7 9 Vol. 7 No. 9 2016 9 Journal of Food Safety and Quality Sep., 2016-4 1, 魏茂琼 2 1,, 刘宏程 2*, 严红梅 2, 和立忠 2, 王丽 2, 林昕 (1. ( ), 650223; 2., 650223) 1, 2 摘要 : 目的 0.3 mol/l 4 ( As III As V MMA DMA) - (liquid chromatography-atomic fluorescence spectrometry, LC-AFS) 方法 60, 40 min, LC-AFS 2 4, 结果 4 0.002~0.01 μg/ml, 89.03%~100.70%, RSD 4.36%(n=5) 结论 1 h,, 关键词 : ; ; ; - ; Determination of 4 kinds of arsenic species in rice by liquid chromatographyatomic fluorescence spectrometry WEI Mao-Qiong 1, 2, LIU Hong-Cheng 1, 2*, YAN Hong-Mei 2, HE Li-Zhong 2, WANG Li 2, LIN Xin 1, 2 (1. Laboratory of Quality & Safety Risk Assessment for Agro-Product, Ministry of Agriculture (Kunming), Kunming 650223, China; 2. Agri-Food Quality Standard & Testing Technology Institute, Yunnan Academy of Agricultural Sciences, Kunming 650223, China) ABSTRACT: Objective Using 0.3 mol/l nitric acid as the extractant, to establish a method for the simultaneous determination of arsenious acid (As III), arsenic acid (As V), dimethylarsinic acid (DMA) and monomethylarsinic acid (MMA) in rice by liquid chromatography-atomic fluorescence spectrometry (LC-AFS). Methods After ultrasonic extraction 40 min at 60, the sample was detected by LC-AFS. The extraction efficiency of two kinds of extracted methods was compared. The concentration of nitric acid, extraction temperature and extraction time were optimized. Results The detection limits of 4 kinds of main arsenic species ( As III, As V, DMA, MMA ) in rice were 0.002~0.01 μg/ml, the recoveries were in the range of 89.03%~100.70%, and the relative standard deviations (RSDs) were less than 4.36%(n=5). Conclusion This method can completely separate the 4 kinds of arsenic species in rice samples within 1 h, which is simple, accurate for the risk assessment of heavy metal arsenic in rice. KEY WORDS: rice; arsenic species; ultrasonic extraction; liquid chromatography-atomic fluorescence spectrometry; nitric acid 基金项目 : (2015HC025) ( )(2014DA001) Fund: Supported by the Innovative Team of Yunnan Province (2015HC025) and the Science and Technology Innovation Platform Construction Plan (Public Service of Science and Technology) (2014DA001) * 通讯作者 :,, E-mail: liuorg@163.com *Corresponding author: LIU Hong-Cheng, Researcher, Laboratory of Quality and Safety Risk Assessment for Agro-products (Kunming), Ministry of Agriculture, Institute of Quality Standards and Testing Technology, Yunnan Academy of Agricultural Sciences, NO.9 Xueyun Road, Kunming 650223, China. E-mail: liuorg@163.com
