6 3 Vol. 6 No. 3 2015 3 Journal of Food Safety and Quality Mar., 2015 - 吴益春 1,2, 祝世军 1,2, 罗海军 1,2, 陈璐 1,2, 鲁华郭海波 1,2, 杨会成 3 1*, 郝云彬 (1., 316000; 2., 316000; 3., 3160) 1,2, 摘要 : 目的 - 方法, + (:, v:v) 结果 GBW(E)0131,, 93.7%~4.4%, 2.75%~4.65%, 0.22~0.44 µg/kg 结论,, 关键词 : ; ; ; Determination of indicator polychlorinated biphenyls residues in the flesh of fish by gas chromatography using acid digestion WU Yi-Chun 1,2, ZHU Shi-Jun 1,2, LUO Hai-Jun 1,2, CHEN Lu 1,2, LU Hua 1,2, GUO Hai-Bo 1,2, YANG Hui-Cheng 3, HAO Yun-Bin 1* (1. Zhoushan Fisheries Test Center, Zhoushan 316000, China; 2. Zhoushan Institute for Food and Drug Control, Zhoushan 316000, China; 3. Zhejiang Marine Development Research Institute, Zhoushan 3160, China) ABSTRACT: Objective To establish a method to detect the residual indicator polychlorinated biphenyls (PCBs) in the flesh of fish by gas chromatography using acid digestion. Methods The sample was digested by H 2 SO 4, then extracted by N-hexane and methylene chloride (:, v:v) and cleaned up by H 2 SO 4, after that determined by capillary gas chromatography. Results PCBs reference material GBW(E)0131 in Cod was detected by this method and the result was in accordance with the assigned value. The recovery was 93.7%~4.4%, RSD was 2.75%~4.65% (n=6), and the detection limit was 0.22~0.44 µg/kg. Conclusion The method is simple, rapid, sensitive, accurate and precise, and it can be used for the determination of indicator polychlorinated biphenyls in the flesh of fish. KEY WORDS: flesh of fish; polychlorinated biphenyls; acid digestion; gas chromatography 基金项目 : (2012BAD29B06) Fund: Supported by National Support Program for Science and Technology (2012BAD29B06) * 通讯作者 :,, E-mail: yunbinhao@163.com *Corresponding author: HAO Yun-Bin, Senior Engineer, Zhoushan Fisheries Test Center, Zhoushan, No.55, Jinsha Road, Putuo District, Zhoushan 316111, China. E-mail: yunbinhao@163.com
924 6 1 引言 (polychlorinated biphenyls, PCBs),, PCBs,,,,, [1-5], PCBs [6-13] PCBs,, PCBs, [6] [6] [7] [8] [9,] [11,12] R134a [13] GB09.190-2014 [6], ( 18~24 h),,, ; R134a,, R134a,,,,,, PCBs [14],,, ( PCB28 PCB52 PCB1 PCB118 PCB153 PCB138 PCB180) 2 材料与方法 2.1 试剂与仪器 (, Fisher Scientific ); (, ); (, ); (, Fisher Scientific ); (, ):,, 225 ; (, ): 660 6 h PCBs (7, 28, 52, 1, 118, 138, 153, 180), o2si ; (GBW(E)0131, ) Agilent 7890A, ( ); (RV, IKA ); (CT14D, ); (IP40, IKA ) 2.2 样品前处理 5 g ( 0.01 g) ml, 12 ml %, 80 1 h, ml + (:, v:v), 2 min, 5 min,, ml, 40 15 ml, ml, ml, 1 min, 7000 r/min 1 min,,, ( 2.5 g 2 g, 15 ml ), 0 ml, 30 ml, 25 ml + (5:95, v:v), 40 1 ml, 2.3 色谱条件 : HP-5MS(Crolinked 5% Pheny1 Methy1 Siloxane, 30 m 0.32 mm, 0.25 µm) : 290 ;, : 300 ; : 90 0.5 min, 15 /min 200, 5 min; 3 /min 2, 2 min; : 60 ml/min 2.4 计算公式与数据处理, :
