107.7±5.1 99.8±5.7 0.232 93.6±1.6 96.4±5.9 112.4±13.0 101.3±6.0 0.348 95.5±4.2 91.5±5.9 106.9±9.8 95.2±6.0 0.580 97.5±1.4 94.7±4.4 102.9±10.5 97.5±4.5 1.16 97.8±1.7 101.1±1.4 101.8±4.9 103.3±1.4

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