7 3 Vol. 7 No. 3 2016 3 Journal of Food Safety and Quality Mar., 2016-9 李梦怡 1, 董喆 1, 费丽娜 2, 曹进 (1., 100050; 2., 132000) 1* 摘要 : 目的 - 3 9 方法 -, 3 9, 103 Rh 185 Re 结果, ; 9 r 0.999 ; ; 9 82%~120% ; 7.8% 结论, 3 9 关键词 : ; ; ; Determination of 9 kinds of elements in health food by microwave digestion-inductively coupled plasma mass spectrometry LI Meng-Yi 1, DONG Zhe 1, FEI Li-Na 2, CAO Jin 1* (1. National Institutes for Food and Drug Control, Beijing 100050, China; 2. Jilin Institutes for Food and Drug Control, Jilin 132000, China) ABSTRACT: Objective To establish a method for simultaneous determination of 9 kinds of elements such as Na, Mg, K, Ca, Mn, Fe, Cu, Zn, and Se, in liquid, solid, and soft capsule types of health food by microwave digestion- inductively coupled plasma mass spectrometry (ICP-MS). Methods Nine kinds of elements in 3 kinds of matrix of health food were firstly decomposed by microwave oven with nitric acid and hydrogen peroxide, and then determined simultaneously by ICP-MS. Samples were corrected by adding internal standard solution on line, with 103 Rh and 185 Re as internal standard. Results This method showed a wide linearity range, and low detection limit. The recoveries were in the range of 82%~120%, and relative standard deviations were under 7.8%. Conclusion This method is rapid, sensitive and accurate, and suitable for the simultaneous determination of Na, Mg, K, Ca, Mn, Fe, Cu, Zn, and Se in 3 kinds of matrix of liquid, solid and soft capsule. KEY WORDS: elements; health food; microwave digestion; inductively coupled plasma mass spectrometry * 通讯作者 :,, E-mail: caojin@nifdc.org.cn *Corresponding author: CAO Jin, Professor, National Institutes for Food and Drug Control, No.2, Tiantanxili, Dongcheng District, Beijing 100050, China. E-mail: caojin@difdc.org.cn
3, : - 9 945 1 引言,,,,,,,,,,,,,,, [1,2],,,,,, [3] [4] [5] [6] [7],, [8, 9],,,,,,, [10, 11], 3 9,,,,,,, 2 材料与方法 2.1 仪器与试剂 icap-q, (Thermo Fisher ); MARS5 (CEM ); Milli-Q (Sartorius ); BHW-09C ( ); METTLER AL204 (Mettler Toledo ) (, ); : (Na) (Mg) (K) (Ca) (Mn) (Fe) (Cu) (Zn) [ρ=1000.0 µg/ml], (Se) [ρ=100.0 µg/ml] ( ); : Re [ρ=10.0 µg/ml] Rh [ρ=10.0 µg/ml]( ); : (Li) (Co) (In) (U) (Ba) (Ce)[ρ=1.0 μg/l] ( ) 2.2 样品前处理 0.3 g,, 5.0 ml, 2.0 ml, 100 20 min,,,,, 1 表 1 微波消解温度时间程序 Table 1 Time-temperature program for digestion / /min /min 120 5 3 160 5 3 180 5 20,, 125 2 ml, 25 ml 2.3 系列标准溶液配制 9, 5%, (Na) 10 mg/l (Mg) 10 mg/l (K) 10 mg/l (Ca) 10 mg/l (Mn) 1 mg/l (Fe) 1 mg/l (Cu) 1 mg/l (Zn) 1 mg/l (Se) 0.5 mg/l
946 7 2,, 5%,, 表 2 系列标准溶液浓度 (mg/l) Table 2 Concentration of serial standard solutions (mg/l) Na Mg K Ca Mn Fe Cu Zn Se Ⅰ 10 1 0.5 Ⅱ 5.0 0.5 0.25 Ⅲ 1.0 0.1 0.05 Ⅳ 0.5 0.05 0.025 V 0.1 0.01 0.005 2.4 样品测定, (Rh Re10 μg/l) : : 1550 W; : 14 L/min; : 1 ml/min; : 0.8 L/min; : 5 mm; : ; : 3 ; : ; : KED; : (>99.999%), : 4.2 ml/min; : 40 r/min; : 0.02 s 3 结果与分析 3.1 消解方法及条件的选择, [13],,, ; ICP-MS, 3, 2, -, 9,,, - 3.2 测定同位素的选择 40 Ca, 40 Ar 40,, 44 Ca 56 Fe, ( 40 Ar+ 16 O) 56, 57 Fe, 3.3 线性范围,, (Rh Re10 μg/l), ICP-MS X, Y,, 0.999 3,,, 0.999, 3.4 检出限与定量限 2.2 11, (SD), 3, ; 10, [14] 0.3 g, 25 ml,, 4 3.5 加标回收率, 3, 6, 2.2,,, 5, 3 82%~120%, 93%~117%, 93%~119%, 3.6 精密度 2.2 3 6,, RSD 2.2 3, 3, 1,, RSD 6
