Bastos Patricia Moreira, Eriksson Johan, Green Nicholas, Bergman Ake
Department of Environmental Chemistry, Stockholm University, SE-106 91 Stockholm, Sweden.
Chemosphere. 2008 Jan;70(7):1196-202. doi: 10.1016/j.chemosphere.2007.08.019. Epub 2007 Sep 25.
The term persistence has been used to confusion since it is used as a conceptual parameter without a uniform definition. Work is therefore being done in order to unite ideas and describe persistence based on the chemical reactivity and chemico-physical properties of compounds via investigation of the main degradation pathways in the environment; photolysis, hydrolysis-substitution-elimination (hse), oxidation, reduction and radical reactions. The present work is focused on developing a method to determine oxidative degradation rates of chemicals and thereby measurement of their susceptibility to undergo oxidation reactions. The method based on potassium permanganate works well for water soluble compounds and is easy, robust, inexpensive and reproducible. By using the method and varying the analysed substances, the degradation rates for brominated phenols, two chlorinated phenols and high volume production compounds such as tetrabromobisphenol A (TBBPA), tetrachlorobisphenol A (TCBPA) and bisphenol A (BPA) have been determined at pH 7.6+/-0.2. The reaction rates of the two halogenated BPA's are particularly fast, giving half-lives in seconds. The other test compounds have slower reaction rates but easily measured under the reaction conditions applied. The reactions are temperature dependent. There is evidence that pK(a) and the substitution pattern of the halogens affects the rate of the reactions. The method is robust and applicable for reaction rate constant measurements of present and potential future environmental contaminants.
“持久性”一词一直被使用得很混乱,因为它被用作一个概念参数却没有统一的定义。因此,人们正在开展工作,以便统一观点,并通过研究环境中的主要降解途径(光解、水解-取代-消除(hse)、氧化、还原和自由基反应),根据化合物的化学反应性和化学物理性质来描述持久性。目前的工作重点是开发一种测定化学品氧化降解速率的方法,从而测量它们发生氧化反应的敏感性。基于高锰酸钾的方法对水溶性化合物效果良好,且简便、可靠、廉价且可重复。通过使用该方法并改变分析的物质,已在pH 7.6±0.2的条件下测定了溴化酚、两种氯化酚以及大量生产的化合物(如四溴双酚A(TBBPA)、四氯双酚A(TCBPA)和双酚A(BPA))的降解速率。两种卤化双酚A的反应速率特别快,半衰期以秒计。其他测试化合物的反应速率较慢,但在所应用的反应条件下易于测量。这些反应与温度有关。有证据表明,pK(a)和卤素的取代模式会影响反应速率。该方法可靠,适用于当前和未来潜在环境污染物的反应速率常数测量。