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1 8 5 Vol. 8 No Journal of Food Safety and Quality May., , 李汉敏 2 1,, 陈岩 3* 1,, 耿安静 3 1, 2,, 王富华 3* 1,, 邹素敏 2, 刘帅 (1., ; 2., ; 3. (), ) 1, 2 摘要 : 目的 16, 方法, (inductively coupled plasma-mass spectrometry, ICP-MS) 2 16, 结果 0.012~0.062 μg/l, 94.6~107.7, 0.3~6.1, (GBW 08513), 2, (2.00~15.73 mg/kg) (0.05~0.14 mg/kg) 结论, 关键词 : ; ; ; Investigation and analysis of heavy metals and rare earth elements content in 2 kinds of Chinese holly leaf LI Han-Min 1,2, CHEN Yan 1,3*, GENG An-Jing 1,3, WANG Fu-Hua 1,2,3*, ZOU Su-Min 1,2, LIU Shuai 1,2 (1. Public Monitoring Center for Agro-product of Guangdong Academy of Agricultural Sciences, Guangzhou , China; 2. College of Resource and Environment, Huazhong Agricultural University, Wuhan , China; 3. Laboratory of Quality and Safety Risk Assessment for Agro-products (Guangzhou), Ministry of Agriculture, Guangzhou , China) ABSTRACT: Objective To investigate the content of chromium (Cr), cadmium (Cd), lead (Pb) and 16 kinds of rare earth elements in 2 kinds of Chinese holly leaf (Ilex Kudingcha C. J. Tseng. and Ilex lartifolia Thunb.), so as to reveal the ingestion risk of each element. Methods The samples were digested by microwave digestion system firstly, and then the content of Cr, Cd, Pb and 16 kinds of rare earth elements were detected by inductively coupled plasma-mass spectrometry (ICP-MS), and the results were compared with the national standards. Results The detection limits of the method were 0.012~0.062 μg/l. The spiked recoveries were in the range of 94.6~107.7, 基金项目 : (GJFP ) ( ) (2013B ) Fund: Supported by the Project of Risk Assessment of Ago-product Quality and Safety (GJFP ), the National Natural Science Foundation of China ( ) and Scientific and Technological Project of Guangdong Province (2013B ) * 通讯作者 :,,, gdaas_cyan@163.com,,, wfhwqs@163.com *Corresponding author: CHEN Yan, Research Assistant, Public Monitoring Center for Agro-product of Guangdong Academy of Agricultural Sciences, No. 29, Jinying Road, Tianhe District, Guangzhou , China. gdaas_cyan@163.com WANG Fu-Hua, Professor, Public Monitoring Center for Agro-product of Guangdong Academy of Agricultural Sciences, No. 29, Jinying Road, Tianhe District, Guangzhou , China @qq.com

2 and the relative standard deviations were 0.3~6.1. This method had been verified accurate by the reference material Tea (GBW 08513). Samples analysis demonstrated that the risk of Cr, Pb and rare earth elements was negligible in 2 kinds of Kudingcha. However, the content of Cd in Ilex Kudingcha C. J. Tseng. (2.00~15.73 mg/kg) was extremely higher than that in Ilex lartifolia Thunb. (0.05~0.14 mg/kg). Conclusion This method is suitable for the multi-element determination and risk assessment in tea. Risk monitoring data shows that Ilex Kudingcha C. J. Tseng exists the potential risk of excess intake of Cd. KEY WORDS: Chinese holly leaf; heavy metal; rare earth element; inductively coupled plasma-mass spectrometry 1 引言, 2000, [1,2], [3],,,, [4-6],,,, [7-9], (inductively coupled plasma-mass spectrometry, ICP-MS) [10],,,,,,, 16,, 2 材料与方法 2.1 材料与试剂 (GSB ) (GSB ) (GSB ) (GSB ) (GSB ), (GSB ) (GSB ) (GSB )( ); (10 mg/l, Agilent ); (GBW 08513)(); HNO 3 (MOS, Merck ); 30H 2 O 2 (, ); ( , ); ( 18.2 mω cm) 2,, 2.2 仪器与设备 7700x, MassHunter ( Agilent ); ETHOS One ( Milestone ); AL204 ( Mettler Toledo ); Milli-Q ( Millipore ) 20HNO 3 24 h 2.3 实验方法 样品前处理, 0.2 g, 4 ml HNO 3 1 ml 30H 2 O 2, 30 min,, ( 1),,, 140,,, 25 ml, 3,, 表 1 微波消解程序 Table 1 Microwave digestion procedures ( ) (min) (min) 质谱条件 ICP-MS,, ICP-MS ,,

