Acta Chimica Sinica ›› 2012, Vol. 70 ›› Issue (17): 1819-1826.DOI: 10.6023/A12060320 Previous Articles     Next Articles

Full Papers


李艳霞, 段晓勇, 李先国, 唐旭利   

  1. 中国海洋大学海洋化学理论与工程技术教育部重点实验室 青岛 266100
  • 投稿日期:2012-06-18 发布日期:2012-07-25
  • 通讯作者: 李先国
  • 基金资助:
    项目受国家自然科学基金(No. 40976041)资助.

Mechanism Study on Photodegradation of Nonylphenol in Water by Intermediate Products Analysis

Li Yanxia, Duan Xiaoyong, Li Xianguo, Tang Xuli   

  1. Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, Ocean University of China, Qingdao 266100, China
  • Received:2012-06-18 Published:2012-07-25
  • Supported by:
    Project supported by the National Natural Science Foundation of China (No. 40976041).

The photodegradation mechanisms of nonylphenol (NP) with the involvement of dissolved oxygen (DO), hydrogen peroxide, nitrate ion and chloride ion in water by simulated sunlight were studied, respectively. The influence of each factor on the photodegradation of NP has been assessed through contrasting the residual rate of NP. And the photodegradation pathways in different conditions have been proposed according to the intermediate products identified by GC-MS. DO was a key factor in the photodegradation of NP and the rate of photoreaction depended on O2 concentration; the existence of H2O2 or NO3- increased the NP degradation rate significantly; with the existence of H2O2, the addition of Cl- first accelerated then slowed down the NP degradation rate. When NP reacted with DO, 4-nonylcatechol, nonanol, nonanal and nonoic acid have been identified as the degradation products. The accumulated amount of nonoic acid was the most. The proposed mechanism was that the 4-nonylcatechol and ortho-quinone derivative were produced after the formation of 4-nonylphenoxyl radical and superoxide radical anions (O2·-), then the intermediates underwent conjugate addition, nonanol, nonanal and nonoic acid were produced. In the presence of H2O2, 4-n-akylphenol (HOC6H4-CnH2n+1, n=2~8), 4-nonylcatechol, nonanol, nonanal and nonoic acid were the degradation products. And the accumulated amount of nonanal was the most. The hydroxyl radicals (·OH) generated by the photolysis of H2O2 attacked the electronic gathered positions of NP molecules. The products detected in the presence of NO3- were same as which detected in the presence of H2O2. The irradiated NO3- can produce ·OH and ·NO2, so 2-nitryl-4-nonylphenol was found as the product of ·NO2 attacking the ortho-position of phenolic hydroxyl. In the presence of Cl- and H2O2, the nonanoyl chloride was found. The accumulated amount of nonanal was the most, so the probable mechanism was that the chlorine radical which generated from the reaction of ·OH and Cl- reacted with nonanal.

Key words: nonylphenol, photodegradation, dissolved oxygen, hydrogen peroxide, nitrate ion, chloride ion