Chemistry Department, The City College of The City University of New York, New York, NY 10031, United States; Chemistry Department, Graduate School and University Center of The City University of New York, New York, NY 10016, United States.
Chemosphere. 2013 Nov;93(9):2033-9. doi: 10.1016/j.chemosphere.2013.07.028. Epub 2013 Aug 12.
Tris(haloalkyl)phosphates (THAPs) are among the most widely used flame retardants in the U.S. They have been identified as one of the most frequently detected contaminants in U.S. streams. These contaminants are of toxicological concern in sensitive coastal ecosystems such as estuaries and salt marshes. It is likely that reactions with reduced sulfur species such as polysulfides (Sn(2-)) and bisulfide (HS(-)), present in anoxic subregions of coastal water bodies could have a significant impact on rates of removal of such contaminants, especially since no significant degradation reactions in the environment (e.g., hydrolysis, biological degradation) is reported for these compounds. The kinetics of the reaction of reduced sulfur species with three structurally related THAPs have been determined in well-defined aqueous solutions under anoxic conditions. Reactions were monitored at varying concentrations of reduced sulfur species to obtain second-order rate constants from the observed pseudo-first order rate constants. The degradation products were studied with GC-FID and LC-MS. The reactivity of Sn(2-), thiophenolate, and HS(-) were compared and steric, as well as electronic factors are used to explain the relative reactivity of the three THAPs with these three sulfur species.
三（卤代烷基）磷酸盐（THAPs）是美国最广泛使用的阻燃剂之一。它们已被确定为美国溪流中最常检测到的污染物之一。这些污染物在敏感的沿海生态系统（如河口和盐沼）中具有毒理学关注。与缺氧水体中存在的还原硫物种（如多硫化物（Sn(2-)）和 硫氢根（HS(-)））的反应很可能对这些污染物的去除速率产生重大影响，特别是因为没有报道这些化合物在环境中会发生明显的降解反应（例如水解、生物降解）。在缺氧条件下，在定义明确的水溶液中确定了三种结构相关的 THAPs 与还原硫物种的反应动力学。通过监测不同浓度的还原硫物种来获得观察到的假一级速率常数的二级速率常数。使用 GC-FID 和 LC-MS 研究了降解产物。比较了 Sn(2-)、苯硫酚和 HS(-)的反应性，并使用空间和电子因素来解释这三种 THAPs 与这三种硫物种的相对反应性。