3 5, : ~100 μg/l, 0~500 μg/l, 2 3 结果与分析 3.1 样品前处理优化 消解方式的选择, 2,,,, [11], [12] (GBW 08513), 2,, 6~8 h, 2 h,, 消解液及消解时间优化,, [13] HNO 3 HClO 4, 4:1(V:V) HClO 4,, [14], HNO 3, H 2 O 2 HClO 4, 4:1(V:V) Cr Cd Pb ( 1),, H 2 O 2 [15] H 2 O ICP-MS 仪器条件的优化 内标元素的选择 ICP-MS,,, [16],,, ( ) [14], 3 72 Ge 115 In 209 Bi, VIS, Table 2 表 x ICP-MS 仪器工作条件 Operating conditions of Agilent 7700 ICP-MS (W) (V) 0.0 (mm) (V) (L/min) 15 1 (V) (L/min) (V) 10.0 (L/min) 0.55 He (L/min) 3.8 Fig. 1 1 Comparison of microwave digestion with single or mixed acids

4 待测元素质量数的选择 ICP-MS,, [17] ICP-MS, 45 Sc 52 Cr 89 Y 114 Cd 139 La 140 Ce 141 Pr 146 Nd 147 Sm 153 Eu 157 Gd 159 Tb 163 Dy 165 Ho 166 Er 169 Tm 172 Yb 175 Lu 208 Pb 3.3 线性范围 回归方程及检出限, 11, 精密度与加标回收率 GBW 08513,,, 4, ~101.0, (relative standard deviation, RSD) 0.3~6.1, ~107.7, RSD 0.4~5.5, 3.5 样品检测结果分析 铬 镉 铅的测定 2,, ICP-MS 2 5 5, 0.72~0.83 mg/kg, 0.63~0.67 mg/kg GB 2762, 0.5 mg/kg [18],,, ( mg/kg) (0.06~0.08 mg/kg), GB 2762,,,, mg/kg [18], Table 3 表 3 铬 镉 铅和 16 种稀土元素的线性范围 回归方程及检出限 Linear ranges, regression equations and detection limits of Cr, Cd, Pb and 16 kinds of rare earth elements Cr 0~200 Y=0.0047X Eu 0~100 Y=0.0283X Cd 0~200 Y=0.0035X Gd 0~100 Y=0.0113X Pb 0~500 Y=0.0074X Tb 0~100 Y=0.0702X Sc 0~100 Y=0.0165X Dy 0~100 Y=0.0191X Y 0~100 Y=0.0196X Ho 0~100 Y=0.0820X La 0~100 Y=0.0276X Er 0~100 Y=0.0289X Ce 0~100 Y=0.0326X Tm 0~100 Y=0.0990X Pr 0~100 Y=0.0364X Yb 0~100 Y=0.0247X Nd 0~100 Y=0.0076X Lu 0~100 Y=0.0920X Sm 0~100 Y=0.0066X

5 5, : Table 4 表 4 精密度和准确度实验 (n=6) Precision and accuracy experiment(n=6) * * RSD * * RSD Cr 0.92± Cd 0.076± Pb 1.6± Sc Y 0.52± La 0.54± Ce 0.81± Pr* 93±8 99 Nd 0.35± Sm* 66± Eu* 22± Gd* 76± Tb* 11.4± Dy* 65± Ho* 13± Er* 37± Tm* 5.9± Yb* 38± Lu* 6.2± : * μg/kg Table 5 表 5 苦丁茶中铬 镉 铅和稀土元素含量 Contents of Cr, Cd, Pb and rare earths in Kudingcha (n) Cr Cd Pb REO * ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ * REO:,

