高效液相色谱-四极杆飞行时间质谱测定塑料中短链氯化石蜡

注册 English

高效液相色谱-四极杆飞行时间质谱测定塑料中短链氯化石蜡

周熙 , 吴惠勤 , 黄芳 , 黄晓兰 , 林晓珊 , 侯思润 , 李荣锡

引用本文: 周熙, 吴惠勤, 黄芳, 黄晓兰, 林晓珊, 侯思润, 李荣锡. 高效液相色谱-四极杆飞行时间质谱测定塑料中短链氯化石蜡[J]. 分析化学, 2019, 47(4): 519-526. doi: 10.19756/j.issn.0253-3820.181646 shu

shu

Citation: ZHOU Xi, WU Hui-Qin, HUANG Fang, HUANG Xiao-Lan, LIN Xiao-Shan, HOU Si-Run, LI Rong-Xi. Determination of Short Chain Chlorinated Paraffins in Plastic by High Performance Liquid Chromatography Coupled with Electron Spray Ionization Quadrupole Time-of-flight Mass Spectrometry[J]. Chinese Journal of Analytical Chemistry, 2019, 47(4): 519-526. doi: 10.19756/j.issn.0253-3820.181646 shu

shu

高效液相色谱-四极杆飞行时间质谱测定塑料中短链氯化石蜡

广东省测试分析研究所, 广东省化学危害应急检测技术重点实验室, 广东省分析测试技术公共实验室, 广州 510070
基金项目:
本文系广东省实施创新驱动发展能力建设专项资金项目（No.2018GDASCX-0919）资助

摘要: 建立了固相萃取结合高效液相色谱-电喷雾离子化-四极杆串联飞行时间质谱（HPLC-ESI-QTOF/MS）测定塑料制品中短链氯化石蜡（SCCPs）的方法。在ESI离子源中，无需添加氯代有机溶剂，以[M-H]^-离子检测。选取C_10-13，Cl_5-13共30个SCCPs分子中丰度最高的两个同位素峰为定量与定性离子，通过高分辨质谱的精确质量数排除了相近分子量中链氯化石蜡（MCCPs）的干扰，解决了低分辨质谱对SCCPs检测结果不佳的问题。样品经二氯甲烷超声提取，提取液经硅胶柱净化，用正己烷-二氯甲烷（4∶1，V/V）洗脱。氯含量51.5%~63.0%的SCCPs仪器检出限为0.01~0.05 mg/L，方法检出限与定量限分别为1.4和4.6 μg/g。在5、20和50 μg/g加标水平下，回收率分别为118.0%±8.2%、81.9%±6.9%、77.8%±6.6%，日内相对标准偏差与日间相对标准偏差分别为5.7%与8.1%。对已知C_10-13含量的烷烃原料氯化后SCCPs含量进行测定，结果表明，烷烃中C_10-13含量与氯化后SCCPs含量一致，表明本方法的检测结果准确。4类塑料制品中SCCPs的测定结果表明，电缆与跑道中SCCPs含量较高（555~1049 μg/g），玩具中SCCPs浓度较低（1.86~6.56 μg/g）。

关键词:

English

Determination of Short Chain Chlorinated Paraffins in Plastic by High Performance Liquid Chromatography Coupled with Electron Spray Ionization Quadrupole Time-of-flight Mass Spectrometry

Guangdong Provincial Key Laboratory of Emergency Test for Dangerous Chemicals, Guangdong Provincial Public Laboratory of Analysis and Testing Technology, Guangdong Institute of Analysis, Guangzhou 510070, China
Received Date: 31 October 2018
Revised Date: 26 December 2018
Fund Project:
This work was supported by the Provincial Innovative Talents Introduction Foundation of Guangdong, China (No. 2018GDASCX-0919).

Abstract: A method of high performance liquid chromatography coupled with electron spray ionization quadrupole time-of-flight mass spectrometry was established for analysis of short chain chlorinated paraffins (SCCPs) in plastic. No chlorine solvent was added and SCCPs were quantified by their[M-H]^- ions. For each congener group of SCCPs with carbon chain lengths in 10-13 and chlorine substituents in 5-13, the two most abundant m/z signals were extracted from the full-scan mass spectra as the quantitative and qualitative ions. The influence of medium chain chlorinated paraffins (MCCPs) was eliminated efficiently based on the high resolution of the mass spectrometry. Plastic samples were extracted by dichloride methane and purified by silica gel solid phase extraction column. SCCPs were eluted by hexane/dichloride methane (1:1, V/V). The instrumental detection limits (IDLs) were 0.01-0.05 mg/L for SCCPs with chlorine content from 51.5%-63%. Method detection limit (MDL) and quantitative limit were 1.4 μg/g and 4.6 μg/g, respectively. Recoveries of SCCPs were 118.0%±8.2%, 81.9%±6.9% and 77.8%±6.6%, at spiking concentrations of 5 μg/g, 20 μg/g and 50 μg/g, respectively. The intra- and inter-day variations were 5.7% and 8.1%, respectively. The quantitative results verified that SCCPs concentration in CPs were similar with the short chain alkane in the corresponding paraffin, which demonstrated the accuracy of this method. This method was applied in determination of four kinds of plastic samples. Cable and track presented to have a high concentration of SCCPs within the range of 555-1049 μg/g. Plastic toys had lower concentrations of SCCPs in the range of 1.86-6.56 μg/g.

