6 3 Vol. 6 No. 3 15 3 Journal of Food Safety and Quality Mar., 15 4 李 菊 1*, 谢建军 2, 杨丽 1, 刘淑君 1, 资医 1 (1., 523072; 2., 510623) 摘要 : 目的 4 方法,, - (GC/MS) 结果 4 0.1~1.0 μg/ml, 0.9999~1.0000 μg/kg, 81.3 %~97.5 %, 2.5% 7.5%, 4 5.0 μg/kg 结论, 4 关键词 : ; ; Rapid determination of 4 kinds of artificial musk in beverages by gas chromatography-mass spectrometry LI Ju 1*, XIE Jian-Jun 2, YANG Li 1, LIU Shu-Jun 1, ZI Yi 1 (1. Dongguan Entry-Exit Inspection and Quarantine Bureau, Dongguan 523072, China; 2. Guangdong Entry-Exit Inspection and Quarantine Bureau, Guangzhou 510623, China) ABSTRACT: Objective A rapid analytical method was developed for the determination of 4 kinds of artificial musk (musk ambrette, galaxolide abbalide, musk xylene, and ketone musk) in beverages by gas chromatography-mass spectrometry (GC/MS). Methods Totally 4 artificial musk residues were extracted from the samples(mango juice, tea, coffee, strawberry milk and other beverages different substrates) with Hexane, and then detected by GC/MS with external standard method. Results The linearity was obtained among 0.1~1.0 μg/ml with correlation coefficients above 0.9999. The recoveries of all artificial musk were in the range from 81.3% to 97.5% at the spiked levels of,, and μg/kg in beverages, and the relative standard deviations (RSDs) were between 2.5%~7.5%. The limits of detections (LODs) of the 4 kinds of musk were 5.0 μg/kg. Conclusion The method is simple, rapid and accurate, and suitable for the simultaneous analysis and evidence of 4 artificial musk in beverages. KEY WORDS: artificial musk; gas chromatography mass spectrometry; beverages 基金项目 : (13GDK30) Fund: Supported by the Guangdong Entry-Exit Inspection and Quarantine Bureau of Science and Technology Project (13GDK30) * 通讯作者 :,, E-mail: gddgjuju@163.com *Corresponding author: LI Ju, Engineer, Dongguan Entry-Exit Inspection and Quarantine Bureau, No.3, Jianshe Road, Nancheng District, Dongguan 523072, China. E-mail: gddgjuju@163.com
3, : - 4 975 1 引言 (artificial musk) : (nitro musk) (polycyclic musk) (macrocyclic musk) [1],, [1-6],,,,,, [1],,, [7-9], :, [17], [3,11-15], [10,16,],, (MX) (MK) (PoHS ) [16],, [4-6,18,19], [12-14] [11] [11,15] [17] [7,9] [8,10,16,],,,,, 2 材料与方法 2.1 试剂与仪器 Agilent 7890A-5975C ; IKA ; Sigma ;, 650 4 h, ; 4 ( ),, 98%, -4 2.2 标准溶液的配制和样品处理 :,, 10 ml, (1000 μg/ml) : 0.01 0.05 0.10 0.50 1.00 μg/ml, 5.0 g 15 ml, 2.0 ml, 1 min, 8000 r/min 5 min,, 1 min, 2.3 仪器条件 HP-5MS(30 mm 0.25 mm 0.25 μm); : 260 ; : 100 ( /min) 180 (1 / min) 192 (30 /min) 280 ; : 280 ; : 1 μl (); : ( 99.999%); : EI; (SIM), 3 4, 3 表 1 4 种人造麝香的保留时间与特征离子 Table 1 Retention time(t R ) and characteristic ions of the 4 artificial musks (min) (m/z) 8.28 253,268,254 253 8.60 243,213,258 243 8.75 282,297,265 282 11.50 279,294,128 279 3 结果与讨论 3.1 样品前处理条件的选择优化 3.1.1 提取溶液的选择 :, 0. mg/kg
