Structure relationship for catalytic dechlorination rate of dichlorobenzenes in water

Three isomers of dichlorobenzene (o-, m- and p-DCB) were dechlorinated by Pd/Fe catalyst in aqueous solutions through catalytic reduction. The dechlorination reaction took place on the surface site of the catalyst via a pseudo-first-order kinetics, and resulted in benzene as the final reduction product. The rate constants of the reductive dechlorination for the three dichlorobenzenes (DCBs) in the presence of Pd/Fe as a catalyst were measured experimentally. In all cases, the reaction rate constants were found to increase with the decrease in the Gibbs free energy of the formation of DCBs. The reaction rate constant for o-, m- and p-DCBs in the presence of 0.020% (w/w) Pd/Fe at 25 °C was determined to be 0.0213, 0.0223, and 0.0254 min⁻¹, respectively. While the activation energy of each dechlorination reaction was measured to be 102.5, 96.6 and 80.0 kJ mol⁻¹ for o-, m- and p-DCBs, respectively. The results demonstrated that p-DCBs were reduced more easily than o- or m-DCBs, and the order of the tendency of the dechlorination was p-DCB > m-DCB > o-DCB. The presented data show the catalytic reduction using Pd/Fe as a catalyst is a fast and easy approach for the dechlorination of DCBs.     

Biotransformation and antioxidant response in Ceratophyllum demersum experimentally exposed to 1,2- and 1,4-dichlorobenzene

We report the effects of 1,2- and 1,4-dichlorobenzene (1,2-DCB and 1,4-DCB) on the aquatic macrophyte Ceratophyllum demersum. We evaluated the response of the antioxidant system through the assay of glutathione reductase (GR), guaiacol peroxidase (POD) and glutathione peroxidase (GPx). Additionally, the effect of DCBs on the detoxication system by measuring the activity of glutathione-S-transferase (GST) was evaluated.

C. demersum showed elevated GST activities when exposed to 10 and 20 mg l⁻¹ 1,2-DCB, and at 10 mg l⁻¹ for 1,4-DCB. These results show that glutathione conjugation take place at relatively high concentrations of both isomers. Significantly increased activities of POD were also detected in C. demersum exposed to concentrations above 5 mg l⁻¹ of the corresponding isomer.

The GR activity was enhanced in plants exposed to 1,2-DCB (5 mg l⁻¹) and 1,4-DCB (10 mg l⁻¹). GPx was also significantly increased in exposures to the corresponding isomer, each at a concentration of 10 mg l⁻¹. However, plants exposed to low doses of 1,4-DCB (1 mg l⁻¹) showed significantly decreased activities of both enzymes GR and GPx.

Consequently, it is clear that the exposure of the aquatic macrophyte C. demersum to DCBs is able to cause an activation of the antioxidant system, showing an isomer specific pattern, which suggests that the defence system of this plant is playing an important role in scavenging ROS, helping to protect the organism against adverse oxidative effects generated by the prooxidant action of the tested xenobiotics. Furthermore, increased GST activities give indirect evidence on the conjugation of either DCBs or the corresponding metabolites during phase II of detoxication, which supports the elimination process of toxic metabolites from cells of C. demersum.