3, : - 925 = PCBs / PCBs 0% SPSS 13.0,, P<0.05 3 结果与分析 3.1 酸消化时间的选择 %, 5, 1 %, 0.5 h, 42.4%~65.0%, 1.0 h, 93.7%~4.4%,,, % 1.0 h,,,, 表 1 不同消化时间对提取率的影响 (n=5) Table 1 Effect of different incubation time on extraction efficiency(n=5) (%) 0.5 h 1 h 2 h 3 h PCB28 42.4±3.69 94.5±4.19 96.3±3.74 2.8±4.05 PCB52 52.5±4.66 97.1±2.98 95.5±4.82 97.3±5.75 PCB1 65.0±4.23 93.7±3.98 3.6±4.17 99.5±3.82 PCB118 59.7±3.41 96.3±3.74 97.3±4.42 95.6±2.16 PCB153 62.4±3.23 95.5±4.82 4.2±4.84 97.7±3.78 PCB138 52.4±4.33 94.2±2.92 95.5±3.02 95.2±3.52 PCB180 48.5±3.53 4.4±3.78 94.2±2.35 98.2±3.59 3.2 萃取用试剂的选择, [2], 2, + (:, v:v), (P<0.05), + (:, v:v) Table 2 表 2 不同萃取试剂对提取率的影响 Effect of different incubation time on extraction efficiency (%) + (:, v:v) + (:, v:v) PCB28 72.6±4.68 67.2±3.52 73.4±2.65 94.5±4.19 PCB52 51.5±5.62 75.2±4.56 72.9±3.78 97.1±2.98 PCB1 62.0±6.21 72.5±4.59 73.6±3.42 93.7±3.98 PCB118 59.7±4.21 67.1±3.49 72.3±4.42 96.3±3.74 PCB153 69.2±3.85 73.6±4.52 72.5±4.84 95.5±4.82 PCB138 72.7±5.93 72.6±4.58 79.5±3.02 94.2±2.92 PCB180 68.5±7.52 73.5±4.47 63.2±2.25 4.4±3.78 3.3 色谱柱的选择, : HP-35 PCB123 PCB118,, HP-5MS, [15] 7 1 Fig. 1 1 7 (80 ng/ml) Chromatogram of 7 kinds of PCBs in samples (80 ng/ml)
926 6 3.4 线性回归方程 检出限与定量限 7 5 20 40 60 80 0 200 ng/ml,,, 3, 0.9990, 0.22~0.44 µg/kg, 0.5 µg/kg 3.5 回收率和精密度试验 0 µg/kg 7,,, 93.7%~4.4%, (RSD, n=6) 2.75%~4.65%, 4 表 3 7 种 PCBs 的线性关系及其检出限 Table 3 Regression equations and detecting limits of 7 kinds of PCBs PCB (min) R (µg/kg) PCB28 9.355 Y=25.33116X+70.38427 0.99939 0.22 PCB52.9 Y=15.64134X+65.54265 0.99932 0.33 PCB1 12.860 Y=26.16222X+122.20060 0.99916 0.38 PCB118 15.587 Y=37.36629X+145.42618 0.99920 0.30 PCB153 16.664 Y=35.16537X+152.49641 0.99922 0.41 PCB138 17.980 Y=45.25879X+169.78957 0.99930 0.23 PCB180 21.437 Y=55.82786X+144.67499 0.99959 0.44 表 4 鲳鱼样品中添加多氯联苯回收率和精密度 (n=6) Table 4 Recoveries and relative standard deviations (RSDs) of PCBs adding in Pomfret (n=6) /(µg/kg) /% RSD/% PCB28 PCB52 PCB1 PCB118 PCB153 PCB138 PCB180 0.5 3.31 98.7 3.41 0 97.6 4.12 4.4 3.35 99.0 3.21 0 97.9 4.40 94.9 4.01 96.1 4.02 0 95.2 4.11 98.7 2.87 99.8 2.75 0 98.6 3.24 95.3 4.03 98.8 3.62 0 1.8 4.03 93.7 4.26 98.9 4.65 0 99.2 4.31 98.7 3.54 0.6 4.19 0 99.5 4.26
