食品中有机磷酸酯阻燃剂检测技术的研究进展

引用本文: 杨吉双, 张庆合, 苏立强. 食品中有机磷酸酯阻燃剂检测技术的研究进展[J]. 色谱, 2020, 38(12): 1369-1380. doi: 10.3724/SP.J.1123.2020.03026 shu

Citation: YANG Jishuang, ZAHNG Qinghe, SU Liqiang. Advances in the development of detection techniques for organophosphate ester flame retardants in food[J]. Chinese Journal of Chromatography, 2020, 38(12): 1369-1380. doi: 10.3724/SP.J.1123.2020.03026 shu

食品中有机磷酸酯阻燃剂检测技术的研究进展

1.
齐齐哈尔大学化学与化学工程学院, 黑龙江齐齐哈尔 161006;
2.
中国计量科学研究院化学计量与分析科学研究所, 北京 100029

通讯作者: 张庆合, E-mail:zhangqh@nim.ac.cn

基金项目:
公益性科研院所基本科研项目（AKYZD1906）.

摘要: 有机磷酸酯（OPEs）是阻燃剂和塑化剂的主要原料，通常以添加形式存在于各种材料中，在生产和使用过程中伴随磨损和挥发易释放到环境中，现已成为新兴污染物。因为该类化合物的神经毒性、致癌性、破坏内分泌系统以及生殖系统等毒性，食品样品中OPEs的检测成为近年来关注的热点。该文重点围绕食品基质中OPEs检测存在的含量低、本底干扰严重、缺乏灵敏可靠分析方法等问题，对OPEs类化合物的性质、样品前处理、检测技术、质量控制等进行了全面评述。首先总结了30余种常见OPEs类化合物的类型、官能团、极性、沸点等理化性质，对可能的前处理和检测技术进行了理论分析；其次梳理了加速溶剂萃取（ASE）、基质固相分散萃取（MSPD）、微波辅助萃取（MAE）、超声辅助萃取（UAE）、QuEChERS、固相萃取（SPE）、凝胶渗透色谱（GPC）、分散固相萃取（d-SPE）等前处理方法在食品中OPEs化合物分析中的特点，其中UAE和QuEChERS结合多步净化能够有效降低高脂类食品的基质效应，具有良好应用前景；此外比较了气相色谱和液相色谱在分离和检测方面的优缺点，比较已有文献的检出限、回收率等数据；概括了标准品和内标物来源、过程污染与基质效应的产生原因和预防措施；最后对高分辨质谱筛查和鉴别OPEs未知代谢物，以及相关分析方法趋势进行了展望。

关键词:

English

Advances in the development of detection techniques for organophosphate ester flame retardants in food

1.
College of Chemistry and Chemical Engineering, Qiqihar University, Qiqihar 161006, China;
2.
Division of Chemical Metrology and Analytical Science, National Institute of Metrology, Beijing 100029, China

Corresponding author: ZAHNG Qinghe, zhangqh@nim.ac.cn

Received Date: 23 March 2020
Fund Project:
Basic Research Projects of Non-Profit Research Institutes (No. AKYZD1906).