6 稀土的测定,, [19], ~0.62 mg/kg, 0.18~0.34 mg/kg, GB mg/kg,,,, 4 结论, ICP-MS 16,, 参考文献 [1] Li WH, Zhou HP, Li N, et al. Chromium level and intake from Chinese made tea [J]. Food Addit Contam B, 2013, 6(4): [2],,,. [J]., 2014, 35(9): Cai J, Huang MT, Huang YF, et al. Dynamic change in bioactive polysaccharides and antimicrobial activity of Kudingcha (Ilex Kudingcha C. J. Tseng.) [J]. Food Sci, 2014, 35(9): [3]. [J]., 2015, 33(1): Liu GM. Development and utilization on resources of Kudingcha species in oleaceae and general situation in China[J]. Guizhou Sci, 2015, 33(1): [4] Li X, Zhang ZW, Li PW, et al. Determination for major chemical contaminants in tea (Camellia sinensis) matrices: A review [J]. Food Res Int, 2013, 53(2): [5],,,. [J]., 2014, 26(5): Luo HD, Wang WW, Wang TT, et al. Progress on residues of rare earth elements and their limitations in Chinese tea [J]. Chin J Food Hyg, 2014, 26(5): [6] Ning PB, Gong CM, Zhang YM, et al. La, Ce, Pr, Nd and Sm concentrations in Pu'er tea of Yunnan, China [J]. J Rare Earth, 2010, 28(4): [7] GB [S]. GB National standard for food safety-determination of chromium in food [S]. [8] GB [S]. GB National standard for food safety-determination of cadmium in food [S]. [9] GB [S]. GB National standard for food safety-determination of lead in food [S]. [10] GB [S]. GB National standard for food safety-determination of rare earth elements in food [S]. [11],,,. [J]., 2016, 26(17): Zhang RX, Cui ZY, Wang JX, et al. Comparison of high pressure tank digestion and wet digestion in the determination of lead in food [J]. Chin J Health Lab Technol, 2016, 26(17): [12],,. - [J]., 2016, 7(4): Wang X, Shao L, Teng ZY. Determination of heavy metal elements in vegetables by microwave digestion-inductively coupled plasma mass spectrometry [J]. J Food Saf Qual, 2016, 7(4): [13],,, [J]., 2016, 33(5): Wang J, Huang WX, Liang XX, et al. Selection of mix-acids digestion system and elimination of background interference on scandium applied in determination of 16 rare earth elements in soil and ocean sediments by ICP-MS [J]. J Environ Health, 2016, 33(5): [14],,,. ICP-MS 15 [J]., 2015, 34(7): Chen Y, Zhao XL, Yang H, et al. Determination of 15 trace and hazardous elements in edible Laver and kelp by inductively coupled plasma mass spectrometry with wet digestion [J]. Chin J Anal Lab, 2015, 34(7): [15],,. [J]., 2009, 28(1): Lin L, Chen G, Chen YH. Determination of inorganic arsenic in animal seafood by HPLC-ICP-MS [J]. Environ Chem, 2009, 28(1): [16],,, [J]., 2014, 26(4): Li M, Lian XW, Yao J, et al. Determination method of 12 metals in soy sauce by ICP-MS [J]. Chin J Food Hyg, 2014, 26(4): [17],,,. -ICP-MS 8 ( )[J]., 2014, 33(10): Sun XM, Lei M, Li L, et al. Simultaneous determination of eight heavy metals elements in soil by microwave digestion-inductively coupled plasma mass spectrometry [J]. Chin J Anal Lab, 2014, 33(10): [18] GB [S]. GB National standard for food safety-limits of contaminants in food[s]. [19]. [J]., 2016, (03): 4 5. Chen ZM. Limit standard of rare earth elements in tea is possible to repeal [J]. China Tea, 2016, (03): 4 5.

7 5, : 作者简介 ( 责任编辑 : 杨翠娜 ) 陈岩, 博士, 助理研究员, 主要研究方向为农产品质量安全与监测 gdaas_cyan@163.com 李汉敏, 硕士研究生, 主要研究方向为主要研究方向为农产品质量安全与植物营养 @com 王富华, 研究员, 博士生导师, 主要研究方向为农产品质量安全与风险评估 @com 乳及乳制品质量与安全 专题征稿函,,,,,,,, ,, 投稿方式 : : jfoodsq@126.com 食品安全质量检测学报 编辑部