3, : - 927, 7 3.6 样品检测结果 ( ) ( : GBW(E)0131), 3,, 5 5,, RSD 5% 表 5 标准物质中多氯联苯检测结果 (n=3) Table 5 The PCBs content in sample(n=3) (ng/g) (ng/g) (%) ( ) (ng/g) (%) PCB28 77.9±4.5 78.3 4.36% 77.0 3.26 PCB52 42.9±3.7 44.3 3.26% 41.8 4.15 PCB1 40.5±3.5 41.8 3.21% 39.5 3.89 PCB118 44.1±3.3 45.3 2.72% 43.5 2.56 PCB153 42.7±2.9 41.5 2.81% 43.6 3.66 PCB138 41.8±3.4 40.2 3.83% 40.9 3.77 PCB180 25.5±2.7 25.0 1.96% 25.8 2.13 4 结论, ( ), [3] 18~24 h, 3~4 h,, 0~200 µg/l,, 0.9990, 93.7%~4.4%, RSD 5%,, 参考文献 [1] Maria Maddalena Storelli, Grazia Barone, Veronica Giuliana Perrone, et al. Polychlorinated biphenyls(pcbs), dioxins and furans(pcdd/fs): Occurrence in fishery products and dietary intake [J]. Food Chem, 2011, 127(4): 1648 1652. [2] Gemma Perelló, Roser Martí-Cid, Victoria Castell, et al. Influence of various cooking processes on the concentrations of PCDD/PCDFs, PCBs and PCDEs in foods [J]. Food Control, 20, 21(2): 178 185. [3] Ottonello G, Ferrari A, Magi E. Determination of polychlorinated biphenyls in fish: optimisation and validation of a method based on accelerated solvent extraction and gas chromatography-mass spectrometry [J]. Food Chem, 2014, 1(142): 327 333. [4] Bocio A, Domingo JL, Falcó G, et al. Concentrations of PCDD/PCDFs and PCBs in fish and seafood from the Catalan (Spain) market: estimated human intake [J]. Environ Inter, 2007, 33(2): 170 175. [5],. [J]., 2004, 16(6): 540 545. Li JG, Wu YN. Progress in press in pretreatment for determination of polychlorinated biphenyls from food matrices [J]. Chin J Food Hyg, 2004, 16(6): 540 545. [6] GB 09.190-2014 [S]. GB 09.190-2014 National food safety standards determination of indicator polychlorinated biphenyls in foods [S]. [7],,,. - 7 [J]., 2011, 45(6): 22 25. Ma LS, ZHU XP, Zheng GM, et al. Determination of seven kinds of polychlorinated biphenyls in aquatic products by matrix solid-phase dispersion and gas chromatography [J]. Chin J Vet Drug, 2011, 45(6): 22 25. [8],,,. [J]., 2014, 42(14): 134 136. Sun XM, Hu HM, Zhong Z, et al. Determination of polychlorinated biphenyls and organochlorinated pesticides in mussel by gas chromatography [J]. Guangzhou Chem Ind, 2014, 42(14): 134 136. [9],,,. - [J]., 2013, 32(1): 156 161. Wu JH, Li A, Liu GY, et al. Determinaiton of polychlorinated biphenyls and organochlorine pesticide residues in wakame by gas chromatography with electron capture detection using microwave-assisted extraction [J]. Environ Chem, 2013, 32(1): 156 161. [] Xiong GH, He XQ, Zhang ZX. Microwave-assisted extraction or saponification combined with microwave-assisted decomposition applied in pretreatment of soil or mussel sample for the
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