Abstract: Organophosphate ester (OPE)-based flame retardants and plasticizers are widely utilized in various industrial products, and are being increasingly used as substitutes for gradually phased brominated flame retardants (BFRs). According to the different types of substituents used, OPEs are mainly divided into alkyls, halogenated compounds, and aromatics, which have widely varying physicochemical properties. OPEs can induce neurotoxicity, carcinogenicity, and damage in endocrine and reproductive systems in humans. Examples of halogenated OPE are tris(2-chloroisopropyl) phosphate (TCIPP) and tris(1,3-dichloropropyl) phosphate (TDCIPP), which are suspected to be carcinogenic. OPEs have emerged as pollutants in environmental and food matrices as a result of volatilization and abrasion processes. Due to its low content in the food matrix and serious background interference, there is a lack of reliable and sensitive analytical methods. Recently, there has been a focus on the detection of OPE flame retardants in food. In this paper, we have reviewed the current status and development trends of OPE detection methods in various foodstuffs. First, the physicochemical properties of more than 30 common OPEs were summarized. Even when using the same extraction solvent, there are obvious differences in extraction efficiency according to different compound properties. To simultaneously analyze multi-component OPE flame retardants in food, it is very important to choose the appropriate extraction solvent to meet the required extraction efficiency of compounds with a wide range of polarities. In addition, although OPE flame retardants are not easily hydrolyzed under neutral conditions, they will degrade to a certain extent under strong acidic and alkaline conditions. It is worth mentioning that avoiding the removal of lipids and other interferences in food matrices under strong acidic and alkaline conditions. Different pretreatment methods, such as accelerated solvent extraction, matrix solid-phase dispersion extraction, microwave-assisted extraction, ultrasonic-assisted extraction, QuEChERS, solid-phase extraction, gel permeation chromatography, and dispersive solid-phase extraction are also compared. Combining the advantages of ultrasonic assisted extraction (UAE) and QuEChERS pretreatment technology can reduce the waste of extraction solvent and internal standard solution. For lipid-rich matrices like biological samples, it is necessary to remove lipid interference by SPE columns or GPC purification. Furthermore, the characteristics of separation and detection techniques, such as GC, GC-MS/MS, and LC-MS/MS, are discussed. Comparing detection limits and recovery data with those reported in the literature, GC-MS/MS can provide improved selectivity, precision, and limits of detection in complex food matrices, but LC-MS often suffers from ion suppression, matrix interferences, and incomplete separation of some OPEs. Since electron impact (EI) has higher ionization efficiency, it produces many fragment ions, thus creating a more complete spectral library, which is conducive to structural identification. When using GC-MS/MS to determine OPE flame retardants, the EI mode was usually used. However, positive chemical ionization (PCI) and electron capture negative ionization (ECNI) modes were also used sometimes. In the section on quality control, the main sources of standards and internal standards, possible sources of blank contamination, and the research status of measures to reduce matrix effects have been reviewed. To avoid blank contamination, all the laboratory equipment should be carefully cleaned, heated at high temperatures, and rinsed with polar or non-polar organic solvents in order to remove all interfering organic residues. Isotopically labeled internal standard and isotopic dilution mass spectrum quantification methods are used to reduce matrix effects. Owing to the limited availability of commercial standards and the relatively high cost, alternative approaches, such as matrix-matched calibration or standard addition methods, are required. The screening and identification of unknown metabolites of OPEs and related analytical methods based on high resolution mass spectrometry could also be studied for precursor OPEs in foodstuffs in the future.

Key words:

