溶解沉淀-气相色谱-串联质谱法测定塑料玩具中的58种致敏性芳香剂
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摘要
基于溶解沉淀-气相色谱-串联质谱(GC-MS/MS)技术,建立了ABS和PVC塑料玩具中58种致敏性芳香剂的同时测定方法。玩具样品在经四氢呋喃溶解、甲醇沉淀后,取上清液过0.22μm滤膜后检测,通过DB-17MS色谱柱分离,串联质谱多反应监测模式(SRM)测定,外标法定量。对色谱-质谱条件进行优化,通过测定自制阳性样品的回收率,证明溶解沉淀法具有较高的提取率。实验结果表明,GC-MS/MS具有较强的抗基质背景干扰能力,由于存在溶剂效应和基质效应,需要采用空白基质匹配的标准曲线进行定量分析。方法对于不同物质的定量限(LOQ)为0.1～10 mg/kg,在线性范围0.1～600 mg/kg内相关系数(R2)大于0.9926,在ABS和PVC样品中的回收率分别为76. 9%～129. 6%和70. 3%～126. 5,相对标准偏差(RSD,n=6)在0.9%～10.2%和1.1%～9.6%之间。最后,对市售的65个玩具样品进行检测,检出的10种芳香剂含量在3.0～46.8 mg/kg之间。本方法简便、快速、准确、灵敏,适用于塑料玩具中58种致敏性芳香剂的检测。
A method was developed for simultaneous determination of 58 kinds of fragrance allergens in acrylonitrile-butadiene-styrene( ABS) and polyvinyl chloride( PVC) plastic toys based on dissolution precipitation-gas chromatography tandem mass spectrometry( GC-MS/MS). Sample was dissolved by tetrahydrofuran,and precipitated by methanol,and then its supernatant was taken through a 0. 22-μm filter membrane. After separated by DB-17 MS column,the analytes were determined by tandem mass spectrometry in SRM mode,and then quantified by the external standard method. The study optimized the GC-MS parameters for determination of 58 analytes and further proved that the dissolution precipitation method had a high extraction rate by determining the recovery of the homemade positive sample. Its results showed that GCMS/MS had strong anti-matrix background interference ability. Due to the existence of solvent effect and matrix effect,the matrix matching standard curve method should be used for quantitative analysis. The limits of quantification( LOQs) for different substances were 0.1-10 mg/kg,and the correlation coefficient( R2) was larger than 0. 9926 in the linear range of 0. 1-600 mg/kg. The recoveries of fragrances in ABS and PVC samples ranged from 76.9% to 129.6% and 70.3% to 126.5%,respectively. The relative standard deviations( RSD,n = 6) ranged from 0.9% to 10.2% and 1.1% to 9.6%,respectively. Finally,65 commercial toys were detected,and the contents of 10 fragrances ranged from 3.0 to 46.8 mg/kg. The method was simple,rapid,accurate,sensitive and low cost,and suitable for the detection of 58 fragrance allergens in plastic toys.
A method was developed for simultaneous determination of 58 kinds of fragrance allergens in acrylonitrile-butadiene-styrene( ABS) and polyvinyl chloride( PVC) plastic toys based on dissolution precipitation-gas chromatography tandem mass spectrometry( GC-MS/MS). Sample was dissolved by tetrahydrofuran,and precipitated by methanol,and then its supernatant was taken through a 0. 22-μm filter membrane. After separated by DB-17 MS column,the analytes were determined by tandem mass spectrometry in SRM mode,and then quantified by the external standard method. The study optimized the GC-MS parameters for determination of 58 analytes and further proved that the dissolution precipitation method had a high extraction rate by determining the recovery of the homemade positive sample. Its results showed that GCMS/MS had strong anti-matrix background interference ability. Due to the existence of solvent effect and matrix effect,the matrix matching standard curve method should be used for quantitative analysis. The limits of quantification( LOQs) for different substances were 0.1-10 mg/kg,and the correlation coefficient( R2) was larger than 0. 9926 in the linear range of 0. 1-600 mg/kg. The recoveries of fragrances in ABS and PVC samples ranged from 76.9% to 129.6% and 70.3% to 126.5%,respectively. The relative standard deviations( RSD,n = 6) ranged from 0.9% to 10.2% and 1.1% to 9.6%,respectively. Finally,65 commercial toys were detected,and the contents of 10 fragrances ranged from 3.0 to 46.8 mg/kg. The method was simple,rapid,accurate,sensitive and low cost,and suitable for the detection of 58 fragrance allergens in plastic toys.
