7 11 Vol. 7 No. 11 2016 11 Journal of Food Safety and Quality Nov., 2016 滕妙珠 1, 郑睿行 2, 祝华明 (1., 322100; 2., 324000) 2* 摘要 : 目的 (PAHs) (GPC) 方法 PAHs, GPC,, 2, PAHs, 结果 GB/T 24893-2010, PAHs,, 10~50 μg/kg 78.21% 95.64%, 1.39% 4.55% 结论, 关键词 : ; ; Establishment of highly efficient pretreatment method for determination of polycyclic aromatic hydrocarbons in camellia seed oil TENG Miao-Zhu 1, ZHENG Rui-Hang 2, ZHU Hua-Ming 2 * (1. Dongyang Management Station of Quality and Technology Supervision, Dongyang 322100, China; 2. Quzhou Center of Quality Supervision and Technology Testing, Quzhou 324000, China) ABSTRACT: Objective To establish an efficient method for the determination of polycyclic aromatic hydrocarbons (PAHs) in camellia seed oil by gel permeation chromatography (GPC) purification and concentration method. Methods The camellia seed oil samples were treated with and without PAHs mixed standard solution, purified by GPC system, and the separation time of each component of monitoring samples were compared by the fluorescence detector of the system, so as to obtain the best collection time of PAHs, and the verification of the recovery rate was supplemented. Results The detection method of GB/T24893-2010 was optimized, and the samples of camellia seed oil were treated by adding standard PAHs. The recovery rates of the method were 78.21% to 95.64% in the range of 10~50 μg/kg, and standard deviations were 1.39%~4.55%. Conclusion The method simplifies the sample pretreatment process of camellia seed oil, reduces the manual time, and improves the detection efficiency, which is suitable for laboratory batch testing. KEY WORDS: camellia seed oil; polycyclic aromatic hydrocarbons; pretreatment 基金项目 : 2014 (2014214-24) 2015~2016 (2015C02060) Fund: Supported by the Ecological Province Construction Target Responsibility System for the Assessment of Major Scientific and Technological Projects in 2014 (2014214-24) and the Key Agricultural Foundation of Special Science and Technology Project of Zhejiang Province in 2015~2016 (2015C02060) * 通讯作者 :,, E-mail: zsbzhm@163.com *Corresponding author: ZHU Hua-Ming, Senior Engineer, Quzhou Supervision and Testing Center of Quality and Technology, Quzhou 324000, China. E-mail: zsbzhm@163.com
11, : 4621 1 引言 (PAHs), [1] 16 [2],,,,,,,, [3-5], (a) [6-8], [9] GB/T 24893-2010 C 18,,,,,,,,, ( TOFMS ), [10], ;,,,,,,,, [11],,, [12],,,, 2 - -, PAHs, PAHs,, 30,,,, 600, PAHs,, 3000 (GPC), (HPLC-FLD), 2 材料与方法 2.1 实验材料 ( PAHs): ; 15 PAHs ( ): 1, ; : : 2.2 仪器与设备 Agilent1200 ( ); GPC ( Bio Beads, Type S X3, 500 mm 25 mm, LCTech ) Table 1 表 1 15 种 PAHs 混合标准溶液的基本信息 Basic information of 15 kinds of PAHs mixed standard solution PAHs (%) (mg /L) PAHs (%) (mg /L) 99.0 1000±4.40 䓛 99.0 1000±1.05 99.0 1000±4.37 (b) 99.0 1000±2.09 99.0 1000±2.09 (k) 99.0 1000±1.04 99.0 1000±1.04 (a) 99.0 1000±1.04 99.0 1000±1.04 (a,h) 99.0 1000±1.05 99.0 1000±2.09 (g,h,i) 苝 99.0 1000±2.09 99.0 10000±1.04 (1,2,3-c,d) 99.0 1000±1.05 (a) 99.0 1000±1.04
4622 7 2.3 试验方法 2.3.1 空白样品的制备 0.8 g, 10 ml : (V:V=1:1),, 0.45 μm 16 ml, GPC, 2.3.2 标准样品的制备 0.8 g, PAHs 0.2 ml, 10 ml : (V:V=1:1),, 0.45 μm 16 ml, GPC, PAHs 2.3.3 GPC 仪器条件 254 nm, 5.0 ml, 40, 4, (V:V=1:1), 5.0 ml/min, 1 h, 0.018 0.021 MPa 3 结果与讨论 3.1 监测的图谱结果, 1 2 GPC,, GPC 9.0 16.0 min, PAHs 2, 1,, 2 PAHs, 26.0 48.0 min, 3.2 GPC 条件优化选择 [13] FAPAS PAHs, 250 mm 15 mm, Bio-Beads S-X3 GPC, 3 ml/min,, Bio-Beads, Type S-X3 ( 500 mm 25 mm, LCTech GPC ),,,, : 1: 1 (V:V),, 5 ml/min, 40, 5.0 ml 60 min, 26 47 min, 2.0 ml 3.3 液相色谱条件优化 GB/T 24893-2010, PAHs,, 2~4 1 Fig. 1 UV spectrum of camellia seed oil black sample
11, : 4623 Fig. 2 2 PAHs UV spectrum of PAHs mixed standard sample in camellia seed oil Table 2 表 2 液相色谱条件 Determination condition for HPLC 表 4 检测波长参数设置 Table 4 Detection wavelength parameter setting HPLC Agilent 1200 Eclipse PAH (4.6 mmⅹ150 mm, 5 μm) /min Ex /nm Em : 248~292 nm; : 324~507 nm A: ( ); B: - =50: 50(V:V) 1.2 ml/min 1 0 270 324 2 0 270 324 3 0 270 324 25 4 15.5 248 375 20 μl 5 15.5 248 375 6 19.8 280 462 表 3 PAH 柱梯度洗脱程序 Table 3 PAH column gradient elution program /min A/% B/% 0 0 100 20 60 40 36 100 0 43 0 100 3.4 液相色谱分离效果 PAHs PAHs 3 4 7 21.5 270 385 8 (a) 21.5 270 385 9 䓛 21.5 270 385 10 (b) 29.0 256 446 11 (k) 32.7 292 410 12 (α) 32.7 292 410 13 (α,h) 32.7 292 410 14 (α,h,i) 32.7 292 410 15 (1,2,3-c,d) 40.2 274 507
4624 7 1- ; 2- ; 3- ; 4- ; 5- ; 6- ; 7- ; 8- (a) ; 9- 䓛 ; 10- (b) ; 11- (k) ; 12- (a) ; 13- (a,h) ; 14- (g,h,i) 苝 ; 15- (1,2,3-c,d) 3 15 PAHS HPLC-FLD Fig. 3 HPLC-FLD chromatogram of 15 kinds of PAHS standard samples Fig. 4 4 PAHs HPLC-FLD HPLC-FLD chromatogram of PAHS in camellia seed oil 3.5 加标样品测定, PAHs (10 25 50 μg/kg), GPC [14,15] PAHs HPLC-FLD GB/T 24893-2010,, 15 PAHs, 3, 15 PAHs 5, 15 PAHs 10 50 μg/kg, 78.21% 95.64%, 1.39% 4.55%, PAHs,, 3.6 比对样品测定 2 L,,, (a) 6, 4 结论 GB/T 24893-2010 PAHs,,,, PAHs,, GPC C 18,,, ;,,
11, : 4625 Table 5 表 5 GPC 净化 -HPLC-FLD 法检测油茶籽油中 15 种 PAHs 的加标回收率与精密度试验结果 (n=3) Recoveries of 15 kinds of PAHs in camellia seed oil determined by GPC purification -HPLC-FLD method and the precision test results (n=3) PAHs 1(μg/kg) (%) 2(μg/kg) (%) 3(μg/kg) (%) 1 10 82.45±2.84 25 87.24±1.39 50 89.73±2.96 2 10 78.26±1.62 25 85.19±2.68 50 92.45±3.64 3 10 84.15±2.13 25 88.65±3.52 50 90.84±2.83 4 10 78.56±3.57 25 82.28±4.21 50 87.57±3.52 5 10 78.32±2.28 25 86.22±3.18 50 93.61±3.67 6 10 86.18±1.45 25 87.31±2.93 50 94.66±2.81 7 10 79.42±2.67 25 83.47±3.54 50 87.42±3.64 8 (a) 10 81.77±3.49 25 87.59±2.73 50 93.94±2.59 9 䓛 10 83.92±2.84 25 90.42±2.38 50 90.12±3.47 10 (b) 10 79.29±2.38 25 85.37±4.38 50 91.26±2.89 11 (k) 10 85.43±1.55 25 89.64±2.68 50 95.64±3.37 12 (a) 10 82.74±2.73 25 91.95±2.49 50 92.37±4.23 13 (a,h) 10 85.16±2.82 25 88.72±3.26 50 91.54±4.55 14 (g,h,i) 10 83.34±1.85 25 89.43±4.15 50 91.85±3.67 15 (1,2,3-c,d) 10 78.21±2.48 25 84.46±3.54 50 89.63±3.49 Table 6 表 6 油茶籽油苯并 (a) 芘比对检测结果 (n=3) Comparison of the detection results of benzo(a)pyrene in camellia seed oil (n=3) (μg/kg) SD(%) GB/T24893-2010 (a) 5.81 GPC+ HPLC-FLD (a) 5.91 2.66 参考文献 [1],,,. [J]., 2008, 29(12): 1774 1777. Gong ZQ, Hu XM, Xu XY, et al. Screening Adsorbents for polycyclic aromatic hydrocarbons in plant oil used to treat contaminated soil and performance evaluations [J]. J Northeast Univ, 2008, 29 (12): 1774 1777. [2],,. [J]., 2010, 36(8): 1 4. Liu H, Deng HP, Liu Z. Analysis of Heterogeneous catalytic ozonation for polycyclic aromatic hydrocarbons treatment [J]. Technol Water Treatment, 2010, 36(8): 1 4. [3]. [J]., 2006, (1): 25 27. Liang YX. Industrial development in china and the quality of camellia oil camellia [J]. Macroecon Res, 2006, (1): 25 27. [4],,,. [J]., 2015, 40(8): 42 45. Sun YJ, Zhu HM, Chen ZH. Fatty acid composition and oxidation stability of cold pressed oil - tea camellia seed oil [J]. China Oils Fats, 2015, 40(8): 42 45. [5],,. [J]., 2012, 27(6): 56 60. Shen JF, Chen ZH, Xiao RX. Effects of different processing methods on the quality of oil- tea of Camellia cheklangoleosa Hu [J]. J Chin Cereals Oils Ass, 2012, 27(6): 56 60. [6],,. [J]., 2015, 31(4): 59 62. Zhu HM, Dai J, Zheng RH. Effect of processing technology on composition and concentration of PAHs in camellia seed oil [J]. Food Mach, 2015, 31(4): 59 62. [7],,. [J]., 2014, 22(2): 49 51. Liu BG, Liu GQ, Wang XD. Producing approaches of benzo(a)pyrene during processing vegetable oil and the control measures [J]. Sci Technol Cereals Oils Food, 2014, 22(2): 49 51.
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