Kovács Krisztina, He Shijun, Mile Viktoria, Csay Tamás, Takács Erzsébet, Wojnárovits László
Institute for Energy Security and Environmental Safety, Centre for Energy Research, Hungarian Academy of Sciences, Budapest, Hungary.
Institute of Nuclear and New Energy Technology (INET), Tsinghua University, Beijing, 100084 China.
Chem Cent J. 2015 Apr 18;9:21. doi: 10.1186/s13065-015-0097-0. eCollection 2015.
Cutting edge technologies based on Advanced Oxidation Processes (AOP) are under development for the elimination of highly persistent organic molecules (like pesticides) from water matrices. Among them, ionizing radiation treatment represents a promising technology that requires no additives and can be easily adapted to an industrial scale. In these processes several reactive species are produced, mainly powerful oxidizing radicals inducing the degradation. This paper investigates the reactions taking place in dilute aqueous solutions of a hazardous pollutant (diuron) during irradiation.
Irradiation of aqueous diuron solutions resulted in effective degradation of the solute mainly due to the reactions of hydroxyl radicals formed in water radiolysis. Hydroxyl radical reacts with diuron with a second order rate constant of (5.8 ± 0.3) × 10(9) mol(-1) dm(3) s(-1). The main reaction is addition to the ring forming hydroxycyclohexadienyl radical. 30 - 50% of hydroxyl radical reactions induce dechlorination. Reactions with the methyl groups or with the α-amino group have low contribution to the transformation. The presence of dissolved oxygen enhances the rate of degradation; one hydroxyl radical on average induces five-electron oxidations. The high oxidation rate is attributed to the reaction of some of the primarily formed organic radicals with dissolved O2 and the subsequent reactions of the peroxy radicals.
The presence of dissolved oxygen is highly important to achieve efficient ionizing radiation induced degradation of diuron in dilute aqueous solution.
基于高级氧化工艺(AOP)的前沿技术正在开发中,用于从水基质中去除高度持久的有机分子(如农药)。其中,电离辐射处理是一项很有前景的技术,无需添加任何物质,且易于扩展至工业规模。在这些过程中会产生多种活性物种,主要是能引发降解的强氧化性自由基。本文研究了危险污染物(敌草隆)稀水溶液在辐照过程中发生的反应。
敌草隆水溶液的辐照导致溶质有效降解,主要原因是水辐射分解产生的羟基自由基的反应。羟基自由基与敌草隆反应的二级速率常数为(5.8 ± 0.3)×10⁹ mol⁻¹ dm³ s⁻¹。主要反应是加成到环上形成羟基环己二烯基自由基。30% - 50%的羟基自由基反应会导致脱氯。与甲基或α-氨基的反应对转化的贡献较小。溶解氧的存在提高了降解速率;平均一个羟基自由基能引发五次电子氧化。高氧化速率归因于一些最初形成的有机自由基与溶解氧的反应以及随后过氧自由基的反应。
溶解氧的存在对于在稀水溶液中实现高效电离辐射诱导的敌草隆降解非常重要。