State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, China.
J Hazard Mater. 2011 Feb 15;186(1):227-35. doi: 10.1016/j.jhazmat.2010.10.106. Epub 2010 Nov 3.
The oxidation of triclosan by commercial grade aqueous ferrate (Fe(VI)) was investigated and the reaction kinetics as a function of pH (7.0-10.0) were experimentally determined. Intermediate products of the oxidation process were characterized using both GC-MS and RRLC-MS/MS techniques. Changes in toxicity during the oxidation process of triclosan using Fe(VI) were investigated using Pseudokirchneriella subcapitata growth inhibition tests. The results show that triclosan reacted rapidly with Fe(VI), with the apparent second-order rate constant, k(app), being 754.7 M(-1) s(-1) at pH 7. At a stoichiometric ratio of 10:1 (Fe(VI):triclosan), complete removal of triclosan was achieved. Species-specific rate constants, k, were determined for reaction of Fe(VI) with both the protonated and deprotonated triclosan species. The value of k determined for neutral triclosan was 6.7(±1.9)×10(2) M(-1) s(-1), while that measured for anionic triclosan was 7.6(±0.6)×10(3) M(-1) s(-1). The proposed mechanism for the oxidation of triclosan by the Fe(VI) involves the scission of ether bond and phenoxy radical addition reaction. Coupling reaction may also occur during Fe(VI) degradation of triclosan. Overall, the degradation processes of triclosan resulted in a significant decrease in algal toxicity. The toxicity tests showed that Fe(VI) itself dosed in the reaction did not inhibit green algae growth.
研究了商业级铁酸盐(Fe(VI))对三氯生的氧化作用,并通过实验确定了 pH 值(7.0-10.0)下的反应动力学。使用 GC-MS 和 RRLC-MS/MS 技术对氧化过程中的中间产物进行了表征。使用斜生栅藻生长抑制试验研究了铁酸盐(Fe(VI))氧化三氯生过程中的毒性变化。结果表明,三氯生与 Fe(VI)反应迅速,在 pH 7 时,表观二级反应速率常数 k(app)为 754.7 M(-1) s(-1)。在 10:1(Fe(VI):三氯生)的化学计量比下,三氯生完全去除。确定了 Fe(VI)与质子化和去质子化三氯生物种反应的物种特异性速率常数 k。中性三氯生的 k 值为 6.7(±1.9)×10(2) M(-1) s(-1),而阴离子三氯生的 k 值为 7.6(±0.6)×10(3) M(-1) s(-1)。Fe(VI)氧化三氯生的拟议机制涉及醚键的断裂和苯氧基自由基加成反应。在 Fe(VI)降解三氯生的过程中也可能发生偶联反应。总的来说,三氯生的降解过程导致藻类毒性显著降低。毒性试验表明,反应中加入的 Fe(VI)本身不会抑制绿藻的生长。