6 10 Vol. 6 No. 10 2015 10 Journal of Food Safety and Quality Oct., 2015 N,N- 刘 印 平 1, 刘 玉 欣 1, 云 鹏 1, 路 杨 1, 王 丽 英 1, 常 凤 启 1, 杨 立 新 (1.,, 050021; 2., 100871) 1, 2* 摘 要 : 目 的 - (gas chromatography-mass spectrometry, GC-MS) N,N- 方 法, SILICA/PSA /, D6-N,N- 结 果 66.9%~103.4%, (RSD) 2.5%~7.7%, 30 N,N-, 8 2, N,N- 3.0 µg/kg 结 论,, N,N- 关 键 词 : N,N- ; - ; ; ; Determination of N-dimethyl nitrosamine in beer and sausage LIU Yin-Ping 1, YUN Peng 1, LU Yang 1, WANG Li-Ying 1 1, 2*, YANG Li-Xin (1. Hebei Provincial Center for Disease Control and Prevention, Hebei Provincial Key Laboratory of Food Safety Risk Monitoring, Shijiazhuang 050021, China; 2. College of Environmental Sciences and Engineering, Peking University, Beijing 100871, China) ABSTRACT: Objective To establish a method for the determination of N-dimethyl nitrosamine in beer and sausage by gas chromatography-mass spectrometry. Methods Homogenized samples sequentially were extracted by methylene chloride, centrifugation, and SILICA/PSA columns cleanup before analyzed by gas chromatography-mass spectrometry. Quantification of N-dimethyl nitrosamine was based on the use of D6-N-dimethyl nitrosamine. Results The present method showed acceptable recoveries of 66.9%~103.4%, with relative standard deviation (RSD) ranging from 2.5% to 7.7%. Analysis of 30 beer samples and 8 sausage samples by the current method were successfully performed. N,N-dimethyl nitrosamine were not detected in beer samples. Two positive sausage samples were detected and the content was lower than the limited value of 3.0 µg/kg in meat products. Conclusion This quantitative method is demonstrated to be rapid, simple, and high sensitive, which can be applied in the accurate determination of N-dimethyl nitrosamine in beer and sausage. KEY WORDS: N-dimethyl nitrosamine; gas chromatography-mass spectrometry; internal standard; beer; sausage * 通 讯 作 者 :,, E-mail: yanglixin241@163.com *Corresponding author: YANG Lin-Xin, Senior Technical Personnel, Hebei Provincial Center for Disease Control and Prevention, No.97, Huai an East Road, Shijiazhuang 050021, China. E-mail: yanglixin241@163.com
10, : N,N- 3835 1 引 言 N,N- (NDMA), N-,,, [1-3] (ACGIH) NDMA,,,, N,N-,, [4,5],,,, [4-7] N,N-,, ( TEA), GB/T 5009.26-2003 N- [8] (30~200 g) N,N-, D 6 -N,N-,,, [9,10],,,,,, N,N- 2 材 料 与 方 法 2.1 仪 器 与 试 剂 : - DSQ(Thermo, USA); TDL-5-A ( ); AE200 ( METTLER ); SILICA/PSA ( 1.0 g/6 ml)( ) : N,N- (1 mg/ml), ; D 6 -N,N- (1 mg/ml), Cambridge : (, Fisher ); (, ) 2.2 样 品 前 处 理 50 ml, 5 min, 10 ml 50 ml, 100 μl D6-N,N- (2.0 mg/l),, 3.0 g, 15 ml, 30 s, 10 min, 10000 r/min 4 min,,,, 1 ml, 10 g,, 40 ml, 10 min, 10000 r/min 4 min,,, 1 ml, SILICA/PSA (1.0 g/6 ml), 5 ml 5 ml,, 5 ml 10% /, 5 ml,, 1.0 ml, - (gas chromatographymass spectrometry, GC-MS), 2.3 气 相 色 谱 质 谱 条 件 : : ( 99.999), DB-INNOWAX (30 m 0.25 mm 0.25 µm), : 1.0 ml/min; : 250, : 1 μl, ; : : 35, 3 min, 10 /min 120, 15 /min 200, 250, 5 min : : 280 ; : 230 ; : (EI); : (SIM), 1 2.4 标 准 储 备 液 和 标 准 溶 液 的 配 制 N,N-,,, (10 50 100 200 500 1000 ng/ml), 200 ng/ml
