8 5 Vol. 8 No. 5 2017 5 Journal of Food Safety and Quality May., 2017 - 韩晓鸥 *, 平小红, 张媛媛 (, 110005) 摘要 : 目的 - As( Ⅲ) ; 方法 20 ml 0.15 mol/l HNO 3, 90 3.0 h, 2, @RISK6.2 结果 As( Ⅲ) 7.6%, As( Ⅴ) 3.1% 结论, 关键词 : ; ; ; ; Determination of inorganic arsenic content in seafood by liquid chromatography-atomic fluorescence spectrometry and its risk assessment HAN Xiao-Ou *, PING Xiao-Hong, ZHANG Yuan-Yuan (Liaoning Provincial Center for Disease Control and Prevention, Shenyang 110005, China) ABSTRACT: Objective To establish a method for determination of 2 kinds of inorganic arsenic including arsenite As (Ⅲ) and arsenate As (Ⅴ) in seafood by liquid chromatography-atomic fluorescence spectrometry (LC-AFS), and to establish a mathematical model to infer the probability of inorganic arsenic positive samples in the markets. Methods Samples were soaked in 20 ml 0.15 mol/l HNO 3 solutions over night, and were heat extracted in a thermostat at 90 for 3 h. After being cooled, the extract was introduced for LC-AFS analysis. The mathematical model was established by using the risk assessment software @RISK6.2. Results The prevalence rate of arsenite As (Ⅲ) was 7.6% and the prevalence rate of arsenate As (Ⅴ) was 3.1%. Conclusion The established model can infer the probability of inorganic arsenic positive samples in seafood and water samples in large supermarkets and small markets, which can provide technical support for the risk management of seafood. KEY WORDS: liquid chromatography; atomic fluorescence spectrometry; seafood; inorganic arsenic; risk assessment * 通讯作者 :,,,. E-mail: 147000840@qq.com *Corresponding author: HAN Xiao-Ou, Engineer, Liaoning Provincial Center for Disease Control and Prevention, Shenyang 110005, China. E-mail: 147000840@qq.com
5, : - 1927 1 引言, Omega-3(ω-3) [1],,, [2],,,,,, [3-5] (As),, [As(Ⅲ) As( Ⅴ )], (monomethylarsine, MMA) (dimethylarsine DMA), GB 2762-2012 [6], 0.1 mg/kg, 0.5 mg/kg, [As(Ⅲ) As( Ⅴ )], GB 5009.11-2014 [7], - (liquid chromatography-atomic fluorescence spectrometry, LC-AFS) -(liquid chromatography-inductively coupled plasma mass spectrometry, LC-ICP/MS), LC-ICP/MS, [8-14] LC-AFS, 100, @RISK6.2,, [15] 2 材料和方法 2.1 材料与试剂 200, 30, 30, 70, 70, (, ) (, 96%, ); (, 85%, ); (, 65%~68%, ); (, 36%~38%, ); (, 99.9%, ); As(Ⅲ)(GBW 08667, ); As(Ⅴ)(GBW08666, ) 2.2 仪器与设备 e2695 ( ); AFS-9730 (); KQ5200DB ( ); Milli-Q ( Millipore ); ( ); LAB DANCER S25 ( ); BS110S ( ); S25 ( ); (1000 200 ml, Eppendorf ); ( ) 2.3 试验方法 2.3.1 标准溶液的配制 As(Ⅲ): 124.3 μg/g 20 μl, 1.5 ml, 1000 ng/ml As(Ⅴ): 32.4 μg/g 86 μl, 1.5 ml, 1000 ng/ml 2.3.2 仪器条件 : :, Hamilton PRP X-100(250 mm 4.1 mm,10 μm); 30 ; : 5 mmol/l, 45 mmol/l, ph 5.92; 100 μl : 75 ma, 300 V, 400 ml/min, 800 ml/min, 8 mm 2.3.3 线性范围和检出限 : As( Ⅲ) As( Ⅴ)2 20 40 80 100 μl 2.0 ml, 10.0 20.0 30.0 40.0 50.0 ng/ml, 100 μl (Y), (X), 1.000 g, 11, 3 2.3.4 样品前处理, 1.000 g( 0.001 g), 50 ml, 20 ml 0.15 mol/l HNO 3, 90 3.0 h, 0.5 h 1 min,, 10000 r/min 15 min, 5 ml, 5 ml, 1 min, 10000 r/min 15 min, 1,, 0.45 μm 2.3.5 回收率和精密度,, 1000 μg/l 0.4 0.8 1.2 ml, 24 h, 2.3.3
1928 8, 6, 2.3.6 数学模型, @RISK6.2, 2 3 结果与分析 3.1 线性范围和检出限 1 : 2 1.8, 2 ( 1) 2, 1.000 g, As( Ⅲ ) 0.015 mg/kg, 0.040 mg/kg, As( Ⅴ) 0.030 mg/kg, 0.080 mg/kg 3.2 提取条件的选择 3.2.1 提取溶剂 (10 20 30 40 50 ml) As( Ⅲ) As( Ⅴ)2, 2 2, 20 30 40 50 ml, As( Ⅲ),,,, 20 ml 3.2.2 提取温度和时间 70 80 90 105 As( Ⅲ) 2,, 90, 90 1 2 3 4 h As( Ⅲ) As( Ⅴ),, 3 h, 3 h 3.3 方法回收率和精密度 2 2, As( Ⅲ) 91.3% 97.5%, (relative standard deviation, RSD) 0.6% 2.8%,, Fig. 1 1 2 Chromatogram of standard mixture of 2 kinds of inorganic arsenic Table 1 表 1 线性回归方程和相关系数 Regression equations and correlation coefficients (ng/ml) (mg/kg) (mg/kg) As( Ⅲ ) 0 50 Y=0.04X+5.379e 0.9994 0.015 0.040 As( Ⅴ ) 0 50 Y=0.04X+3.59e 0.9991 0.030 0.080
5, : - 1929 As( Ⅲ), RiskTriang (0.06, 0.07, 0.1) 3 Table 3 表 3 样品检测结果 Analytical results of samples ( ) 30 30 70 70 200 As( Ⅲ) (%) 6.7% 10.0% 5.7% 8.6% 7.5% Fig. 2 As( Ⅲ ) As( Ⅴ ) Table 2 2 Effects of extraction solvent volumes on recoveries 表 2 回收率与精密度 (n=6) Results of precision and recovery (n=6) (ng/ml) 3.4 暴露评估模型建立 (ng/ml) (%) (%) 20 19.5 97.5 1.8 40 37.6 94.0 1.9 60 57.8 96.3 1.5 20 18.6 93.0 2.8 40 36.5 91.3 1.3 60 57.8 96.3 0.6 200, 3 As( Ⅲ), (0.5 mg/kg) As( Ⅲ) As( Ⅴ), 3.4.1 亚砷酸盐 As( Ⅲ ) 阳性样品流行率模型 3, As( Ⅴ) (%) 3.3% 3.3% 2.9% 2.9% 4.0%, As( Ⅲ) 6.472%~9.206%, As( Ⅲ) 7.6%, As( Ⅲ) 7.6% 3.4.2 超级市场水产品和水产制品中 As( Ⅲ ) 阳性样品预测模型 50, As( Ⅲ) 7.6%, 50 As( Ⅲ) RiskBinomial(50,0.076) 4 As( Ⅲ) 1 3.8% 3.4.3 中小市场水产品和水产制品中 As( Ⅲ ) 阳性样品预测模型 30, 7.6%, 30 As( Ⅲ) RiskBinomial(30,0.076) Fig. 3 3 As( Ⅲ) The prevalence rate of arsenite As(Ⅲ) in Liaoning
1930 8 4 As( Ⅲ) Fig. 4 The inferior quality of sea food of arsenite As(Ⅲ) in supermarkets Fig. 5 5 As( Ⅲ) The inferior quality of sea food of arsenite As(Ⅲ) in medium and small markets 5 As( Ⅲ) 1 2.28% 3.4.4 水产品和水产制品中 As( Ⅴ ) 阳性样品流行率模型 3, As( Ⅴ), RiskTriang (0.029, 0.031, 0.033) 6, As( Ⅴ) 2.9597%~3.2331%, As( Ⅴ) 3.1%, As( Ⅲ) 3.1% 3.4.5 大型超级市场水产品和水产制品中 As( Ⅴ ) 阳性样品预测模型 50, As( Ⅴ) 3.1%, 50 As( Ⅴ) RiskBinomial (50,0.031) 7 As( Ⅴ) 1 1.6% 3.4.6 中小市场水产品和水产制品 As( Ⅴ ) 阳性样品预测模型 30, 3.1%, 30 RiskBinomial(30,0.031) 8 As( Ⅲ) 1 0.93%
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