3, : - 9 947 Table 3 表 3 各元素线性方程 相关系数及线性范围 Linear equations, correlation coefficients and linear range for each element r (mg/kg) 23 Na Y=2456871X+35986 0.9997 0.1~10 24 Mg Y=1023575X+2235 0.9999 0.1~10 39 K Y=814098X+15175 0.9998 0.1~10 44 Ca Y=55379X+1493 0.9992 0.1~10 55 Mn Y=15230X+876 0.9997 0.01~1 57 Fe Y=621X+801 0.9997 0.01~1 63 Cu Y=32737X+2700 1.0000 0.01~1 66 Zn Y=4971X+4589 0.9999 0.01~1 78 Se Y=429X+10 0.9991 0.005~0.5 Table 4 表 4 检出限与定量限 (mg/kg) LOD and LOQ of the method (mg/kg) 23 Na 0.04 3 0.1 11 24 Mg 0.002 0.2 0.008 0.6 39 K 0.005 0.4 0.02 1 44 Ca 0.01 1 0.05 4 55 Mn 0.0001 0.008 0.0003 0.03 57 Fe 0.003 0.3 0.01 0.9 63 Cu 0.0001 0.009 0.0004 0.03 66 Zn 0.0003 0.03 0.001 0.09 78 Se 0.00004 0.003 0.0001 0.01 Table 5 表 5 加标回收率 (n=6) Recovery test of the method (n=6) 23 Na 120% 119% 120% 106% 112% 106% 111% 117% 105% 24 Mg 106% 110% 111% 104% 104% 105% 109% 108% 106% 39 K 104% 107% 93% 101% 106% 106% 106% 110% 106% 44 Ca 82% 114% 126% 97% 105% 115% 103% 111% 116% 55 Mn 101% 104% 99% 106% 106% 107% 110% 110% 107% 57 Fe 88% 115% 109% 99% 105% 102% 106% 109% 103% 63 Cu 104% 103% 99% 101% 97% 98% 104% 100% 100% 66 Zn 93% 98% 97% 117% 93% 104% 119% 94% 107% 78 Se 87% 94% 104% 93% 94% 106% 93% 95% 111%
948 7 表 6 精密度试验结果 Table 6 Results of precision test (n=6) (n=3) 23 Na 2.4% 2.7% 2.6% 5.3% 0.9% 4.0% 24 Mg 2.4% 2.4% 2.6% 2.0% 0.7% 2.4% 39 K 1.8% 2.0% 2.6% 4.5% 2.8% 5.0% 44 Ca 2.5% 2.7% 7.8% 6.3% 2.3% 5.0% 55 Mn 2.0% 2.5% 3.2% 2.1% 1.1% 2.4% 57 Fe 2.1% 2.5% 3.1% 2.8% 0.4% 1.8% 63 Cu 2.3% 2.5% 2.8% 2.0% 1.9% 3.0% 66 Zn 4.6% 3.1% 4.4% 1.5% 2.3% 0.4% 78 Se 4.1% 2.1% 3.0% 3.4% 2.8% 4.3% 3.7 稳定性, 3, 0 3 6 24 h, RSD, 7, 24 h 表 7 样品稳定性 (n=4) Table 7 Results of stability test (n=4) 23 Na 3.0% 3.3% 4.6% 24 Mg 3.5% 3.8% 4.7% 39 K 4.6% 5.0% 6.2% 44 Ca 4.7% 4.6% 6.2% 55 Mn 3.0% 3.0% 4.8% 57 Fe 2.6% 2.5% 4.4% 63 Cu 2.8% 1.8% 2.8% 66 Zn 6.6% 2.8% 2.7% 78 Se 5.0% 5.0% 5.3% 3.8 样品测定 8, 8 4 讨论 4.1 基质干扰,,,,, -,, 9,,,,,,,,, 9 4.2 检测干扰的消除 ICP-MS,
3, : - 9 949 表 8 Table 8 样品含量测定结果 (mg/kg) Results of sample test (mg/kg) 1 88 17 3.7 15614 0.712 202 ND 120 ND 2 ND 1.6 5.9 6.8 ND ND ND ND ND 38 90 804 6.8 0.26 48 0.33 1.9 0.016 1 ND ND ND ND ND ND ND ND ND 2 67 74 546 406 0.56 3.5 0.27 0.64 ND 7908 430 5447 2213 6.9 143 8.1 17 0.14 6796 3444 15637 937 16 431 2.6 9.4 0.42 ND ND ND ND ND ND ND ND ND : ND 3 [15], ;, [16],, / 5 结论,,,, 3 9 参考文献 [1],,. [J]., 2012, 18(5): 1 4. Yang F, Meng QX, Peng ZH, et al. Progress in application of inductively coupled plasma mass spectrometry hyphenated technique [J]. Mod Instrum, 2012, 18(5): 1 4. [2]. [J]., 2014, 30(2): 118 124. Jiang N. Application and research progress of inductively coupled plasma mass spectrometry in environmental monitoring area [J]. Environ Monitor China, 2014, 30(2):118 