976 6, : (1:1), 88.0%~102.0%,, ( ) : (1:1) ( ), : (1:1) ; ( ),, -, 3.1.2 提取方式的选择, 0.65 mg/kg,,, 1 min 2 min 5 min 10 min, 97.4% 100.2% 99.4% 99.5%, 1 min 2 min 5 min 10 min, 96.0% 97.4% 98.2% 97.8%,, 1 min 3.2 色谱 - 质谱条件的选择优化 3.2.1 升温程序的选择, : 70, 1 min, /min 2, 1 min, 5 /min 280, 4 min; : 100, /min 180, 1 /min 192, 30 /min 280, 3 min,,, 4,,, 1 1 Fig. 1 Comparison of chart of peak area under 2 chromatographic conditions 3.2.2 定性筛选与定量检测方法的建立 (scan) 1.00 μg/ml 4,, 3 ( 3); (scan) (SIM) 4 : GC-MS, (±0.5%),, 3.3 线性关系和检出限 4 0.01 μg/ml~1.0 μg/ml, 2 Table 2 表 2 4 种人造麝香的标准曲线 线性相关系数及检出限 Standard curve, the linear correlation coefficient and detection limit of 4 kinds of artificial musk (μg/ml) r 2 (μg/kg) 0.01 1.0 Y=3.371 10 6 X-3.978 10 4 1.000 5.0 0.01 1.0 Y=6.708 10 6 X+5.124 10 4 0.999 5.0 0.01 1.0 Y=2.639 10 6 X+1.582 10 2 1.000 5.0 0.01 1.0 Y=3.102 10 6 X-2.276 10 4 1.000 5.0
3, : - 4 977 Table 3 表 3 4 种人造麝香的回收率与变异系数 Recovery rate and coefficient of variation of 4 artificial musks (μg/kg) 1 2 3 4 5 6 (RSDs)/% 88.6 90.6 76.2 86.5 90.1 94.1 80.4 91.5 76.5 98.2 86.5 89.4 83.0 91.7 7.5 4.3 102.3 93.8 90.7 86.2 95.2 93.4 5.7 82.1 94.2 87.8 92.5 78.2 95.1 73.4 88.6 79.5 93.5 86.7 91.6 81.3 6.6 2.5 99.2 84.6 96.4 92.1 89.9 93.6 5.5 82.5 96.2 85.6 105.1 81.6 96.7 82.5 98.6 85.9 95.7 92.1 85.0 97.5 4.6 4.3 89.2 93.5 87.6 89.9 94.6 92.5 91.2 3.0 91.0 88.1 87.1 95.1 76.8 86.8 78.6 94.1 85.2 92.2 86.7 97.0 84.2 92.2 6.4 4.3 106.2 95.8 90.4 88.6 93.7 94.6 6.6 3.4 回收率与精密度, 5.0 g,, GC/MS, 3, 4 3.5 样品分析 30, 3, 23.4 μg/kg ( 2); 32.7 μg/kg, 42.6 μg/kg 4 结论, GC/MS, ~ μg/kg, 4 ( ) 81.3%~97.5%, (LOD) 5.0 μg /kg, (n=6) 7.5% 4,,,,,, 2 TIC Fig. 2 Total ion current chromatogram of artificial musk reference solution and sample
978 6 参考文献 [1],,,. [J]. ( ), 11, 2(11): 103 107. Yan JX, Li Q, Cui JJ, et al. Detection progress of musk xylene and musk ketone [J]. J Shanghai Inst Technol (Nat Sci). 11, 2(11): 103 107. [2] [EB/OL]. http: www cccco1 corn~action viewnes itemid 4236, 6-01-09 The listen of EU hazard classification musk ketone [EB/OL]. http: www cccco1 corn~action-viewnes-itemid-4236, 6-01-09 [3],,,. [J]., 8, 2S(1): 1 11. Zbou QX, Wang ME, Fan F, et al. Research progress in environmental pollution, ecological behavior and toxicological effects of synthetic musks [J]. Acta Scientiae Circumstantiae, 28(1): 1 11. [4],,,. (PCPs).[J]., 8, 27(3): 382 384. Lu Y, Hu XF, Wang PH, et al. The determination of trace Personal care products (PCPs) in water environment [J]. Environ Chem, 8, 27(3): 382 384. [5],. [J]., 9, 37(18): 1776 1780. Ma Q, Bai H. Determination of musk xylene in cosmetics by solid phase extraction-isotope Dilution-Gas Chromatography Tandem Mass Spectrometry [J]. Chin J Anal Chem, 9, 37(18): 1776 1780. [6]. GC/MS [J]., 3, 13(4): 456 457. Yang R. The methods of three kinds of artificial musk by GC/MS in Cosmetics [J]. Chin J Health Lab Technol, 