Biodegradability improvement and toxicity reduction of soil washing effluents polluted with atrazine by means of electrochemical pre-treatment: Influence of the anode material.

This work focuses on the partial anodic electro-oxidation of atrazine-polluted soil washing effluents (SWE) in order to reduce its toxicity and to improve its biodegradability. Concretely it has been evaluated the influence of the anodic material used. It is hypothesized that such partial oxidation step could be considered as a pre-treatment for a subsequent biological treatment. At first, atrazine was extracted from a polluted soil by means of a surfactant-aided soil-washing process. Then, four different anodic materials were studied in partial electro-oxidation pre-treatment batch experiments at different electric charges applied: Boron Doped Diamond (BDD), Carbon Felt (CF), and Mixed Metal Oxides Anodes with Iridium and Ruthenium. Atrazine, TOC, surfactant and sulphate species concentrations, as well as changes in toxicity and biodegradability, were monitored during electrochemical experiments, showing important differences in their evolution during the treatment. It was observed that BDD was the most powerful anodic material to completely degrade atrazine. The other materials achieve an atrazine degradation rate about 75%. Regarding mineralization of the organics in SWE, BDD overtakes clearly the rest of anodes tested. CF obtains good atrazine removal but low mineralization results. All the anodes tested slightly reduced the ecotoxicity of the water effluents. About the biodegradability, only the effluent obtained after the pre-treatment with BDD presented a high biodegradability. In this sense, it must be highlighted the mineralization obtained during the BDD pre-treatment was very strong. These results globally indicate that it is necessary to find a compromise between reaching efficient atrazine removal and biodegradability improvement, while also simultaneously avoiding strong mineralization. Additional efforts should be made to find the most adequate working conditions.

Electro Fenton removal of clopyralid in soil washing effluents.

The removal of a commercial herbicide, based on clopyralid, by means of Electro-Fenton (EF) was studied using a soil washing effluent obtained using synthetic ground water as washing fluid. From the results, it was observed that the degradation and mineralization yields of clopyralid were high, even without the addition of supporting electrolyte. The groundwater could be then used as a sustainable supporting electrolyte. The influence of the minerals constituents, the current and the ferrous ions regeneration was evaluated. The highest hydrogen peroxide production was achieved working at 200 mA but regeneration of ferrous ions was not efficient at this current. Iodide ions were one of the main responsible in the EF efficiency decrease due to their reaction with the produced hydrogen peroxide. Electrochemical study proved that clopyralid was not electroactive and that its degradation was mainly due to radical oxidation. Long duration electrolysis carried out at 200 mA in groundwater provided an improvement of the solution biodegradability after 480 min that can be linked to a significant increase in the carboxylic acids production. These results support the feasibility of applying an EF process in order to carry out a subsequent biological mineralization.