Formation of chlorinated breakdown products during degradation of sunscreen agent, 2-ethylhexyl-4-methoxycinnamate in the presence of sodium hypochlorite

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• 作者：Alicja Gackowska ; Maciej Przybyłek…
• 关键词：2 ; Ethylhexyl ; 4 ; methoxycinnamate ; Emerging pollutants ; Chlorination ; Sunscreen ; Halogenated disinfection byproducts ; GC ; MS ; Local reactivity ; Fukui function
• 刊名：Environmental Science and Pollution Research
• 出版年：2016
• 出版时间：January 2016
• 年：2016
• 卷：23
• 期：2
• 页码：1886-1897
• 全文大小：1,238 KB
• 参考文献：Accelrys Materials Studio 7-Inc., San Diego: Accelrys Software Inc. (2014)
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• 作者单位：Alicja Gackowska (1)
  Maciej Przybyłek (2)
  Waldemar Studziński (1)
  Jerzy Gaca (1)
  
  1. Faculty of Chemical Technology and Engineering, University of Technology and Life Science, Seminaryjna 3, 85-326, Bydgoszcz, Poland
  2. Department of Physical Chemistry, Collegium Medicum, Nicolaus Copernicus University, Kurpińskiego 5, 85-950, Bydgoszcz, Poland
  
• 刊物类别：Earth and Environmental Science
• 刊物主题：Environment
  Environment
  Atmospheric Protection, Air Quality Control and Air Pollution
  Waste Water Technology, Water Pollution Control, Water Management and Aquatic Pollution
  Industrial Pollution Prevention
  
• 出版者：Springer Berlin / Heidelberg
• ISSN：1614-7499

文摘

In this study, a new degradation path of sunscreen active ingredient, 2-ethylhexyl-4-methoxycinnamate (EHMC) and 4-methoxycinnamic acid (MCA) in the presence of sodium hypochlorite (NaOCl), was discussed. The reaction products were detected using gas chromatography–mass spectrometry (GC-MS). Since HOCl treatment leads to more polar products than EHMC, application of polar extracting agents, dichloromethane and ethyl acetate/n-hexane mixture, gave better results in terms of chlorinated breakdown products identification than n-hexane. Reaction of EHMC with HOCl lead to the formation of C=C bridge cleavage products such as 2-ethylhexyl chloroacetate, 1-chloro-4-methoxybenzene, 1,3-dichloro-2-methoxybenzene, and 3-chloro-4-methoxybenzaldehyde. High reactivity of C=C bond attached to benzene ring is also characteristic for MCA, since it can be converted in the presence of HOCl to 2,4-dichlorophenole, 2,6-dichloro-1,4-benzoquinone, 1,3-dichloro-2-methoxybenzene, 1,2,4-trichloro-3-methoxybenzene, 2,4,6-trichlorophenole, and 3,5-dichloro-2-hydroxyacetophenone. Surprisingly, in case of EHMC/HOCl/UV, much less breakdown products were formed compared to non-UV radiation treatment. In order to describe the nature of EHMC and MCA degradation, local reactivity analysis based on the density functional theory (DFT) was performed. Fukui function values showed that electrophilic attack of HOCl to the C=C bridge in EHMC and MCA is highly favorable (even more preferable than phenyl ring chlorination). This suggests that HOCl electrophilic addition is probably the initial step of EHMC degradation. Keywords 2-Ethylhexyl-4-methoxycinnamate Emerging pollutants Chlorination Sunscreen Halogenated disinfection byproducts GC-MS Local reactivity Fukui function