124. [3]. - [J]., 2014, (11):1706 1709. Zhang JY. Simultaneous determination of trace elements and major elements in food by ICP-MS using microwave digestion for sample preparation [J]. Chin J Anal Chem, 2014, (11):1706 1709. [4],,,. - [J]., 2013, 29(4): 506 510. Ni ZL, Tang FB, Qu MH, et al. Determination of arsenic species in scented tea by HPLC-ICP-MS [J]. J Anal Sci, 2013, 29(4): 506 510. [5],,. - [J]., 2013, 34(12): 300 303. Yan N, Zhao SG, Gao YY. Determination of cadmium, mercury, lead and chromium in alcoholic drinks by inductively coupled plasma-mass spectrometry with dynamic reaction cell [J]. Food Sci, 2013, 34(12): 300 303. [6]. - 28 [J]., 2014, 35(18): 67 79. Qin DL. Simultaneous determination of 28 trace elements in aquatic products by microwave digestion-inductively coupled plasma mass spectrometry method [J]. Sci Technol Food Ind, 2014, 35(18): 67 79. [7],. [J]., 2014, (7):1927 1928. Jiang HL, Xu XQ. Simultaneous determination of heavy metals in honeysuckle by ICP-MS[J]. J Anhui Agric Sci, 2014,
950 7 (7):1927 1928. [8],,,. - 25 [J]., 2014, 45(15): 2172 2177. Tang WG, Wang QZ, Yin M, et al. Determination of 25 kinds of minerals in mailuoning injection by inductively coupled plasma mass pectrometry with microwave digestion [J]. Chin Tradit Herbal Drug, 2014, 45(15): 2172 2177. [9],,,. - [J]., 2014, (04): 462 465. Liu W, Hu JD, Yang HX, et al. Rapid determination of inorganic arsenic in natural water by high performance liquid chromatography inductively coupled plasma mass spectrometry[j]. Chin J Anal Lab, 2014, (04): 462 465. [10],,,. - 6 [J]., 2013, 41(11): 1669 1674. Wang X, Xing YN, Chen ZY, et al. Determination of inorganic selenium in selenium-enriched foods by high performance liquid chromatography inductively coupled plasma mass spectrometry [J]. Chin J Anal Chem, 2013, 41(11): 1669 1674. [11] NY/T 1653-2008 [S]. NY/T 1653-2008 Determination for mineral elements in vegetables, fruits and derived products -Inductively coupled plasma atomic emission spectrometry [S]. [12] GB 5009.94-2012 [S]. GB 5009.94-2012 National standards for food safety-determination of rare earths in vegetable foods [S]. [13],,,. [J]., 2014, 28(11): 1209 1212. Feng KR, Liu HJ, Wei Y, et al. Proficiency testing on the determination of chromium in cosmetic emulsion [J]. Chin Pharm Affairs, 2014, 28(11): 1209 1212. [14] GB/T 27415-2013 [S]. GB/T 27415-2013 Detection limit and quantitative limit of analysis method [S]. [15],,,. 15 [J]., 2009, 38(6): 747 749. Tian PY, Liu YH, Wang P, et al. Fifteen rare earth elements in cosmetics determinated by inductively coupled plasma-mass spectrometry [J]. J Hyg Res, 2009, 38(6): 747 749. [16] 喆,,,. 37 [J]., 2015, 38(6): 20 25. Dong Z, Li MY, Pan WJ, et al. Determination of 37 elements in cosmetics by inductively coupled plasma-mass spectrometry [J]. Deter Cosm, 2015, 38(6): 20 25. 作者简介 ( 责任编辑 : 杨翠娜 ) 李梦怡, 硕士, 助理研究员, 主要研究方向为食品安全检测 E-mail: limengyi@nifdc.org.cn 曹进, 博士, 研究员, 主要研究方向为食品安全检测 E-mail: caojin@nifdc.org.cn