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1 5 1 Vol. 5 No Journal of Food Safety and Quality Jan., 江志刚 1*, 刘淇 2 1,, 赵梦醒 2, 李宗芮 1, 牟志春 (1., ; 2., ) 1 摘要 : 目的 -(high pressure liquid chromatography coupled to inductively coupled plasma mass spectrometry, HPLC-ICP-MS) 方法, 结果 mg/l, 85.1%~112.1%, (relative standard deviations, RSD) 6.0%~8.2% 结论, 关键词 : ; ; ; Determination of boric acid in aquatic products by high pressure liquid chromatography coupled to inductively coupled plasma mass spectrometry JIANG Zhi-Gang 1*, LIU Qi 2, ZHAO Meng-Xing 1, 2, LI Zong-Rui 1, MU Zhi-Chun 1 (1. Shandong Entry-Exit Inspection and Quarantine Bureau Technology Center, Qingdao , China; 2. Yellow Sea Fisheries Research Institute, Chinese Academy of Fishery Sciences, Qingdao , China) ABSTRACT: Objective To establish the method for the determination of boric acid in aquatic products by high pressure liquid chromatography coupled to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). Methods The protein precipitation solution, extracting time and mobile phase were optimized and the ultrasonic extraction was used for extracting boric acid in aquatic products, and was compared with the content of boric acid by microwave digestion pretreatment. Results The limit of detection was mg/l and the average recoveries ranged from 85.1% to 112.1%, with the relative standard deviations of 6.0%~ 8.2%. Conclusion The method is accurate and reliable, which is suitable for the determination of boric acid added in aquatic products. KEY WORDS: high pressure liquid chromatography(hplc); inductively coupled plasma mass spectrometry (ICP-MS); aquatic products; boric acid 基金项目 : (SK201351)(2012YQ090229) Fund: Supported by the Research Foundation of Shandong Entry-Exit Inspection and Quarantine Bureau(SK201351) and National Major Scientific Instruments and Equipment Development Projects(2012YQ090229) * 通讯作者 :,, zhigangjiang@126.com *Corresponding author: JIANG Zhi-Gang, Researcher, Shandong Entry-Exit Inspection and Quarantine Bureau Technology Center, No.70, Qutangxia Road, Qingdao , China. zhigangjiang@126.com

2 48 5, [1] [2],, [3] [4],, [5-6], [7],,, LD ~900 mg/kg bw, LD ~350 mg/kg bw [8] [9] JECFA [2] 1961,, [10],, [11], (inductively coupled plasma-atomic emission spectrometry, ICP-AES) (inductively coupled plasma mass spectrometry, ICP-MS)(high pressure liquid chromatography, HPLC) (ion chromatography, IC) [12-19], GB/T [20],,, -, -,,, 1 材料与方法 1.1 材料与试剂 (, ); (, ); (, ); (, MERCK );, ( ), 仪器与设备 7500cx ( Agilent ); 1260 ( Agilent ); MARS EXPRESS ( CEM ); Milli-Q ( Millipore ); KQ5200DE (); TGL-20B ( ); Hamilton PRP-X100 (10 μm, 250 mm 4.1 mm) 1.3 样品前处理 1 g( g) 50 ml, 9 ml,, 15 min; 1, ; 10% 2 ml, 30 min; 8000 r/min 10 min,, 0.45 μm, HPLC-ICP-MS 1.4 HPLC-ICP-MS 工作条件 HPLC-ICP-MS 1 表 1 HPLC-ICP-MS 工作条件 Table 1 Operating conditions of ICP-MS and chromatographic systems ICP-MS 1550 W 7.4 mm 0.89 L/min 0.22 L/min r/s HPLC Halmilton PRP-X100 (10 μm, 250 mm 4.1 mm) 3.2 mmol/l NaOH 0.5 mmol/l Na 2 CO 3 10 μl 0.8 ml/min