1. [1] Li S Z, Fu W Q, Feng C L. Environmental Engineering, 2018, 36(9):180 李素珍, 付卫强, 冯承莲. 环境工程, 2018, 36(9):180
2. [2] Pantelaki I, Voutsa D. Sci Total Environ, 2019, 649:247
3. [3] Van der Veen I, de Boer J. Chemosphere, 2012, 88(10):1119
4. [4] Shan Y, Wang S Y, Gu L Y, et al. Environmental Science and Management, 2019, 44(6):15 单岳, 王诗雨, 谷雷严, 等. 环境科学与管理, 2019, 44(6):15
5. [5] Guo J J, Yao B B, Zhu H L. Anhui Chemical Industry, 2018, 44(6):3 郭佳佳, 姚帮本, 祝红蕾. 安徽化工, 2018, 44(6):3
6. [6] Sui Q N, Zhai W, Geng C Z. Environmental Science and Management, 2015, 40(10):31 隋强男, 翟玮, 耿存珍. 环境科学与管理, 2015, 40(10):31
7. [7] Reemtsma T, Quintana J B, Rodil R, et al. TrAC-Trends Anal Chem, 2008, 27(9):727
8. [8] Lu J X, Ji W, Ma S T, et al. Chinese Journal of Analytical Chemistry, 2014, 42(6):859 鹿建霞, 季雯, 马盛韬, 等. 分析化学, 2014, 42(6):859
9. [9] Vykoukalová M, Venier M, Vojta Š, et al. Environ Int, 2017, 106:97
10. [10] Kademoglou K, Xu F, Padilla-Sanchez J A, et al. Environ Int, 2017, 102:48
11. [11] Gao X Z, Xu Y P, Wang Z J. Asian Journal of Ecotoxicology, 2015, 10(2):56 高小中, 许宜平, 王子健. 生态毒理学报, 2015, 10(2):56
12. [12] He L X, Cao S X, Zeng X Y, et al. Journal of Instrumental Analysis, 2013, 32(4):437 何丽雄, 曹曙霞, 曾祥英, 等. 分析测试学报, 2013, 32(4):437
13. [13] Zhong M M, Wang T L, Qi C D, et al. J Chromatogr A, 2019, 1602:350
14. [14] Chen M H, Xu H Z, Song N H, et al. Chinese Journal of Analytical Chemistry, 2017, 45(7):987 陈玫宏, 徐怀洲, 宋宁慧, 等. 分析化学, 2017, 45(7):987
15. [15] Yan X J, He H, Peng Y, et al. Chinese Journal of Analytical Chemistry, 2012, 40(11):1693 严小菊, 何欢, 彭英, 等. 分析化学, 2012, 40(11):1693
16. [16] Liu S L, Zhang H, Hu X H, et al. Chinese Journal of Analytical Chemistry, 2016, 44(2):192 刘世龙, 张华, 胡晓辉, 等. 分析化学, 2016, 44(2):192
17. [17] Zhong M Y, Wu H F, Mi W Y, et al. Sci Total Environ, 2018, 615:1305
18. [18] Li J H, Zhao L M, Letcher R J, et al. Environ int, 2019, 127:35
19. [19] Ding J J, Deng T Q, Xu M M. Environmental Chemistry, 2017, 36(10):2155 丁锦建, 邓童庆, 徐萌萌. 环境化学, 2017, 36(10):2155
20. [20] Li P, Zeng X Y, Cui J T, et al. Chinese Journal of Analytical Chemistry, 2017, 45(11):1648 李佩, 曾祥英, 崔君涛, 等. 分析化学, 2017, 45(11):1648
21. [21] He C, English K, Baduel C, et al. Environ Res, 2018, 164:262
22. [22] Chen Y, Fang J Z, Ren L, et al. Environ Pollut, 2018, 235:358
23. [23] Kim J W, Isobe T, Muto M, et al. Chemosphere, 2014, 116:91
24. [24] Beser M I, Pardo O, Beltrán J, et al. Anal Chim Acta, 2019, 1049:123
25. [25] Li P, Li Q X, Ma Y L, et al. Chinese Journal of Analytical Chemistry, 2015, 43(7):1033 李鹏, 李秋旭, 马玉龙, 等. 分析化学, 2015, 43(7):1033
26. [26] Shah M, Meija J, Cabovska B, et al. J Chromatogr A, 2006, 1103(2):329
27. [27] Xu H Z, Wang Z Z, Zhang S H, et al, Asian Journal of Ecotoxicology, 2018, 13(3):19 徐怀洲, 王智志, 张圣虎, 等. 生态毒理学报, 2018, 13(3):19
28. [28] Gao L H, Li Wen W H, Shi Y L, et al. Environmental Chemistry, 2014, 33(10):1750 高立红, 厉文辉, 史亚利, 等. 环境化学, 2014, 33(10):1750
29. [29] Meeker J D, Stapleton H M. Environ Health Persp, 2010, 118(3):318
30. [30] Egloff C, Crump D, Porter E, et al. Toxicol Appl Pharm, 2014, 279(3):303
31. [31] Du J, Li H, Xu S, et al. Environ Sci Pollut R, 2019:1
32. [32] Huang Q H, Wei L, Bignert A, et al. Chemosphere, 2019, 236:124327
33. [33] Liu Y E, Luo X J, Huang L Q, et al. Sci Total Environ, 2019, 663:125
34. [34] Santín G, Eljarrat E, Barceló D. J Chromatogr A, 2016, 1441:34
