6 1 Vol. 6 No. 1 2015 1 Jornal of Food Safety and Qality Jan., 2015 高宏 *, 徐慧, 郭芳芳, 李青 (, 210042) 摘要 : 目的 GB/T 5009.19-2008, (gas chromatography, GC) 方法 GC,,,,, 结果 0.0760.059, (5.21±0.79) μg/kg, (4.9±0.56) μg/kg; 结论 关键词 : ; ; ; Evalation of ncertainty of aldrin and dieldrin in milk GAO Hong *, XU Hi, GUO Fang-Fang, LI Qing (Jiangs Test Center for Physics and Chemistry, Nanjing 210042, China) ABSTRACT: Objective To evalate the test reslts of ncertainty of aldrin and dieldrin detected by gas chromatography(gc) in milk, according to GB/T 5009.19-2008 Determination of organo chlorine pesticides in foods mlticomponent resides. Methods The factors affecting the ncertainty were dedced by establishing mathematical model for the determination by GC method. Each component of ncertainty was evalated and calclated, from which the combined ncertainty and the extended ncertainty were obtained. Reslts The combined ncertainty of aldrin and dieldrin in milk for determination was 0.076 and 0.059, and the determined content of aldrin and dieldrin was (5.21±0.79) μg/kg and (4.9±0.56) μg/kg, respectively. The standard crve, pre-treatment process and instrment measrement repeatability was the primary factor for determination of aldrin and dieldrin. Conclsion The establishment of the methodology for the evalation of measrement ncertainty is important for the determination of aldrin and dieldrin pesticides in milk. KEY WORDS: milk; aldrin; dieldrin; ncertainty 1 引言 (aldrin)(dieldrin) [1], * 通讯作者 :,,, E-mail: 190919402@qq.com *Corresponding athor: GAO Hong, Intermediate Engineer, Jiangs Test Center for Physics and Chemistry, Nanjing 210042, China. E-mail: 190919402@qq.com
16 6, [2] 2001 (POPs), [],, [4], [5-7], [8] (JJF 1059.1-2012) [9],,,,, 2 材料与方法 2.1 仪器与试剂 Agilent 7890B, (ECD) OpenLAB CDS ( ); HZQ-100A ( ); EYELA SB-2000 ( ); MTN-2800W ( ) (, ) (), 100 μg/ml 2.2 色谱条件 : BR-5, 0 m 0.25 mm, i.d. 1.0 μm df : 80 2 min 10 /min 250 min, 10 /min 280 5 min; : 00 ; : 270 : 99.99%, ; : 1 ml/min; : 0 ml/min; : 1 μl; : 2. 标准系列溶液的配制 1.0 ml, 10 ml,, 10 μg/ml 1 ml 10 ml,, 1 μg/ml, 12.525.050.0100200 ng/ml 2.4 样品的处理 ()500 g 20 g ( 0.01 g), 0 ml, 0 min 6 g,, 0 ml, 0 min,, 5 ml 10 ml, + (1:1, v:v),,, 5 ml 2.5 样品的测定 1 μl,,, 数学模型, : cv f X Frep m R ec : X:, mg/kg; c:, μg/ml; V:, ml; f: ; m:, g; R ec : ; F: ; rep: 4 不确定度来源分析,, : (1) () ; (2) ;
