8 1 Vol. 8 No. 1 2017 1 Journal of Food Safety and Quality Jan., 2017 - 樊祥 *, 张润何, 刘博, 王敏, 邓晓军, 何宇平 (, 200135) 摘要 : 目的 - (high efficiency liquid chromatography-atomic fluorescence spectroscopy, HPLC-AFS), - (high efficiency liquid chromatography-inductively coupled plasma-mass spectrometry, HPLC-ICP-MS) 方法 5 mol/l HCl, 6 mol/l NaOH, L-, 结果 1.0~20.0 μg/l, : 0.009 mg/kg 0.006 mg/kg 0.009 mg/kg; 81.0%~117.0%, 3.59%~7.30% FAPAS T07231QC, 结论, 关键词 : - ; - ; ; ; ; Determination the content of mercury in different speciations in aquatic products by high performance liquid chromatography-atomic fluorescence spectrometry FAN Xiang *, ZHANG Run-He, LIU Bo, WANG Min, DENG Xiao-Jun, HE Yu-Ping (Animals, Plants and Food Inspection & Quarantine Technical Center of Shanghai Entry-Exit Inspection and Quarantine Bureau, Shanghai 200135, China) ABSTRACT: Objective To establish A method for to determination the content of mercury in different speciations in aquatic products by high performance liquid chromatography-atomic fluorescence spectrometry and to confirm this method by high performance liquid chromatography coupled with inductively coupled plasma mass spectrometry. Methods The mercury element in samples were extracted by 5 mol/l HCl solution, 6 mol/l NaOH solution was used to neutralize the sample, and L-cysteine was used as mercury complexing agent in mobile phase. Results The mercury compounds showed a good linear relationship between concentration and peak area in the range of 1.0~20.0 g/l. The detection limits of quantification of inorganic mercury, methylmercury and ethylmercury were 0.009 mg/kg, 0.006 mg/kg and 0.009 mg/kg, respectively. Recoveries and relative standard deviations were 81.0%~117.0% and 基金项目 : (15395810100) Fund: Supported by Science and Technology Joint Project of the Yangtze River Delta (15395810100) * 通讯作者 :,, E-mail: fanx@shciq.gov.cn *Corresponding author: FAN Xiang, Senior Engineer, Shanghai Entry-Exit Inspection and Quarantine Bureau, No 1208, Minsheng Road, Shanghai 200135, China. E-mail: fanx@shciq.gov.cn
1, : - 77 3.59%~7.30%, respectively. The method was used to determine the methyl mercury in canned of FAPAS T07231QC sample, and the measured results were in good agreement with the reference values. Conclusion This method is simple, sensitive and reproducible, and it can be used for the determination of mercury in aquatic products. KEY WORDS: high efficiency liquid chromatography-atomic fluorescence spectroscopy; high efficiency liquid chromatography-inductively coupled plasma-mass spectrometry; inorganic mercury; methylmercury; ethyl mercury; aquatic products 1 引言,,, 5000,, ( ) (CH 3 )Hg +,,,,,,,,,, [1] [2] [3] [4] [5] [6] [7],,,,, (gas chromatography, GC) [8,9] (high efficiency liquid chromatography, HPLC)(atomic fluorescence spectroscopy, AFS) [10-12] (inductively coupled plasma-mass spectrometry, ICP-MS) [13], HPLC-AFS,,, GB 5009.17-2014 [14] 2007, EPA1630 [15] -, /, HPLC-ICP/MS, 5 mol/l HCl 6 mol/l NaOH L-,,, HPLC-ICP/MS 2 材料与方法 2.1 仪器与试剂 Agilent 1260 ( Agilent ), ; AFS-9760, FUV-320 ( ); Aglient 8800 ICP-MS (ICP-QQQ)( Agilent ); ( ) : (1.0 g/l) (76.6 μg/g) (75.3 μg/g)() : (food analysis performance assessment scheme, FAPAS) (T07231QC); 2.2 实验方法,,, 0.2~0.5 g ( 0.001 g), 0.5~1.0 g ( 0.001 g), 15 ml, 10 ml 5 mol/l HCl, 3 min, ; 60 min, ; 4 8000 r/min 10 min; 2 ml 15 ml, 1.5 ml 6 mol/l NaOH, 0.2 ml 10 g/l, 5.0 ml, 4 8000 r/min 15 min; 0.45 µm, HPLC-AFS, HPLC-ICP/MS, ( : 6 mol/l NaOH,,,, )
