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1 4 3 Vol. 4 No Journal of Food Safety and Quality Jun., 2013 朱 * 舟, 刘桂华 (, ) 摘要 : 目的, 方法,, ph 5.2 SCX, (BSTFA), (SIM) (Scan) NIST, 结果, μg/kg 结论,, 关键词 : ; ; ; ; Emergency determination of clenbuterol hydrochloride residue first found in food poisoning accident induced by intake of snake ZHU Zhou, LIU Gui-Hua *. (Shenzhen Center for Disease Control & Prevention, Shenzhen , China) ABSTRACT: Objective Samples concerned two consecutive food poisoning accidents occurred in the same restaurant located at Shenzhen, Guangdong province, were taken and sent to laboratory for emergency determination to find the cause of poisoning. Methods Samples were alkalified and extracted using ethyl acetate, then re-extracted by hydrochloric acid. After adjusted to ph 5.2, the acidic extraction was purified by solid-phase extraction using SCX cartridges. After isolated with BSTFA, clentuberol hydrochloride in the solution was detected by gas chromatography-mass spectrometry. Identification was achieved by electron impact ionization (EI) using selected ion monitoring (SIM) combined with full scan of mass spectrum. Quantification was performed by internal standard calibration using metoprolol. Results The muscle, blood and gall of snake (Vipera ruselli siamensis) were collected from the restaurant where the food poisoning accidents happened, as well as the urine of a patient were determined and the content of clenbuterol hydrochloride were 1331, 463, and 4.3 μg/kg, respectively. However, there was no positive result of clenbuterol hydrochloride in other food samples including subsequent snake samples collected for traceability. Conclusion The reason of two consecutive food poisoning accidents was finally determined to be the intake of snake (Vipera ruselli siamensis) contaminated by clenbuterol hydrochloride, which was first remarkably reported at home and abroad. * 通讯作者 : [email protected] *Corresponding author: LIU Gui-Hua, Professor, Shenzhen Center for Disease Control & Prevention, No.8, Longyuan Road, Nanshan District, Shenzhen , China. [email protected]

(Shenzhen Center for Disease Control & Prevention, Shenzhen 518055, China) ABSTRACT: Objective Samples concerned two consecutive food poisoning accidents occurred in the same restaurant located at

2 666 4 KEY WORDS: snake; clenbuterol hydrochloride; residue; food poisoning; emergency determination (clenbuterol hydrochloride), 2-[( ) ]-4- -3,5-,,, 2.5 μg [1],,, [2-4] [5] - (GC/MS) ,,,,,,,,, 1 材料与方法 1.1 试剂与仪器 ( ), 99%( Sigma ); 1000 mg/l, 20 ; 10 mg/l ; 2.5 mg/l ;, Merck ;, ; Supelco (SCX) (3 ml/ 500 mg, Supelco ); (BSTFA, Supelco ) %( ) (Shimadzu GC 17A/ MS QP5050A, ), (EI) GC solution, ; : DB-5MS 30 m 0.25 mm, 0.25 μm( Agilent ); 0.22 μm ( ); ( IKA ); ( Supelco ); ( IKA ); ( Beckman ); ( ±2, Binder ) 1.2 实验方法 NY/T /,,,, ph 5.2 SCX, (BSTFA) GC/MS, (EI), (SIM) Scan, 1.3 GC/MS 分析条件 : ; 1 μl, ; 250 ; min, 25 /min min, 25 /min min, 14 min; 0.9 ml/min : I/F 280 ; 7 min; (EM) 200 V; (EI) 230 ; 150 ; (SIM) m/z , m/z , m/z 86 72; (full scan) m/z 50~350 SIM 样品前处理提取 (5±0.05) g

5 mg/l ;, Merck ;, ; Supelco (SCX) (3 ml/ 500 mg, Supelco ); (BSTFA, Supelco ) 99.999%( ) (Shimadzu GC 17A/ MS QP5050A, ), (EI) GC solution, ; : DB-5MS 30 m 0.25 mm, 0.25 μm( Agilent ); 0.

3 3, : SIM ( 2.5 mg/l; 0.5 mg/l) Fig. 1 SIM chromatogram of clenbuterol (2.5 mg/l) and metoprolol (internal standard, 0.5 mg/l), 15 ml, 5 ml 10%, r/min 1 min, 6000 r/min 5 min,, 10 ml, 1 min, 6000 r/min 5 min, 5 ml 0.10 mol/l, 1 min, 6000 r/min 5 min,,,, 2.5 mol/l ph 净化 SCX 5 ml 5 ml 5 ml 30 mmol/l,, 5 ml 5 ml,, SCX, 5 ml 4%, 氮气浓缩及衍生化 2.5 mg/l ( ) 100 μl, 40, 50 μl 50 μl BSTFA, 1 min, 80 1 h( ); μl 10 mg/l 4.5 ml 4%, 2.5 mg/l 100 μl, 400 μl, 0.22 μm, GC/MS 1.5 定性定量方法 2 s,, 3 ( ) ±20% 3 ( ), GC/MS, EI NIST, mg/l, 0.5 mg/l, (m/z 86) (m/z 72)

5 mol/l ph 5.2 1.4.2 净化 SCX 5 ml 5 ml 5 ml 30 mmol/l,, 5 ml 5 ml,, SCX, 5 ml 4%, 1.4.3 氮气浓缩及衍生化 2.