3674 7 1 引言, : (arsenite, As III) (arsenate, As V) (dimethyl arsenic acid, DMA) (monomethyl arsenic acid, MMA) [1] LD 50,, (MMA) (DMA) (AsC), (AsB) [2,3] As V AsC AsB, AsB [4],, [5,6],,,, MMA DMA, [7,8],, [9] - [10] : [11,12] [13] Melgar [14] 晞 [15] - (liquid chromatographyatomic fluorescence spectrometry, LC-AFS), 0.3 mol/l, 4, 2.2.2 样品前处理,, 80, 0.5 g( 0.001 g), 10 ml, 5 ml 0.3 mol/l,, 60 40 min, 8000 r/min 20 min, 0.22 μm, 2.2.3 液相色谱条件及 LC-AFS 条件 -, ph 5.92, (0.45 μm), ; : 1 ml/min; : 50 r/min, : 100 ma; 330 V, 200, 8 mm, 400 ml/min, 800 ml/min 3 结果与分析 3.1 前处理条件的优化 3.1.1 提取方法的选择 0.3 mol/l, 60 18 h 60 40 min 1, 18 h As III As V MMA 3, 54.70% 13.26% 85.70%, DMA 13.70%, 2 材料与方法 2.1 仪器与试剂 - ( ) ( ), (1.011±0.016) mol/g (0.233±0.005) mol/g (0.335±0.011) mol/g (0.706±0.024) mol/g;, ( ), : 2.2 试验方法 2.2.1 溶液配制, 0 5 10 20 40 80 100 ng/ml ( As ), LC-AFS,, 1 4 (n 3) Fig. 1 Extraction amounts of the 4 kinds of arsenics species by 2 kinds of extraction methods (n=3) 3.1.2 提取剂浓度的选择 (0 0.15 0.3 0.5 0.8 mol/l) (0 20 40 60 100 min), 60 40 min, (0~0.8 mol/l), 2 DMA As III
9, : - 4 3675 As V MMA, 0.3 mol/l, 3 0.15 mol/l, 3,, 3, 0.5 mol/l, 3 0.5 mol/l, As-III As-V, 0.3 mol/l 0.52% 0.56%, 0.3 mol/l Fig.3 3 4 (n 3) Extraction amounts of the 4 kinds of arsenic species with different extraction time(n=3) 3.2 线性范围及检出限 2 4 (n=3) Fig. 2 Extraction amounts of the 4 kinds of arsenics species with different concentrations of nitric acid(n=3) 3.1.3 提取时间的选择 3.1.2, 60 0.3 mol/l,, 3 HNO 3,, >40 min,,,, 40 min, 0.3 mol/l 4, 5 10 20 30 50 80 ng/ml, 2.2, 4, 4 7 min, X, (Y), 1 0~0.1 μg/ml, 4, 0.998, (S/N=3), 0.002~0.01 μg/ml 3.3 方法准确度与精密度 20 μg/kg 4, 2.2.2, 4, 2 : 89.03%~100.70%, RSD 1.30%~4.36% Table 1 表 1 线性范围及检出限 Linear range and detection limit /min (μg/ml) (r) (μg/ml) As III 2.6900 0~0.100 Y=-1.674*10 5 +1.474*105 X 0.999526 0.002 DMA 3.1567 0~0.100 Y=-5.03*10 5 +9.961*104 X 0.998405 0.004 MMA 3.7567 0~0.100 Y=-5.962*10 5 +1.882*105 X 0.999447 0.004 As V 5.4717 0~0.100 Y=-3.543*10 5 +7.32*104 X 0.999136 0.010
3676 7, 表 2 方法精密度结果 (n=6) Table 2 Precision test (n=6) (μg/kg) (μg/kg) (%) RSD(%) Fig. 4 4 4 Separation chromatogram of 4 kinds of mixed standards of arsenic species As III 15.65 20 96.60 1.65 DMA 5.97 20 98.01 3.43 MMA 3.57 20 89.03 4.36 As V 6.87 20 100.70 1.30 3.4 样品测定 4, 3, 14, As III 0.82~36.34 μg/kg, As V 0~81.29 μg/kg, DMA MMA, 0~10.77 μg/kg 0~9.58 μg/kg (As III As V ) (200 μg/kg),, 4 结论 0.3 mol/l, 60 40 min 4 :,, 1 h,, Table 3 表 3 大米样品中 4 种砷形态的测定结果 (μg/kg) Results of the 4 kinds of arsenic species in rice samples (μg/kg) As III DMA MMA As V 1 3.31 1.56 0.40 81.29 84.60 2 2.53 2.12 0 0 33.47 3 14.54 10.77 9.58 5.63 20.17 4 6.07 4.84 5.41 0 6.07 5 21.39 0.96 2.15 32.17 53.56 6 1.50 3.85 1.78 41.58 43.09 7 11.82 0 0 0.71 12.53 8 2.18 0 1.53 61.26 63.44 9 1.05 0 2.28 4.79 5.84 10 9.23 5.33 0 38.33 47.56 11 1.50 0 0.92 49.12 50.63 12 1.84 5.24 0 2.58 4.43 13 0.82 0.21 2.90 52.13 52.95 14 36.34 2.76 2.65 72.54 108.88
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