OH自由基降解二英OCDD的反应机理及动力学研究

采用量子化学计算研究了OH自由基降解八氯代二苯并对-二英（OCDD）的微观反应机理,计算分析了微观反应进程,结果表明该反应存在两条途径：①α-氯取代：1,4,6,9位置氯取代,该路径反应活化能较高,反应难以进行,并以中间产物积聚,无法使OCDD的毒性消失;②β-氯取代：2,3,7,8位置氯取代,该路径的反应能相对较低,且能使OCDD的毒性消失,是有效降解OCDD的主要途径.结合过渡态理论,计算获得动力学参数：反应活化能为8.32 kJ·mol^-1（B3LYP/6-311G++（d,g）//B3LYP/6-31G（d））,阿仑尼乌斯表达式为k=1.29×10¹⁴exp（-1049.6/T）（cm³·mole^-1·s^-1）.这与文献实验结果取得了很好的吻合,说明本文对OH自由基降解OCDD的反应机理及动力学研究是合理且可靠的.本文的计算结果可为催化氧化降解二英的进一步研究提供理论参考.     

Estimation of OCDD degradation rate in soil

The current concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans （PCDD/Fs） were determined in soils contaminated with Chinese technical product sodium pentachlorophenate （ Na- PCP）. The estimated half-life of octachlorodioxin （OCDD） was about 14 years in contaminated soils based on the local historical record and mass balance calculation during the past 43 years（ 1960-2003）. The isomer profiles remained the same regardless of paddy field soil or riverbank soil. The results indicated that the congenerspecific information was efficient in estimating the PCDD/Fs fate in contaminated soils.     

The Dechlorination of H6CDD,OCDD and OCDF on an Alumina support: Elucidation of the isomer pattern by multi linear regression and thermodynamic data

The dechlorination of OCDD, OCDF and 1,2,3,4,7,8‐H₆CDD is studies on an alumina support impregnated with activated carbon, copper chloride and potassium chloride. There is a high correlation between the isomer pattern found after dechlorination and molecular structure properties. We also found a substantial correlation between the isomer pattern and the Gibbs free energy of formation of the individual isomers. This suggests a thermodynamically controlled process.     

Dioxins in the Venice lagoon

Venice is famous around the world for its uniqueness and architectural splendours, arts and the history of the “Serenissima Repubblica”, as it was known in the past, but few are aware that Venice economy is strongly dependent on the industrial activities based mainly on the adjacent Porto Marghera area. For many years, the lagoon that physically separates the city from the dry land has avoided association between the concern connected with the pollution derived from these industrial activities and the public perception of Venice. Since 1995, dioxins have appeared as a lagoon contaminant, and their presence, at such a level requiring immediate “in depth” studies and interventions, has been fully realized for decades.     

五氯酚和八氯代二苯并二噁英复合暴露对斑马鱼胚胎发育的毒性效应

为了评价环境中五氯酚(PCP)和八氯代二苯并二噁英(OCDD)对水环境以及鱼类的影响,以斑马鱼为模式生物,研究了PCP和OCDD对其胚胎发育的单一及复合毒性效应.结果表明,PCP单独暴露(浓度25μg·L-1～5mg·L-1)对斑马鱼胚胎发育具有较强的毒性效应,可导致胚胎孵化率显著下降,死亡率、畸形率显著上升,而OCDD单独暴露(200、500μg·L-1)对斑马鱼胚胎发育没有明显的毒性效应;OCDD与环境浓度的PCP复合暴露(OCDD+PCP1:250μg·L-1+25μg·L-1;OCDD+PCP2:250μg·L-1+50μg·L-1)对斑马鱼胚胎的存活与发育等没有显著影响,对斑马鱼胚胎内CYP1A基因表达以及超氧化物歧化酶(SOD)、过氧化氢酶(CAT)的酶活力也没有显著影响,在实验浓度下二者共存没有明显的复合毒性效应。     

五氯酚和八氯代二苯并二嗯英复合暴露对斑马鱼胚胎发育的毒性效应

为了评价环境中五氯酚(PCP)和八氯代二苯并二嚼英(OCDD)对水环境以及鱼类的影响,以斑马鱼为模式生物,研究了PCP和OCDD对其胚胎发育的单一及复合毒性效应.结果表明,PCP单独暴露(浓度25μg·L-1～5mg·L-1)对斑马鱼胚胎发育具有较强的毒性效应,可导致胚胎孵化率显著下降,死亡率、畸形率显著上升,而OCDD单独暴露(200、500μg·L-1)对斑马鱼胚胎发育没有明显的毒性效应;OCDD与环境浓度的PCP复合暴露(OCDD PCP1:250μg·L-1 25μg·L-1;OCDD PCP2:250μg·L-1 50μg·L-1)对斑马鱼胚胎的存活与发育等没有显著影响,对斑马鱼胚胎内CYP1A基因表达以及超氧化物歧化酶(SOD)、过氧化氢酶(CAT)的酶活力也没有显著影响,在实验浓度下二者共存没有明显的复合毒性效应.     

Theoretical study on the degradation reaction of octachlorinated dibenzo-p-dioxin with atomic oxygen O(3P) in dielectric barrier discharge reactor

Dielectric barrier discharges （DBD） have been used in the degradation of dioxins due to the large number of excimers and free radicals produced in discharge process. In this article, the density functional theory （DFT） is used to study the degradation mechanism of octachlorinated dibenzo-p-dioxin （OCDD） with the atomic oxygen O（3P） in DBD reactor. The reactants, intermediates, transition states and products are optimized at the MPWB1K/6- 31 ＋ G（d,p） level. The vibrational frequencies have been calculated at the same level. The reaction pathways and mechanisms are analyzed in detail. The effect of removing the chlorine atom on environment also has been discussed.