78 8 2.3 仪器条件 (1) Eclipse Plus C 18 (150 mm 4.6 mm, 5 µm); 5.0% (V:V)- (1 g/l)- (50 mmol/l); 1.0 ml/min; 100 µl (2) 300 V; 30 ma; : ; : 5% HCl (V:V), 40 r/min; : 20 g/l, 40 r/min; : 10 g/l, 40 r/min; : 300 ml/min; : 800 ml/min (3) : 1550 W; : 16 ml/min; : 1.0 ml/min; : 8.0 mm; : ; : 0.3 s; : (4) HPLC-AFS:, PEEK (Φ=0.13 mm),,,,,, HPLC-ICP/MS: PEEK (Φ=0.13 mm), 3 结果与分析 3.1 提取溶剂的选择,,, L-,,,,, 3.2 标准曲线和检出限 3, 1.0 2.0 5.0 10.0 20.0 μg/l,,,, (r) 0.999 3 3 (S/N=3), 1 Table 1 表 1 方法的线性关系和检出限 Linear relationship and detection limit of method (r) (mg/kg) Y=6.236923X-18.78 0.9997 0.006 Y=3.958974X-13.13 0.9994 0.009 Y=4.254214X-12.93 0.9992 0.009 3.3 加标回收率实验 1.0 g 0.125 0.250 0.500 mg/kg 3, 3 2 81.0%~117.0%, 89.0%~107.0%, 86.6%~109.0% (relative standard deviation, RSD) 5.47%~7.30%, 3.59%~5.32%, 4.47%~5.14%,,, Table 2 表 2 黄花鱼样品中 3 种汞化合物的加标回收率和测定相对标准偏差 (n=8) Recoveries and relative standard deviations (RSDs) of 3 mercury compounds in yellow croaker samples (n=8) (μg/l) (μg/l) (%) RSD (%) 5 10 4.45~5.55 9.12~10.50 89.0~101.0 91.2~105.0 5.32 3.59 20 19.40~21.40 97.0~107.0 4.81 5 10 4.33~5.25 9.07~10.50 86.6~105.0 90.7~105.0 4.78 5.14 20 18.20~21.80 91.0~109.0 4.47 5 10 4.05~5.85 9.40~10.80 81.0~117.0 94.0~108.0 7.30 5.60 20 18.80~19.80 94.0~99.0 5.47
1, : - 79 3.4 方法准确度确证 HPLC-AFS, 345 μg/kg,, ( 2 μg/l) 1, 2 GB 5009.17-2014 [14],, 360 μg/kg, HPLC-AFS FAPAS T07231QC, 402 μg/kg, HPLC-ICP/MS, 3, 4, 406 μg/kg,, HPLC-AFS 412 μg/kg, Fig. 1 1 HPLC-AFS (2 μg/l) Chromatogram of mixed standard solution of mercury compounds determined by HPLC-AFS (2 μg/l) Fig. 2 2 HPLC-AFS Chromatogram of methylmercury in tynny sample determined by HPLC-AFS Fig. 3 3 HPLC-ICP/MS (2 μg/l) Chromatogram of mixed standard solution of mercury compounds determined by HPLC-ICP/MS (2 μg/l)
80 8 Fig. 4 4 HPLC-ICP/MS FAPAS Chromatogram of methyl mercury in canned of FAPAS sample determined by HPLC-ICP/MS Table 3 表 3 样品中汞形态和总汞含量的测定结果 Determination results of mercury speciation and total mercury content in samples (μg/kg) (μg/kg) (μg/kg) 1(μg/kg) 2(μg/kg) (%) ND 2068 ND 2068 2122 97 174 869 ND 1043 1098 95 ND 345 ND 345 350 99 ND 132 ND 132 136 97 ND 89 ND 89 91 98 132 ND ND 132 157 84 ND 53 ND 53 61 87 ND 47 ND 47 53 89 ND 132 ND 132 161 82 ND 28 ND 28 30 93 ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND : ND 3.5 实际样品检测, 3 1, 2,,,,, GB 2762-2012 [16] : 1000 μg/kg,,,,, 4 结论 HPLC-AFS, HPLC-ICP/MS,, FAPAS T07231QC, HPLC-AFS HPLC-ICP/MS, 参考文献 [1],,,. - - [J]., 2010, 29(2): 64 68. Lv C, Liu LP, Dong HR, et al. Hydrochloric acid extract-mercury speciation analysis by high performance liquid chromatography coupled atomic fluorescence spectrometry [J]. Chin J Anal Lab, 2010, 29(2): 64 68. [2],,,. - [J]., 2006, 25(9): 49 52. Zhu XP, Wang MH, Ni SJ, et al. Determination of trace methyl-mercury in fish samples by solid-phase micro-extraction atomic fluorescence
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