Cobalt mediated electro-scrubbers for the degradation of gaseous perchloroethylene.

This work focuses on the treatment of gaseous perchloroethylene (PCE) using electro-scrubbing with diamond electrodes and cobalt mediators. PCE was obtained by direct desorption from an aqueous solution containing 150 mg L-1, trying to a real pollution case. The electro-scrubber consisted of a packed absorption column connected with an undivided electrochemical cell. Diamond anodes supported on two different substrates (tantalum and silicon) were used and the results indicated that Ta/BDD was more successful in the production of Co (III) species and in the degradation of PCE. Three experimental systems were studied for comparison purposes: absorbent free of Co (III) precursors, absorbent containing Co (III) precursors, and absorbent containing Co (III) precursors undergoing previous electrolysis to the electro-scrubbing to facilitate the accumulation of oxidants. The most successful option was the last, confirming the important role of mediated electrochemical processes in the degradation of PCE. Trichloroacetic acid (TCA) and carbon tetrachloride (CCl4) were found as the primary reaction products and ethyl chloroacetate esters were also identified. A comprehensive mechanism of the processes happening inside electro-scrubber is proposed.

Improvement of electrochemical oxidation efficiency through combination with adsorption processes.

In this work, a three-step process (adsorption-desorption-electrolysis) is evaluated as an interesting approach for the removal of organochlorinated compounds (clopyralid, lindane and perchloroethylene) with different physical properties (solubility and vapor pressure) from low concentrated wastewater. First steps are based on the adsorptive capacity of granular active carbon (GAC) particles to retain organics and on the solvent capacity of methanol to extract them to concentrated solution and regenerate GAC. In the last step of electrolysis with conductive diamond electrodes, the degradation of pesticide is projected, as well as the recovery of methanol. Results show that clopyralid, lindane and PCE are efficiently retained in GAC, although adsorption efficiency depend on pollutant/GAC ratio and physicochemical properties of pollutant. Pretreatment allows the concentration of clopyralid and PCE solutions up to 8 times, but worse results are obtained in case of lindane solutions. Electrolysis of concentrated methanol solution seems to be more efficient than electrolysis of diluted aqueous wastes, mainly in the case of clopyralid. In all cases, electrochemical degradation fits a first order kinetics confirming mixed oxidation mechanisms with diffusion control of the direct processes and mediated oxidation. Results obtained in terms of current efficiency and energy consumption of electrolysis step point out the lower operation cost of concentrated liquid wastes and encourage further works on the development of cost-effective combined processes for the treatment of diluted solutions polluted with polar compounds (such as clopyralid).

Clopyralid degradation by AOPs enhanced with zero valent iron.

Four different technologies have been compared (photolysis, ZVI + photolysis, electrolysis and ZVI + electrolysis) regarding the: (1) degradation of clopyralid, (2) extent of its mineralization, (3) formation of by-products and main reaction pathways. Results show that photolysis is the less efficient treatment and it only attains 5 % removal of the pollutant, much less than ZVI, which reaches 45 % removal and that electrolysis, which attains complete removal and 78 % mineralization within 4 h. When ZVI is used as pre-treatment of electrolysis, it was obtained the most efficient technology. The identification of transformation products was carried out for each treatment by LCMS. In total, ten products were identified. Tentative pathways for preferential clopyralid degradation for all processes were proposed. This work draws attention of the synergisms caused by the coupling of techniques involving the treatment of chlorinated compound and sheds light on how the preferential mechanisms of each treatment evaluated occurred.

Improving biotreatability of hazardous effluents combining ZVI, electrolysis and photolysis.

