Fang Guo-Dong, Si You-Bin
School of Resources and Environment, Anhui Agricultural University, Hefei 230036, China.
Huan Jing Ke Xue. 2010 Jun;31(6):1499-505.
Reductive transformation of 2,4-Dichlorophenoxyacetic acid (2,4-D) by nanoscale Fe3O4 was studied, and the effects of 2,4-D initial concentration, the dosage of nanoscale Fe3O4, pH and temperature on degradation rate of 2,4-D were investigated. The results showed that 48% 2,4-D with initial concentration of 10 mg/L was transformed within 48 h in the presence of 300 mg/L nanoscale Fe3O4. The degradation of 2,4-D was a reductive dechlorination process, and the concentration of chloride ion increased sharply with the degration of the 2,4-D. Disappearance of parent species and formation of reaction intermediates and products were analyzed by LC/MS. The transformation of 2,4-D followed a primary pathway of its complete reduction to phenol and a secondary pathway of sequential reductive hydrogenolysis to 2,4-dichlorophenol (2,4-DCP), 4-chlorophenol (4-CP) or 2-chlorophenol (2-CP) and phenol. The degradation equations of 2,4-D by nanoscale Fe3O4 conformed to pseudo-first-order kinetics, and the reaction rate constant (K) of 4-CP, 2,4-DCP and phenol were 0.0043 h(-1), 0.0026 h(-1) and 0.0032 h(-1), respectively. The degradation rate increased with an increase in initial concentration of 2,4-D from 0 mg/L to 10 mg/L, and increasing the dosage of nanoscale Fe3O4 from 0 mg/L to 300 mg/L. The pH of reaction solution significantly influenced reductive degradation of 2,4-D, and the optimum pH value was 3.0. Besides, high temperature could improve dechlorination rate of 2,4-D.
研究了纳米级Fe3O4对2,4-二氯苯氧乙酸(2,4-D)的还原转化,并考察了2,4-D初始浓度、纳米级Fe3O4用量、pH值和温度对2,4-D降解率的影响。结果表明,在300 mg/L纳米级Fe3O4存在下,初始浓度为10 mg/L的2,4-D在48 h内有48%发生转化。2,4-D的降解是一个还原脱氯过程,随着2,4-D的降解,氯离子浓度急剧增加。通过液相色谱/质谱联用仪分析了母体物种的消失以及反应中间体和产物的形成。2,4-D的转化遵循其完全还原为苯酚的主要途径和依次还原氢解为2,4-二氯苯酚(2,4-DCP)、4-氯苯酚(4-CP)或2-氯苯酚(2-CP)和苯酚的次要途径。纳米级Fe3O4对2,4-D的降解方程符合准一级动力学,4-CP、2,4-DCP和苯酚的反应速率常数(K)分别为0.0043 h(-1)、0.0026 h(-1)和0.0032 h(-1)。降解率随着2,4-D初始浓度从0 mg/L增加到10 mg/L以及纳米级Fe3O4用量从0 mg/L增加到300 mg/L而提高。反应溶液的pH值显著影响2,4-D的还原降解,最佳pH值为3.0。此外,高温可以提高2,4-D的脱氯率。