4 结果与分析 2.1 食物中毒事件回顾 : (1)9 1 7, 8, 7,,, ; (2)9 2 8, 6,,,, [6], 2.2 检测结果 , ;, ;, , , 21, 29 (0903-1~0903-8, ~0910-9, ~ ), >0.99, 1 29, ~0903-8, SIM( ), EI NIST, 90% ; ( ), μg/kg; 4.3 μg/kg; ~ , (<2.0 μg/kg), ( ), ( 600 μg/kg),, >80%,, ~0903-8, ~ ~ (<2.0 μg/kg) SIM, NIST 2~5 表 1 29 份样品中克伦特罗的 GC/MS 测定结果 Table 1 GC/MS analytical results of clenbuterol in 29 collected samples X (μg/kg) X (μg/kg) < < < < < < < < < < < < < < < < < < < < < < < < <2.0 : 2.0 μg/kg

0 μg/kg) SIM, NIST 2~5 表 1 29 份样品中克伦特罗的 GC/MS 测定结果 Table 1 GC/MS analytical results of clenbuterol in 29 collected samples X (μg/kg) X (μg/kg) 0903-1 <2.0 0910-8 <2.0 0903-2 <2.0 0910-9 <2.

5 第3期朱图2 Fig. 2 空白猪肉及克伦特罗加标猪肉(加标 600 μg/kg)的 SIM 模式色谱图 SIM chromatogram of clenbuterol in blank samples and spiked pork (600 μg/kg) 图3 Fig. 3 舟, 等: 首例蛇中盐酸克伦特罗残留引起的食物中毒应急检测阴性八步蛇肉(0911-6)及阳性八步蛇肉(0903-5)的 SIM 模式色谱图 SIM chromatogram of clenbuterol in negative (0911-6) and positive (0903-5) snake muscle 669

6 670 4 Fig. 4 4 Scan EI NIST Full scan spectrum of clenbuterol in standard solution and corresponding similarity report of NIST library (EI source) search Fig Scan EI NIST Full scan spectrum of clenbuterol in positive snake (Vipera ruselli siamensis) muscle (0903-5) and corresponding similarity report of NIST library (EI source) search 3 讨论,, ;, ( ),

similarity report of NIST library (EI source) search Fig.

7 3, : 671 1, 72 h [6],, μg/kg, 4.3 μg/kg (<2.0 μg/kg);,,,, μg/kg, 1331 μg/kg, 463 μg/kg,,,,,, 1,, (<2.0 μg/kg);, 1,,, ;,,,, 4 结论,, GC/MS,,,,,, [7] ; [8] ;,,, ( ) [9-10],,,,,,,,,,,, 参考文献 [1] Smith DJ. Total radioactive residues and clenbuterol residues in swine after dietary administration of [14C] clenbuterol for seven days and preslaughter withdrawal periods of zero, three or seven days [J]. J Anim Sci, 2000, 78(11): [2],. 20 [J]., 2011, 17(3): Wang W, Zhang KL. Analysis for 20 cases of food poisoning in children induced by clenbuterol hydrochloride [J]. Anhui J Prev Med, 2011, 17(3): [3],, [J]., 2008, 25(1): 1 8. Hu P, Yu SW, Li H, et al. Analysis of the food poisoning cases caused by the clenbuterol in 13 provinces of China from 1999 to 2005 [J]. J Shenzhen Univ Sci Eng, 2008, 25(1): 1 8. [4],. 17 [J]., 2011, 37(6): Li B, Li SY. Analysis for 17 cases of food poisoning induced by clenbuterol hydrochloride in TianHe district of Guangzhou [J]. South China J Prev Med, 2011, 37(6): [5]. [J]., 2007, 13(2):

Total radioactive residues and clenbuterol residues in swine after dietary administration of [14C] clenbuterol for seven days and preslaughter withdrawal periods of zero, three or seven days [J].

8 672 4 Zou ZG. Research progress for food poisoning of clenbuterol hydrochloride and corresponding residue detection [J]. Prev Med Trib, 2007, 13(2): [6],,,. [J]., 2011, 40(1): Peng CQ, Huang W, Zhu Z, et al. Report for 2 cases of food poisoning induced by clenbuterol hydrochloride through intake of snake muscle [J]. J Hyg Res, 2011, 40(1): [7],,,. 85 [J]., 2008, 9(1): Hu P, Yu SW, Li ZL, et al. Analysis for 85 cases of food poisoning induced by clenbuterol hydrochloride [J]. Chin Prev Med, 2008, 9(1): [8],, [J]., 2006, 22(4): Wu XL, Wang ML, Zou ZM, et al. Detection for clenbuterol hydrochloride residue in livestock and poultry meat of Jiaxing from 1999 to 2005 [J]. Chin J PHM, 2006, 22(4): [9],,,. [J]., 2003, 15(4): Ye LX, Liu X, Dong SL, et al. Food poisoning of clenbuterol hydrochloride induced by cultivated chub fish [J]. Chin J Food Hyg, 2003, 15(4): [10],,. [J]., 2001, 13(3): 40. Hong WH, Dai CF, Chen H. Food poisoning of clenbuterol hydrochloride induced by misusing porcine somatotropin as starch [J]. Chin J Food Hyg, 2001, 13(3): 40. 作者简介 ( 责任编辑 : 赵静 ) 朱舟, 硕士, 主管技师, 主要研究方向为卫生理化检验 [email protected] 刘桂华, 硕士, 主任技师, 主要研究方向为卫生理化检验 [email protected]

, 2008, 9(1): 65 67. Hu P, Yu SW, Li ZL, et al. Analysis for 85 cases of food poisoning induced by clenbuterol hydrochloride [J]. Chin Prev Med, 2008, 9(1): 65 67. [8],,. 1999 2005 [J].

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