7 1 Vol. 7 No. 1 2016 1 Journal of Food Safety and Quality Jan., 2016 李锦花 1*, 李赛花 2, 许海峰 1, 陈丹超 1, 马明 (1., 315012; 2., 315040) 1 摘要 : 目的 方法 ( ) 1 cm 1 cm,, - (1:1, V:V), 150, 1500 psi, 10 min, 3, -,, 226 nm 结果 8 PBDEs 95%~105%, (n=6) RSD<3%, 0.1~0.2 μg/ml, >0.999 结论 GB/Z 21276-2007, ( ) PBDEs 关键词 : ; ; ( ); Determination of polybrominated diphenyl ethers in corrugated box (cardboard) by accelerated solvent extraction-high performance liquid chromatography LI Jin-Hua 1*, LI Sai-Hua 2, XU Hai-Feng 1, CHEN Dan-Chao 1, MA Ming 1 (1. Technology Center of Ningbo Entry-Exit Inspection and Quarantine Bureau, Ningbo 315012, China; 2. Societe Generale de Surveillance S.A.-China Standard Technology Development Corp. Standards Technical Services Co., Ltd. Ningbo Branch, Ningbo 315040, China) ABSTRACT: Objective To establish a method for the determination of polybrominated diphenyl ethers (PBDEs) in corrugated box (cardboard) by high performance liquid chromatography (HPLC) with accelerated solvent extraction. Methods The corrugated box (cardboard) was cut to 1 cm 1 cm. The PBDEs were extracted with ethanol: acetone (1:1, V:V) as extraction solvent in 10 min with static extraction mode and repeated three times by accelerated solvent extraction (ASE) at 150 and pressure of 1500 psi. The extraction was analyzed by HPLC after using a gradient elution program of methanol-h 2 O as mobile phase, and detected at 226 nm. Results The recoveries of 8 PBDEs were 95%~105%, the relative standard deviations (RSDs) were under 3% (n=6), the limits of detection were 0.1~0.2 μg/ml, and the linear regression coefficients were above 0.9991. Conclusion The analysis results of PBDEs were satisfied by comparing with the standard method GB/Z 21276-2007. It can be used for the detection of PBDEs in the corrugated box (cardboard). KEY WORDS: accelerated solvent extraction; high performance liquid chromatography; corrugated box (cardboard); polybrominated diphenyl ethers 基金项目 : (2013IK210 2014IK075) Fund: Supported by Scientific Research Project of National Quality Supervision, Inspection and Quarantine Bureau (2013IK210, 2014IK075) * 通讯作者 :,, E-mail: lijh@nbciq.gov.cn *Corresponding author: LI Jin-Hua, Engineer, Technical Center of Ningbo Entry-Exit Inspection and Quarantine Bureau, Ningbo 315012, China. E-mail: lijh@nbciq.gov.cn
160 7 1 引言 (polybrominated diphenyl ethers, PBDEs),, 209 PBDEs,,, PBDEs [1], PBDEs,,, [2], [3] PBDEs, PBDEs [4-6], PBDEs, WEEE [7] RoHS [8] PBDEs, (GC) (GC-MS) (LC) (LC-MS), PBDEs, GC-MS (HPLC-MS),,, [9], 12 min, (HPLC-MS/MS),, [1] PBDEs,, -(1:1, V:V) (ASE),, [10,11] [12] [13] [14] [15],, - (1:1, V:V),,,,,, ( ) ( ), ( ) 2 材料与方法 2.1 材料 2.1.1 试验材料 ( ), 7, 3 ; ProElut Silica; 0.45 μm ( ) 2.1.2 仪器与试剂 (ASE 300, Dionex ), 34 ml ; (Allaince 2695e-2998, Waters ); (R-210, BUCHI ); Milli-Q (A-10, Millipore ), ;, ; AccuStandard ( 2,4,4-19.94 μg/ml; 2,2,4,4-20.08 μg/ml; 2,2,4,4,5-19.84 μg/ml; 2,2,4,4, 6-20.38 μg/ml; 2,2,4,4,5,5-19.92 μg/ml; 2,2,4,4,5,6-20.06 μg/ml; 2,2,3,4,4,5,6-20.38 μg/ml; 2,2,3,3,4,4, 5,5,6,6-39.36 μg/ml) Milli-Q, 18.2 ΜΩ 2.2 方法 2.2.1 V( ): V( )=4: 1 1,,, 2.2.2 色谱分离条件 SunFire C 18 (250 mm 4.6 mm, 5 μm),, : 0~10 min 90% (V:V), 1 ml/min; 10~18 min 100%, 1 ml/min; 18~28 min 100%, 1 ml/min; 28~32 min 90% (V:V), 1 ml/min 226 nm, 35, 10 μl,