引文
1 Basketter D,Kimber I. Regul. Toxicol. Pharm.,2015,73:897-902
2 Smith V M,Clark S M,Wilkinson M. Contact Dermatitis,2016,74:37-43
3 Wolkoff P,Nielsen G D. Environ. Int.,2017,101:96-107
4 Directive 2009/48/EC of the European Parliament and of the Council of 18 June 2009 on the Safety of Toys
5 BS EN 71-13:2014 Safety of toys-Part 13:Olfactory board games,cosmetic kits and gustative games
6 Rastogi S C,Johansen J D,Menne T,Frosch P,Bruze M,Andersen K E,Lepoittevin J P,Wakelin S,White I R. Contact Dermatitis,1999,41:84-88
7 Masuck I,Hutzler C,Luch A. J. Chromatogr. A,2010,1217:3136-3143
8 Masuck I,Hutzler C,Luch A. Anal. Methods,2013,5:508-515
9 LYU Qing,ZHANG Qing,BAI Hua,LI Hai-Yu,KANG Su-Yuan,WANG Chao. Chinise Journal of Chromatography,2012,30(7):480-486吕庆,张庆,白桦,李海玉,康苏媛,王超.色谱,2012,30(7):480-486
10 Wang Z,Zhang Q,Li H,Lv Q,Wang W,Bai H. J. Sep. Sci.,2017,41:657-668
11 LI Hai-Yu,BAI Hua,LYU Qing,LI Pi,WANG Ye,GUO Xiang-Yu,ZHANG Qing. Chinese J. Anal. Chem.,2013,41(10):1518-1525李海玉,白桦,吕庆,李丕,王烨,郭项雨,张庆.分析化学,2013,41(10):1518-1525
12 Lv Q,Zhang Q,Li W,Li H,Li P,Ma Q,Meng X,Qi M,Bai H. J. Sep. Sci.,2013,36:3534-3549
13 LYU Qing,WANG Zhi-Juan,ZHANG Qing,MA Qiang,BAI Hua,CAI Ya-Qi. Chinese J. Anal. Chem.,2018,46(8):1314-1320吕庆,王志娟,张庆,马强,白桦,蔡亚岐.分析化学,2018,46(8):1314-1320
14 Garrigós M C,Marín M L,CantóA,Sánchez A. J. Chromatogr. A,2004,1061:211-216
15 Al-Natsheh M,Alawi M,Fayyad M,Tarawneh B. J. Chromatogr. B,2015,985:103-109
16 WU Li-Li,SHEN Bing,YING Xiao-Hong,KONG Fan-Di. Chinese J. Anal. Chem.,2012,40(4):617-621吴莉莉,沈兵,应晓虹,孔繁迪.分析化学,2012,40(4):617-621
17 CUI Shu-Hua,NIU Zeng-Yuan,ZHANG Xiao-Mei,QIN Liang-Yong,LUO Xin. Journal of Chinese Mass Spectrometry Society,2016,37(2):163-172崔淑华,牛增元,张晓梅,秦良勇,罗忻.质谱学报,2016,37(2):163-172
18 Lamas J P,Sanchez-Prado L,Garcia-Jares C,Lores M,Llompart M. J. Chromatogr. A,2010,1217:8087-8094
19 Tsiallou T P,Sakkas V A,Albanis T A. J. Sep. Sci.,2012,35:1659-1666
20 Masuck I,Hutzler C,Luch A. J. Sep. Sci.,2011,34:2686-2696
21 Shen H Y. Talanta,2005,66:734-739
2 Smith V M,Clark S M,Wilkinson M. Contact Dermatitis,2016,74:37-43
3 Wolkoff P,Nielsen G D. Environ. Int.,2017,101:96-107
4 Directive 2009/48/EC of the European Parliament and of the Council of 18 June 2009 on the Safety of Toys
5 BS EN 71-13:2014 Safety of toys-Part 13:Olfactory board games,cosmetic kits and gustative games
6 Rastogi S C,Johansen J D,Menne T,Frosch P,Bruze M,Andersen K E,Lepoittevin J P,Wakelin S,White I R. Contact Dermatitis,1999,41:84-88
7 Masuck I,Hutzler C,Luch A. J. Chromatogr. A,2010,1217:3136-3143
8 Masuck I,Hutzler C,Luch A. Anal. Methods,2013,5:508-515
9 LYU Qing,ZHANG Qing,BAI Hua,LI Hai-Yu,KANG Su-Yuan,WANG Chao. Chinise Journal of Chromatography,2012,30(7):480-486吕庆,张庆,白桦,李海玉,康苏媛,王超.色谱,2012,30(7):480-486
10 Wang Z,Zhang Q,Li H,Lv Q,Wang W,Bai H. J. Sep. Sci.,2017,41:657-668
11 LI Hai-Yu,BAI Hua,LYU Qing,LI Pi,WANG Ye,GUO Xiang-Yu,ZHANG Qing. Chinese J. Anal. Chem.,2013,41(10):1518-1525李海玉,白桦,吕庆,李丕,王烨,郭项雨,张庆.分析化学,2013,41(10):1518-1525
12 Lv Q,Zhang Q,Li W,Li H,Li P,Ma Q,Meng X,Qi M,Bai H. J. Sep. Sci.,2013,36:3534-3549
13 LYU Qing,WANG Zhi-Juan,ZHANG Qing,MA Qiang,BAI Hua,CAI Ya-Qi. Chinese J. Anal. Chem.,2018,46(8):1314-1320吕庆,王志娟,张庆,马强,白桦,蔡亚岐.分析化学,2018,46(8):1314-1320
14 Garrigós M C,Marín M L,CantóA,Sánchez A. J. Chromatogr. A,2004,1061:211-216
15 Al-Natsheh M,Alawi M,Fayyad M,Tarawneh B. J. Chromatogr. B,2015,985:103-109
16 WU Li-Li,SHEN Bing,YING Xiao-Hong,KONG Fan-Di. Chinese J. Anal. Chem.,2012,40(4):617-621吴莉莉,沈兵,应晓虹,孔繁迪.分析化学,2012,40(4):617-621
17 CUI Shu-Hua,NIU Zeng-Yuan,ZHANG Xiao-Mei,QIN Liang-Yong,LUO Xin. Journal of Chinese Mass Spectrometry Society,2016,37(2):163-172崔淑华,牛增元,张晓梅,秦良勇,罗忻.质谱学报,2016,37(2):163-172
18 Lamas J P,Sanchez-Prado L,Garcia-Jares C,Lores M,Llompart M. J. Chromatogr. A,2010,1217:8087-8094
19 Tsiallou T P,Sakkas V A,Albanis T A. J. Sep. Sci.,2012,35:1659-1666
20 Masuck I,Hutzler C,Luch A. J. Sep. Sci.,2011,34:2686-2696
21 Shen H Y. Talanta,2005,66:734-739
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