3836 6 Table 1 表 1 N,N- 二 甲 基 亚 硝 胺 监 测 离 子 Monitoring ions of N-dimethyl nitrosamine (min) 9.80 N,N- 42, 43 74 9.80 D6-N,N- 46 80 3 结 果 与 讨 论 3.1 方 法 的 线 性 范 围 和 检 出 限, 10 50 100 200 500 1000 ng/ml N,N-, N,N-, Y=0.00648823X, r=0.9995 1 2 2 N,N- ( 100 ng/ml) Fig. 2 The chromatogram of N-dimethyl nitrosamine spiking in beers at 100 ng/ml 1 N,N- (200 ng/ml) Fig. 1 The chromatogram of N-dimethyl nitrosamine standard solution (200 ng/ml) 3.2 回 收 率 和 精 密 度,,,, 6, 2, 72.9%~103.4%, (RSDs) 2.5%~7.7%,, 3.4 实 际 样 品 测 定 N,N-, 30, N,N- 8 N,N-, 2, 2.5 μg/kg 2.8 μg/kg, N,N- (3 μg/kg)
10, : N,N- 3837 表 2 测 定 N, N- 二 甲 基 亚 硝 胺 的 准 确 度 和 精 密 度 Table 2 Accuracy and precision for N-dimethyl nitrosamine ±RSD(%, n=6) 2.5 µg/l 66.9±2.5 50 µg/l 72.9±3.0 100 µg/l 82.2±4.1 2 µg/kg 74.3±7.7 10 µg/kg 87.5±3.6 50 µg/kg 103.4±2.6 0.45 µg/l 1.5 µg/l 0.60 µg/kg 2.0 µg/kg, [11] 72 N-, N,N- 83.9%, 7 μg/kg [12] 20 N,N- (NDMA) 47.78 μg/kg, 60%~70%, N,N-,,,, 4 结 论 N,N- -,, N,N- N,N-,,, [9], N,N- 参 考 文 献 [1],,,. [J]., 2005, 34: 350 352. Lin K, Yu SJ, Zhang JJ, et al. Study on N-nitroso compound in food and its relevant risk factors for esophageal cancer [J]. J Hyg Res, 2005, 34: 350 352. [2],. N- [J]., 2011, 32: 60 62. Sun WQ, Ma LZ. The online detection of N-nitrosamine of preserved ham [J]. Food Res Devel, 2011, 32: 60 62. [3],,,. GC-MS N- [J]., 2012, 08(4): 16 22. Wu YY, Liu FJ, Li LH, et al. Determination of optimization of N-nitrosamines in salted fish by gas chromatography-mass spectrometry [J]. South China Fish Sci, 2012, 8(4): 16 22. [4],,,. SDE-GC N- [J]., 2004, 23: 54 56. Zhang TZ, Tao YF, Huang HL, et al. Determination of N-nitrosamines in beer samples by single drop-extraction gas chromatography [J]. Chin J Anal Lab, 2004, 23: 54 56. [5],,. GC-LRMS 3 N- [J]., 2011, 30: 84 87. Zhao YX, Wang X, Hu YM. Determination of three nitrosamines in beer by GC-LRMS [J]. Chin J Anal Lab, 2011, 30: 84 87. [6],,,. - / N- [J]., 2014, 32(4): 433 437. Peng QR, Tang T, Yu SX, et al. Determination of N-nitrosodimethylamine in beer by frozen zone melting liquid-liquid extraction/gas chromatography [J]. Chin J Chromatogr, 2014, 32(4): 433 437. [7],,. N- SPME-GC-MS [J]., 2003, 22: 82 84. Tao YF, Huang HL, Zhang TZ. Determination of volatile N-nitrosocompounds in beer by SPME-GC-MS [J]. J Instrum Anal, 2003, 22: 82 84. [8] GB/T 5009.26-2003 N- [S]. GB/T 5009.26-2003 Method for determination of N-nitrosamines in foods [S]. [9]. N- [J]., 2006, 15(4): 18 23.
3838 6 Weng QX. Determination of the content of N-dimethyl nitrosamine by gas chromatography-mass spectrometry [J]. Fujian Anal Test, 2006, 15(4): 18 23. [10],,. GC-MS N- [J]., 2014, 8: 43 46. Feng XJ, Gong H, Zhang XL. Determination of N-dimethylnitrosamine in various food by GC-MS method [J]. Sino-foreign Food Ind, 2001, 28: 27 28. [11],,. N- [J]., 2001, 28: 27 28. Duan FM, Chen KL, Luo HD. Study on the content of N-nitroso compound in beer, soy sauce and sausage [J]. Mod Prev Med, 2001, 28: 27 28. [12],,,. [J]., 2003, 9: 88 90. Li YM, Chen LR, Xue QJ, et al. Determination and analysis of N-nitroso-compounds of pickles in Wuwei city of Gansu province [J]. Anal Test Technol Instrum, 2003, 9: 88 90. 作 者 简 介 ( 责 任 编 辑 : 杨 翠 娜 ) 刘 印 平, 硕 士, 中 级 技 师, 主 要 研 究 方 向 为 食 品 安 全 检 测 E-mail: liuyinping0930@163.com 杨 立 新, 博 士, 中 级 技 师, 主 要 研 究 方 向 为 食 品 安 全 检 测 E-mail: yanglixin241@163.com