In this work, nine types of combination advanced oxidation processes/zero-valent iron (AOP-ZVI) were tested, in order to determine if any of these combinations demonstrate good chances as pretreatment for the biological degradation processes of organochlorinated pollutants. To do this, the changes undergone in the respirometric behavior, toxicity and short-term biodegradability were compared. The three AOPs studied were anodic oxidation with mixed metal oxides anodes (AO-MMO), with boron doped diamond anodes (AO-BDD) and photolysis and they were evaluated in three different modes: without any addition of ZVI, with ZVI-dehalogenation as pre-treatment and with ZVI-dehalogenation simultaneous to the AOP treatment. Clopyralid has been used as a model of chlorinated hydrocarbon pollutant. Results show that technologies proposed can successfully treat wastes polluted with clopyralid and the biological characteristics of the waste are significantly modified by dehalogenating the waste with ZVI, either previously to the treatment or simultaneously to the treatment, being the information provided by the three techniques very important in order to evaluate later combinations of the advanced oxidation technologies with biological treatments.

Enhanced electrolytic treatment for the removal of clopyralid and lindane.

In this work, it is evaluated the more critical point of a new electrochemical technology for the removal of organic pollutants based on the regeneration of granular active carbon (GAC) (that can be used efficiently to concentrate aqueous wastes) with methanol and in the electrochemical treatment of methanol with conductive diamond electrochemical oxidation (CDEO). The system proposed was studied with lindane and clopyralid. Results show that it is possible the complete removal of the raw pesticides and intermediates formed by electrolyzing these species in methanol media and that both sodium chloride and sodium hydroxide can be used as supporting electrolyte to increase the conductivity of methanol. The cell voltages obtained are quite similar to those obtained during the electrolysis of aqueous wastes. The electrolysis of these dilute solutions does not generate significant concentrations of intermediates and the depletion of the raw pollutant fits well to a pseudo-first order kinetic model. Oxidants capable to oxidize iodide to iodine are produced during the electrolysis in methanol media and they have an important influence on the degradation of the pollutants. The new technology, based on the concentration of the pollutant before electrolysis, allows to remove completely pollutants from soil and soil washing fluids in a more efficient way, although the concentration of pollutant attained and, hence, the efficiency of the overall removal process depends on the adsorption equilibria of the pollutant in aqueous and methanol media.

Electrolysis with diamond anodes of the effluents of a combined soil washing - ZVI dechlorination process.

In this work, a new soil washing process in which Soil-Liquid extraction technology is enhanced by adding iron particles (zero valent iron nanoparticles or granules) was investigated to remove clopyralid from spiked soils. This novel approach can be efficiently used to extract chlorinated hydrocarbons from soil and aims to obtain soil-washing wastes with low content of hazardous chlorinated species. The iron particles used were subsequently removed from the treated soil using magnetic fields. Then, the complete mineralization of the produced soil washing effluents was successfully achieved by applying anodic oxidation with diamond anodes in an electrochemical flow cell. Results demonstrated that, opposite to what it was initially expected, no improvements in the efficiency of the electrochemical process were observed by adding iron particles during the soil washing. This behavior is explained in terms of the lower electrochemical reactivity of the dechlorinated derivatives produced. Although results are not as promising as initially expected, it does not mean a completely negative outcome for the use of ZVI during washing, because the hazardousness of the pollutants is rapidly decreased in the initial stages of the soil-washing, opening the possibility for the combination of this technology with other processes, such as biological treatment.

Remediation of soils polluted with lindane using surfactant-aided soil washing and electrochemical oxidation.

In this work the complete treatment of soil spiked with lindane is studied using surfactant-aided soil-washing (SASW) to exhaust lindane from soil and electrolysis with diamond anodes to mineralize lindane from the soil washing fluid (SWF) waste. Results demonstrated that this technological approach is efficient and allow to remove this hazardous pollutant from soil. They also pointed out the significance of the ratio surfactant/soil in the efficiency of the SASW process and in the performance of the later electrolysis used to mineralize the pollutant. Larger values of this parameter lead to effluents that undergo a very efficient treatment which allows the depletion of lindane for applied charges lower than 15AhL-1 and the recovery of more than 70% of the surfactant for the regeneration of the SWF.