3, 13(4): 456 457. [7],,,. [J]., 10, 29(1): 113 116. Liang GF, Wang J, Zhou J, et al. Determination of synthetic musk sinhuman milk samples by Gas Chromatography/Mass Spectrometry [J]. Environ Chem, 10, 29(1): 113 116. [8] Kannan K, Reiner JL, Yun SH, et al. Polyccycli musk compounds in higher trophic level aquatic organisms and humans from the United States [J]. Chemosphere, 5, 61: 693 700. [9] Reiner JL, Wong CM, Arcaro KF, et al. Synthetic musk fregrances in human breast milk from the United States [J]. Environ Sci Technol, 7, 41: 3815 38. [10],,. 9 [J]. ( ), 13, 42(2): 2 6. Ye H, Lin YH, Yang F, et al. Determination of 9 kinds of synthetic musk in aquatic products by GC-MS [J]. J Fujian Agric Forestry Univ (Nat Sci Edit), 13, 32(2): 64 68. [11],,. [J]., 10, 38( 6): 885 888 Hu ZJ, Shi YL, Cai YQ. Determination of synthetic musk fragrances in sewage, sludge, and sedimentand soil using accelerated solvent extraction with Gas Chromatography-Mass Spectrometry [J]. Chin J Anal Chem, 10, 38(6): 885 888. [12],,,. [J]., 8, 27(3): 368 370. Zeng XY, Sheng GY, Zhang XL, et al. The occurrenge and distributilon of polycyclic musks in sediments from river water [J]. Environ Chem, 8, 27(3): 368 370. [13],. - [J]., 11, 24 (4): 54 56. Yang Y, Zhou LJ. The determination of galaxolide in water samples by using SPME-GC-MS [J]. Pollut Control Technol, 11, 24 (4): 54 56. [14],,. [J]. ( ), 10, 10( 3): 224 227 Li GM, Xiang M, Bi DS. Study on translation and conversion behavior of polycyclic musks in municipal wastewater treatment [J]. J Shanghai Inst Technol (Nat Sci), 10, 10(3): 224 227. [15],,. [J]., 11, 30(7): 745 749. Luo Q, Sun LN, Zhang YH. Comparative study of microwave assisted solvent extraction and other extraction methods of polycyclic musks in soil [J]. J Instrum Anal, 11, 30(7): 745 749. [16],,. - [J]., 11, 30(6): 1197 11. Che JS, Wang LP, Song QJ. Determination of synthetic musks in aquatic products by Gas Chromatography-Mass Spectrometry [J]. Environ Chem, 11, 30(6): 1197 11.
3, : - 4 979 [17],,. - [J]., 10, 29(3): 530 535. Hu ZJ, Shi YL, Cai YQ. Determination of synthetic musks inhuman blood by gas chromatography-mass spectrometry [J]. Environ Chem, 10, 29(3): 530 535. [18] Zhang X, Yao Y, Zeng X, et al. Synthetic musks in the aquatic environment and personal care products in Shanghai China [J]. Chemosphere, 8, 72: 1553 1558. [19],,. [J]., 13, 32(2): 64 68. Ye H, Lin YH, Yang F, et al. Determination of 9 synthetic musks in personal care and sanitation products by GC-MS /MS [J]. Chin J Anal Lab, 13, 32(2): 64 68. [],,. / [J]., 11, 30(1): 362 265. Hu ZJ, Shi YL, Cai YQ. Determination of polycycli musks in fish samples by accelerated soventextraction(ase)and Gas Chromatography-Mass Spectrometry [J]. Environ Chem, 11, 30(1): 362 365. 作者简介 ( 责任编辑 : 白洪健 ) 李菊, 本科, 工程师, 主要研究方向为添加剂残留分析 E-mail: gddgjuju@163.com