二氧化锰对壬基酚和辛基酚的氧化：动力学和途径。

Oxidation of nonylphenol and octylphenol by manganese dioxide: kinetics and pathways.

机构信息

Department of Environmental Sciences, University of California, Riverside, CA 92521, USA.

出版信息

Environ Pollut. 2013 Sep;180:214-20. doi: 10.1016/j.envpol.2013.05.047. Epub 2013 Jun 19.

DOI:10.1016/j.envpol.2013.05.047

Abstract

Due to their potent estrogenicity and ubiquitous occurrence, non-ionic surfactant metabolites nonylphenol (NP) and octylphenol (OP) are of significant concern. Abiotic chemical oxidation by naturally abundant metal oxides may be an important route of their environmental attenuation, but is poorly understood. We investigated the reaction kinetics and pathways of NP and OP with MnO2. At pH 5.5 and 100 mg/L δ-MnO2, 92, 84 and 76% of 4-n-NP, 4-tert-OP and technical nonylphenol (tNP) was transformed in 90 min, respectively. A further experiment using a Mn-containing soil and Mn-removed soil confirmed that soil MnO2 caused NP removal. Multiple reaction products, including hydroquinone, hydroxylated products, dimers and trimers were identified through fragmentation analysis by GC-MS/MS and UPLC-MS/MS, allowing the construction of tentative pathways. This study suggested that abiotic oxidation by MnO2 may contribute to the dissipation of tNP, 4-n-NP, 4-tert-OP and their analogues in the natural environment.

摘要

由于其强大的雌激素活性和普遍存在，非离子表面活性剂代谢物壬基酚（NP）和辛基酚（OP）引起了人们的高度关注。自然丰富的金属氧化物的非生物化学氧化可能是它们在环境中衰减的重要途径，但了解甚少。我们研究了 MnO2 与 NP 和 OP 的反应动力学和途径。在 pH 5.5 和 100mg/L δ-MnO2 条件下，4-正-NP、4-叔-OP 和技术壬基酚（tNP）分别在 90 分钟内转化了 92%、84%和 76%。使用含 Mn 土壤和 Mn 去除土壤的进一步实验证实，土壤 MnO2 导致 NP 去除。通过 GC-MS/MS 和 UPLC-MS/MS 的碎片分析鉴定出多种反应产物，包括对苯二酚、羟基化产物、二聚体和三聚体，从而构建了推测的途径。本研究表明，MnO2 的非生物氧化可能有助于天然环境中 tNP、4-正-NP、4-叔-OP 及其类似物的消散。