1, : - ( ) 161 Table 1 表 1 标准曲线多溴二苯醚浓度 Concentration of polybrominated diphenyl ethers for standard curve (PBDEs) 1 2 3 4 5 2,4,4 -tribromodiphynyl ether 0.997 4.985 9.97 14.955 19.94 2,2 4,4 -tetrabromodiphenyl ether 1.004 5.02 10.04 15.06 20.08 2,2,4,4,5-pentabromodiphenyl ether 0.992 4.96 9.92 14.88 19.84 2,2,4,4,6-pentabromodiphenyl ether 1.019 5.095 10.19 15.285 20.38 2,2,4,4,5,5 -hexabromodiphyenyl ether 0.996 4.98 9.96 14.94 19.92 2,2,4,4,5,6 -hexabromodiphenyl ether 1.003 5.015 10.03 15.045 20.06 2,2,3,4,4,5,6-heptabromodiphenyl ether 1.019 5.095 10.19 15.285 20.38 2,2,3,3,4,4,5,5 6,6 -decabromodiphenyl ether 1.968 9.84 19.68 29.52 39.36 2.2.3 加速溶剂萃取 1 cm 1 cm, 1.0 g 34 ml, ; V( ): V( )=1: 1, 150, 1500 psi, 7 min, 10 min, 3, 2.2.4 固相萃取净化 50 5 ml, 10 ml,, 50, V( ): V( )=4: 1 10 ml 2.2.5 对照实验 GB/Z 21276-2007 [16] 3 结果与分析 3.1 色谱条件的优化 PBDEs, C 18, PBDEs,, 2.2.2 3.2 加速溶剂萃取条件的优化 3.2.1 萃取溶剂的选择, PBDEs, PBDEs [9] PBDEs,,,,, PBEDs, PBDEs, PBDEs : 1 2 3 4 5+ (1:1, V:V) 6 + (1:1, V:V) 7+ (1:1, V:V),, + (1:1, V:V) + (1:1, V:V) + (1:1, V:V), PBDEs ;,,, 70%,,, + (1:1, V:V),,, + (1:1, V:V) 3.2.2 萃取温度对萃取效率的影响,,, + (1:1, V:V), 80 ~175, 100%, 1
162 7 100%,, <5 min, <95%, 8 min, 99%,,,, 10 min 1 Fig. 1 Effect of extraction temperature on extraction efficiency 1, 120, 98%, 150, 99%,, 150 3.2.3 萃取次数对萃取效率的影响, PBDEs,, 3,, 3 3.2.4 萃取时间对萃取效率的影响, + (1:1, V:V), 150, 3, 3 5 8 10 15 min, 3.3 标准曲线 线性范围 相关系数 检出限和重现性 PBDEs 1 PBDEs,, 2 2, 8 0.999, 2,2 4,4-2,2,4,4,5-0.2 μg/ml, 0.1 μg/ml, RSD 3% 2,2,3,3,4,4,5,5,6,6-20 μg/ml, 20 μg/ml( 40 μg/ml) 3.4 样品检测 10, PBDEs, HPLC PBDEs, 1 2a, 2b,, GB/Z 21276-2007, GC/MS PBDEs, 3 Table 2 表 2 标准曲线 线性范围 相关系数 检出限和重现性 Linear equation, linear range, correlation coefficient, LOD and RSD PBDEs (r 2 ) RSD (%, n=6) 2,4,4 -tribromodiphynyl ether Y=11222+30676X 0.9999 0.5~20 0.1 2.89 2,2 4,4 -tetrabromodiphenyl ether Y =17704+13538 X 0.9999 1~20 0.2 2.03 2,2,4,4,5-pentabromodiphenyl ether Y =30087+32906 X 1.0000 1~20 0.2 1.98 2,2,4,4,6-pentabromodiphenyl ether Y =20735+35185 X 0.9999 0.5~20 0.1 2.82 2,2,4,4,5,5 -hexabromodiphyenyl ether Y =23178+36917 X 0.9995 0.5~20 0.1 2.97 2,2,4,4,5,6 -hexabromodiphenyl ether Y =88348+33021 X 0.9991 0.5~20 0.1 2.43 2,2,3,4,4,5,6-heptabromodiphenyl ether Y =32318+44332 X 0.9996 0.5~20 0.1 2.64 2,2,3,3,4,4,5,5 6,6 -decabromodiphenyl ether Y =247999+230271 X 0.9999 0.5~40 0.1 2.34
1, : - ( ) 163 2 (a) (b) Fig. 2 Chromatograms of PBDEs standards solution(a) and sample(b) (1-2,4,4 - ; 2-2,2 4,4 - ;3-2,2,4,4,5- ; 4-2,2,4,4,6- ;5-2,2,4,4,5,5 - ; 6-2,2,4,4,5,6 - ;7-2,2,3,4,4,5,6- ; 8-2,2,3,3,4,4,5,5 6,6 - ) (1-2,4,4 -tribromodiphynyl ether; 2-2,2 4,4 -tetrabromodiphenyl ether;3-2,2,4,4,5-pentabromodiphenyl ether; 4-2,2,4,4,6-pentabromodiphenyl ether; 5-2,2,4,4,5,5 -hexabromodiphyenyl ether; 6-2,2,4,4,5,6 -hexabromodiphenyl ether; 7-2,2,3,4,4,5,6-heptabromodiphenyl ether; 8-2,2,3,3,4,4,5,5 6,6 -decabromodiphenyl ether) 表 3 加速溶剂萃取 - 高效液相色谱法分析瓦楞纸中多溴二苯醚含量的结果 (n=6) Table 3 Results of PBDEs concentration in corrugated box (cardboard) by ASE-HPLC (n=6) ASE-HPLC PBDEs (%) RSD (%) * 2,4,4 -tribromodiphynyl ether N.D. 20.0 21.0 105 2.89 N.D. 2,2 4,4 -tetrabromodiphenyl ether N.D. 20.0 19.0 95.0 2.03 N.D. 2,2,4,4,5-pentabromodiphenyl ether N.D. 20.0 20.0 100 1.98 N.D. 2,2,4,4,6-pentabromodiphenyl ether N.D. 20.0 19.0 95.0 2.82 N.D. 2,2,4,4,5,5 -hexabromodiphyenyl ether N.D. 20.0 20.0 100 2.97 N.D. 2,2,4,4,5,6 -hexabromodiphenyl ether N.D. 20.0 21.0 105 2.43 N.D. 2,2,3,4,4,5,6-heptabromodiphenyl ether N.D. 20.0 21.0 105 2.64 N.D. 2,2,3,3,4,4,5,5 6,6 -decabromodiphenyl ether 10.6 20.0 30.5 99.5 2.34 10.6 *: GB/Z 21276-2007, N.D.
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