35. [35] Poma G, Sales C, Bruyland B, et al. Environ Sci Technol, 2018, 52(4):2331
36. [36] Poma G, Glynn A, Malarvannan G, et al. Food Chem Toxicol, 2017, 100:1
37. [37] Xu F, García-Bermejo À, Malarvannan G, et al. J Chromatogr A, 2015, 1401:33
38. [38] Bekele T G, Zhao H, Wang Y, et al. Ecotox Environ Safe, 2018, 166:270
39. [39] Zhang X L, Zou W, Mu L, et al. J Hazard Materials, 2016, 318:686
40. [40] Ma Y Q, Cui K Y, Zeng F, et al. Anal Chim Acta, 2013, 786:47
41. [41] Gao Z Q, Deng Y H, Yuan W T, et al. J Chromatogr A, 2014, 1366:31
42. [42] Liu Y E, Huang L Q, Luo X J, et al. J Chromatogr A, 2018, 1532:68
43. [43] Xu F C, Tay J H, Covaci A, et al. Environ Int, 2017, 102:236
44. [44] Zheng X B, Xu F C, Luo X J, et al. Chemosphere, 2016, 150:545
45. [45] Campone L, Piccinelli A L, Östman C, et al. Anal Bioanal Chem, 2010, 397(2):799
46. [46] Malarvannan G, Belpaire C, Geeraerts C, et al. Environ Res, 2015, 140:604
47. [47] Sundkvist A M, Olofsson U, Haglund P. J Environ Monitor, 2010, 12(4):943
48. [48] He C, Wang X Y, Tang S Y, et al. Environ Sci Technol, 2018, 52(21):12765
49. [49] Zhao L, Jian K, Su H, et al. Environ int, 2019, 128:343
50. [50] Aznar-Alemany Ò, Aminot Y, Vilà-Cano J, et al. Sci Total Environ, 2018, 612:492
51. [51] Ding J J, Deng T Q, Xu M M, et al. Environ Pollut, 2018, 233:986
52. [52] Guo X D, Mu T N, Xian Y P, et al. Food Chem, 2016, 196:673
53. [53] Wang X L, Zhong W J, Xiao B W, et al. Environ int, 2019, 125:25
54. [54] Huang Q H, Wei L, Bignert A, et al. Chemosphere, 2019, 236:124327
55. [55] Chen D, Letcher R J, Chu S. J Chromatogr A, 2012, 1220:169
56. [56] He M J, Lu J F, Wei S Q. Environ Pollut, 2019, 244:388
57. [57] Hou R, Liu C, Gao X Z, et al. Environ Pollut, 2017, 229:548
58. [58] Brandsma S H, Leonards P E G, Leslie H A, et al. Sci Total Environ, 2015, 505:22
59. [59] Wang Y, Kannan K. J Agric Food Chem, 2018, 66(51):13525
60. [60] García-López M, Rodríguez I, Cela R. J Chromatogr A, 2007, 1166(1/2):9
61. [61] García-López M, Rodríguez I, Cela R, et al. Talanta, 2009, 79(3):824
62. [62] He Qing. Food Safety Guide, 2019(18):109 何晴. 食品安全导刊, 2019(18):109
63. [63] Castro V, Montes R, Quintana J B, et al. Talanta, 2020, 208:120470
64. [64] Sapozhnikova Y, Lehotay S. J Anal Chim Acta, 2013, 758:80
65. [65] Rodriguez I, Calvo F, Quintana J B, et al. J Chromatogr A, 2006, 1108(2):158
66. [66] Gustavsson J, Ahrens L, Nguyen M A, et al. J Chromatogr A, 2017, 1481:116
67. [67] Ma Y, Hites R A. J Mass Spectrom, 2013, 48(8):931
68. [68] Teo T L, McDonald J A, Coleman H M, et al. Talanta, 2015, 143:114
69. [69] Tokumura M, Miyake Y C, Wang Q, et al. J Environ Sci Heal Part A, 2018, 53(5):475
70. [70] Han L J, Sapozhnikova Y, Nuñez A. J Agric Food Chem, 2019, 67(46):12652

扫一扫看文章

计量

PDF下载量: 39
文章访问数: 2935
HTML全文浏览量: 373

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

食品中有机磷酸酯阻燃剂检测技术的研究进展

通讯作者: 张庆合, E-mail:zhangqh@nim.ac.cn

English

Advances in the development of detection techniques for organophosphate ester flame retardants in food

Corresponding author: ZAHNG Qinghe, zhangqh@nim.ac.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

食品中有机磷酸酯阻燃剂检测技术的研究进展

通讯作者: 张庆合, E-mail:zhangqh@nim.ac.cn

English

Advances in the development of detection techniques for organophosphate ester flame retardants in food

Corresponding author: ZAHNG Qinghe, zhangqh@nim.ac.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs