水中典型内分泌干扰物质的臭氧氧化研究

在静态实验中,考察了臭氧投加量、HCO^-₃浓度和pH值对O₃氧化去除水中典型内分泌干扰物（EDs）E1、E2、EE2、DES和4-n-NP的影响.结果表明,5种EDs的去除率随O₃投加量的增加而增大,O₃浓度达到63.6 μg/L时可去除92.0%以上的EDs,HCO^-₃（0～100 mg/L）的引入抑制了O₃氧化,O₃氧化去除EDs的能力随溶液pH值升高而大幅度提高.在中性（pH≈7.0）和碱性（pH＞10.6）条件下,O₃氧化5种EDs的表观二级反应速率常数(20℃±0.5℃)分别在(1.67～3.89)×10⁶　Ｌ·(mol·s)^-1和(0.93～1.75)×10⁹　Ｌ·(mol·s)^-1范围内,表明这5种物质在水中可被O₃迅速氧化去除.计算得出5种EDs的基元反应速率常数(20℃±0.5℃),发现O₃与离子态的EDs反应活性［1.21×10⁹～3.81×10⁹　Ｌ·(mol·s)^-1］是其与分子态EDs的反应活性［7.62×10⁵～2.55×10⁶　Ｌ·(mol·s)^-1］的10³～10⁴倍.对比不同水质本底下O₃氧化去除EDs的实验发现,滤后水和江水中EDs的去除率较其在超纯水中分别降低了26.5%～50.3%和57.3%～72.0%,表明实际水体中的有机物通过竞争氧化剂,抑制了EDs的O₃氧化去除.

Ozonation of Representative Endocrine Disruptors (EDs) in Water

The effects of ozone dose, bicarbonate concentration and pH on endocrine disruptors(EDs) removal, such as E1, E2, EE2, DES and 4-n-NP, were investigated through batch experiment. The results indicated that the removal rates were enhanced by increasing ozone dose, and O3 exposures of only 63.6 microg/L were calculated to achieve > or = 92.0% EDs removal efficiency. The presence of bicarbonate (0 - 100 mg/L) inhibited EDs ozonation. Furthermore, the EDs removal rates increased significantly as pH increased. The five apparent rate constants (20 degrees C +/- 0.5 degrees C) of ozone with the five EDs were in the range of (1.67 - 3.89) x 10(6)L (mol s) (-1) at neutral pH (pH approximately 7.0) and (0.93 approximately 1.75) x 10(9) L (mol s)(-1) at basic pH (pH > 10.6). It was indicated that the five EDs were removed rapidly by O3 in water. At the same time, the elementary reaction ozone rate constants (20 degrees C +/- 0.5 degrees C) were calculated, and the reactivity of ozone with ionized EDs i.e. 1.21 x 10(9) - 3.81 x 10(9) L (mol s)(-1)] was 10(3) - 10(4) times higher than with neutral EDs i.e. 7.62 x 10(5) - 2.55 x 10(6) L (mol s)(-1)]. The comparative test of EDs ozonation under different water quality conditions indicated that the removal rates of EDs in filtrated water and river water were reduced 26.5% - 50.3% and 57.3% - 72.0% respectively compared with the case using ultrapurified water as the background. It showed that organics in real water would compete with EDs for ozonation.