3 1, : 结果与讨论 min 2.1 蛋白沉淀剂的选择,, 10% 95% 10% 3, 10%,,, 95%,, ICP-MS,,, 10%,,, 10% 2 ml,,, 2.2 提取时间的选择,, ( min), 1, 15 min, 85%;, 95%,, 15 1 Fig. 1 Effect of different extracting time for extraction efficiency 2.3 色谱柱的选择,, [18] Hamilton PRP-X100,, Hamilton PRP-X100,, mg/l HPLC-ICP-MS Fig. 2 HPLC-ICP-MS chromatogram of 20 mg/l boric acid standard solution

4 流动相的选择 0.1%NH 4 OH(v/v) 0.25 mmol/l (NH 4 ) 2 CO 3 0.1%NH 4 OH(v/v) 0.5 mmol/l (NH 4 ) 2 CO 3 NaOH Na 2 CO 3,,, ph, NH 4 OH (NH 4 ) 2 CO 3,,,,, NaOH Na 2 CO 3 (mmol/l) 2.5:0.5, 2.8:0.5, 3.0:0.5, 3.2:0.5,, NaOH,,, NaOH Na 2 CO 3 (mmol/l) 3.2:0.5 Na, Na,,, ICP-MS 2.5 回收率和精密度,,, mg/l,,, 2, 85.1%~112.1%, (relative standard deviations, RSD) 6.0% ~ 8.2%,, 表 2 加标回收试验 Table 2 Recovery test (μg/ml) % RSD/% 线性范围和检出限 mg/l ( ) HPLC-ICP-MS,,, 3, R=0.9995, 1.0~20.0 mg/l, 3 3 Fig. 3 The standard curve for boric acid,, 3 (n =11) mg/l 2.7 实际样品分析, NY [21] 100 mg/kg GB/T ~19.51 mg/kg [22] ICP-MS,, HPLC-ICP-MS 4, 2.7 min, NaCl 2.7 min, 2.7 min,, 3 结论,

5 1, : - 51 Table 3 表 3 水产品中的硼酸含量 ( 以湿重计 ) The contents of total boron and boric acid in aquatic products (wet weight) (mg/kg) (mg/kg) (mg/kg) 19.51± ± ± 0.91 HPLC-ICP-MS N.D. N.D. N.D. N.D. 4 HPLC-ICP-MS Fig. 4 HPLC-ICP-MS chromatogram of boric acid in the added salted jelly fish head -(HPLC-ICP-MS),,, 14.79~19.51 mg/kg, 参考文献 [1],. [J]., 2004, 18(4): Yang G, Zhong LF. Research progress of boron and its compounds in risk assessment [J]. J Health Toxicol, 2004, 18(4): [2],,,. 12 [J]., 2011, 40(4): Song XY, Li FQ, Liu ZP, et al. Boron background value survey of some foodstuffs in 12 provinces of China and boron primary intake estimation of Chinese habitants [J]. J Hyg Res, 2011, 40(4): [3],,,. [J]., 2007, 24(3): Xing XR, Wu GP, Wei FS, et al. Daily intake of boron through food and drinking water for people living in different environments [J]. J Environ Health, 2007, 24(3): [4] Krejcova A, Cernohorsky T. The determination of boron in tea and coffee by ICP AES method [J]. Food Chem, 2003, 82(2): [5],,,. 45 [J]., 2010, 21(3): Chi WT, Xie SB, Yang GB, et al. Analysis on detection of boron content in 45 kinds of food [J]. Henan J Prev Med, 2010, 21(3): [6] Sungur S, Okur R. Using azomethine-h method determination of boron contents of various foods consumed in Hatay Region in Turkey [J]. Food Chem, 2009, 115: [7] Li ZJ, Cui ZW, Tang J. The determination of boron in food and seed by spectrophotometry using a new reagent 3, 4-dihydroxyazomethine H [J]. Food Chem, 2006, 94 (2): [8],,,. [J]., 2011, 17(4):

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