Key words:

1. [1]
  Zeng L X, Wang T, Ruan T, Liu Q, Wang Y W, Jiang G B. Environ. Pollut.,2012,160(1):88-94
2. [2]
  Xia D, Gao L R, Zheng M H, Tian Q C, Huang H T, Qiao L. Environ. Sci. Technol.,2016,50(14):7601-7609
3. [3]
  Xia D, Gao L, Zhu S, Zheng M H. Anal. Bioanal. Chem.,2014,406(29):7561-7570
4. [4]
  Krätschmer K, Cojocariu C, Schächtele A, Malisch R, Vetter W. J. Chromatogr. A,2018,1539:53-61
5. [5]
  Koh I, Rotard W, Thiemann H P. Chemosphere,2002, 47(2):219-227
6. [6]
  HUANG Shao-Jun, DU Ping, LIU Chun-Xia, YANG Jun, YANG Chao-Fen, SUN Hui, HUANG Qiu-Ling. Chinese Journal of Chromatography,2018,36(10):1022-1027 绍军, 杜萍, 刘春侠, 杨俊, 杨朝芬, 孙卉, 黄秋玲.色谱,2018,36(10):1022-1027
7. [7]
  Zencak Z, Borgen A, Reth M, Oehme M. J. Chromatogr. A,2005,1067(1):295-301
8. [8]
  Korytar P, Parera J, Leonards P E G, Santos F J, de Boer J, Brinkman U A T. J. Chromatogr. A,2005,1086(1-2):71-82
9. [9]
  Zencak Z, Borgen A, Reth M, Oehme M. Anal. Chem.,2003,75(10):2487-2492
10. [10]
  Liu LH, Ma W L, Liu L Y, Huo C Y, Li W L, Gao C J, Li H L, Li Y F, Chan H M. Environ. Pollut.,2017,225:232-243
11. [11]
  Houde M, Muir D C, Tomy G T, Whittle D M, Teixeira C, Moore S. Environ. Sci. Technol.,2008,42(10):3893-3899
12. [12]
  Ma X D, Zhang H J, Wang Z, Yao Z W, Chen J W, Chen J P. Environ. Sci. Technol.,2014,48(10):5964-5971
13. [13]
  GB 36246-2018, Sports Areas with Synthetic Surfaces for Primary and Middle Schools. National Standards of the People's Republic of China 小学合成材料面层运动场地.中华人民共和国国家标准. GB 36246-2018
14. [14]
  Koh I, Rotard W, Thiemann W H P. Chemosphere,2002,47(2):219-227
15. [15]
  Francesca P, Marina R, Andrea H,Hendrik E. Organohalogen Compd.,2008,70:776-780
16. [16]
  Li T, Gao S X, Ben Y J, Zhang H, Kang Q Y, Wan Y. Environ. Sci. Technol.,2018,52(4):1862-1870
17. [17]
  Bogdal C, Alsberg T, Diefenbacher P S, Macleod M, Berger U. Anal. Chem.,2015,87(5):2852-2860
18. [18]
  Reth M, Zencak Z, Oehme M. J. Chromatogr. A,2005,1081(2):225-231
19. [19]
  Castells P, Santos F J, Galceran M T. J. Chromatogr. A,2004,1025(2):157-162
20. [20]
  Zencak Z, Oehme M. Rapid Commun. Mass Spectrom.,2004,18(19):2235-2240
21. [21]
  ZHANG Wei-Ya, WAN Xin, LI Li-Xia, WANG Cheng-Yun, JIN Shu-Pei, XING Jun. Chinese Journal of Chromatography,2014,32(10):1152-1156 伟亚, 万昕, 李丽霞, 王成云, 金淑培, 邢钧.色谱, 2014, 32(10):1152-1156
22. [22]
  XU Ling, WEN Huan, WEN Fu-Qian, QIU Li-Min, YU Ying-Feng. Guangdong Chemical Industry,2017,44(12):101-102 玲, 闻环, 温佛钱, 邱丽敏, 余映枫. 广东化工,2017,44 (12):101-102
23. [23]
  YUAN Bo, WANG Ya-Wei, FU Jian-Jie, ZHANG Qing-Hua, JIANG Gui-Bin. Chinese Science Bulletin,2010,55(19):1879-1885 博, 王亚韡, 傅建捷, 张庆华, 江桂斌. 科学通报,2010,55(19):1879-1885
24. [24]
  Li T, Wan Y, Gao S X, Wang B L, Hu J Y. Environ. Sci. Technol.,2017,51:3346-3354

WeChat

扫一扫看文章

计量

PDF下载量: 22
文章访问数: 925
HTML全文浏览量: 107

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

/

下载: 全尺寸图片幻灯片

分享

用微信扫码二维码

分享至好友和朋友圈