1, : 17 () ; (4) ; (5) ; (6) ; (7) 5 不确定度分量的评定 5.1 标准溶液及配制过程 ( 稀释 定容 ) 中引入的不确定度 (m 1 ) 5.1.1 标准溶液的不确定度 B,, 100 μg/ml, 0.10 μg/ml 0.08 μg/ml P=95%, k=2, 0.10 0.08 (c 艾氏剂 ) 0.0005, (c 狄氏剂 ) 0.0004 2100 2100 5.1.2 标准溶液配制过程引入的不确定度 5.1.2.1 (1) 125 ml, JJG196-2006, 125 ml A ±0.007 ml±0.010 ml±0.015 ml,, k=,, 0.010 1 ( V 吸 2) 0.0058; 0.007 1 ( V 吸 1) 0.0040; 0.015 1 ( V 吸 ) 0.0087 (2) 20±2,, 1.26 10 - ml/,, 21.2610 1 2 ( V 吸 1) 0.0015; 21.2610 2 2 ( V 吸 2 ) 0.0029; 21.2610 10 2 ( V 吸 ) 0.0145 () 1 ( 吸 1 2 ( 吸 1 V ) V ) ( V吸 1) 0.004; 1 1 ( 吸 2 2 ( 吸 2 V ) V ) ( V吸 2 ) 0.002; 2 1 ( 吸 2 ( 吸 V ) V ) ( V吸 ) 0.002 5 5.1.2.2 (1) 10 ml, JJG196-2006, 10 ml A ±0.020 ml,, k=, 0.020, 1 ( V 容 1) = = 0.0115 (2) ±2,, 1.26 10 - ml/,, 21.2610 10 2( V 容 1) = = 0.0145 () 1 ( 容 1) 2 V ( V容 1) = = 0.0019 10 5.1. 标准溶液及配制过程 ( 稀释 定容 ) 中引入的相对不确定度, 125 ml 214, 10 ml 7, : 艾氏剂 ( c ) ( V吸 1) 2 ( m1 ) 0.0097 ( V ) ( V ) 4 ( V ) 7 2 吸 2 吸 容 1 (m 1 ) 0.0097 5.2 标准曲线引入的不确定度 (m 2 ) 12.525.050.0100.0200.0 ng/ml,,,, :
18 6 SR 1 1 ( cx c) c ( x ) ; b p n 2 ( c c) n i i i1 i1 y ( bc a) 2 SR n 2, S R ; ab ; p, p=2; n, n=5; c x ; c i ; c, c =77.5 μg/l, y i i 2.5, GB 276-2012 0.006 mg/kg, 24 ng/ml, c x () 24.60 ng/ml, c x () 25.25 ng/ml 1 2 1 S R, S R ()= 568.1 ng/ml, S R ()= 465.0 ng/ml 2 c x c S R (c x ), (m 2 ) i 2 5. 样品的非均匀性引入的不确定度 (m ) F rep, F 1,,,,, (m ) 0 5.4 样品称量引入的不确定度 (m 4 ) 20.000 g, A, ±0.1 mg,, k=, 0.0001 m ( 4 ) 0.00006, (m 4 )=0.00000 5.5 样品处理后定容引入的不确定度 (m 5 ) 5 ml, 5 ml A ±0.015 ml,, k, 0.015 m ( 4) 0.0087, (m 5 )=0.0017 5.6 样品前处理过程引入的不确定度 (m 6 ),,, 6, H, Table 1 表 1 艾氏剂 狄氏剂标准系列溶液测定结果 Measrement reslts of standard series soltion of aldrin and dieldrin (ng/ml) 12.5 25.0 50.0 100 200 129.8 7000.0 16781.2 518.1 70297. Y=54.5C1514.5 2680. 6020.1 1567.1 27450.9 5780.2 Y=291.1C1120.1 Table 2 表 2 艾氏剂 狄氏剂标准曲线引入的相对不确定度 (m 2 ) Relative ncertainty introdced by standard crve of aldrin and dieldrin c x (ng/ml) c (ng/ml) S R (ng/ml) c ( x) (ng/ml) ( m 2) 24.60 77.5 568.1 1.451 0.0590 25.25 77.5 465.0 1.186 0.0470
1, : 19 Table 表 样品前处理过程引入的相对不确定度 (m 6 ) Relative ncertainty introdced by the sample preparation process. (μg/kg) H 1 (%) H 2 (%) H (%) s(h)(%) (m 6 ) 81.9 82.7 6 88.6 87.4 10 90.2 91.1 78.9 79.1 6 82.1 82.9 10 84.6 8.4 87.0.85 0.044 81.8 2.4 0.0286 表 4 6 份模拟样品中农药残留测定结果 Table 4 Reslts of pesticide resides in 6 samples 1 2 4 5 6 c s(c) (m 7 ) (μg/kg) 5.25 5.14 5.29 5.11 5.15 5.1 5.21 0.0854 0.0164 (μg/kg) 4.95 4.85 4.96 4.87 4.9 5.02 4.9 0.062 0.0126 5.7 测量重复性引入的不确定度 (m 7 ), GB 276-2012 0.006 mg/kg, 6 6 (n=6), 4, 5.8 相对合成标准不确定度和相对扩展不确定度,, : c c ( 1 ( 2 ( ( 4 m) m) m) m) ( w艾氏剂 ) 0.076 m) m) m) 2 ( 5 ( 6 ( 7 ( 1 ( 2 ( ( 4 m) m ) m) m ) ( w艾氏剂 ) 0.057 m) m ) m ) 2 ( 5 ( 6 ( 7 k=2, 95%, : U( w ) 2 ( w 5.21 0.79; 艾氏剂 c 艾氏剂 ) U( w狄氏剂 ) 2 c ( w狄氏剂 ) 4.9 0.56 6 讨论 (1),,,, (2),,, [10,11] [12], [1,14], [15] (),,, 参考文献 [1],,,. - [J]. (), 2011, 4(4): 508512. Pang YH, H XJ, Sn XQ, et al. Determination of reside in food of aldrin and dieldrin gas chromatography-mass spectrometry [J]. J Liaoning Normal Univ (Nat Sci Edit), 2011, 4(4): 508512. [2]. [J].,
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