Subramanian Balaji

Destruction of commercial pesticides by cerium redox couple mediated electrochemical oxidation process in continuous feed mode.

Mediated electrochemical oxidation was carried out for the destruction of commercial pesticide formulations using cerium(IV) in nitric acid as the mediator electrolyte solution in a bench scale set up. The mediator oxidant was regenerated in situ using an electrochemical cell. The real application of this sustainable process for toxic organic pollutant destruction lies in its ability for long term continuous operation with continuous organic feeding and oxidant regeneration with feed water removal. In this report we present the results of fully integrated MEO system. The task of operating the continuous feed MEO system for a long time was made possible by continuously removing the feed water using an evaporator set up. The rate of Ce(IV) regeneration in the electrochemical cell and the consumption for the pesticide destruction was matched based on carbon content of the pesticides. It was found that under the optimized experimental conditions for Ce(III) oxidation, organic addition and water removal destruction efficiency of ca. 99% was obtained for all pesticides studied. It was observed that the Ce(IV) concentration was maintained nearly the same throughout the experiment. The stable operation for 6h proved that the process can be used for real applications and for possible scale up for the destruction of larger volumes of toxic organic wastes.

Influence of cathode on the electro-generation of peroxydisulfuric acid oxidant and its application for effective removal of SO2 by room temperature electro-scrubbing process.

Peroxydisulfuric acid oxidant (H2S2O8) was electro-generated using boron doped diamond (BDD) anode in an undivided electrolytic cell under the optimized conditions and used for the oxidative removal of gaseous SO2. The influence of the nature of cathode material on the formation yield of H2S2O8 was investigated with Ti, Pt, Zr and DSA electrodes in a flow type electrolytic cell under batch recirculation mode. Among the various cathodes employed Ti exhibited a good performance and the formation yield was nearly doubled (0.19 M) compared to the reported value of 0.07 M. The optimization of electrode area ratio between the anode and cathode brought out the fact that for nearly 8 times smaller Ti cathode (8.75:1) the achieved yield was ∼65% higher than the 1:1 ratio of anode and cathode. The highest concentration of 6.8% (0.48 M) H2S2O8 was seen for 35 cm(2) BDD anode with 4 cm(2) Ti at 20 °C with the measured redox potential value of +1200 mV. The oxidative removal of SO2 in an electro-scrubbing column attached to the online production of peroxydisulfuric acid under the optimized conditions of cell parameters shows that SO2 removal efficiency was nearly 100% for 25 and 50 ppm inlet concentrations and 96% for 100 ppm at the room temperature of 25 °C.

Kinetics of sodium ethylenediaminetetraacetate mineralization by cerium(IV) in nitric acid medium

The process of sodium ethylenediaminetetraacetate (EDTA) mineralization by cerium(IV) in nitric acid medium was studied in batch and continuous feeding modes. In the batch mode EDTA solution was fed into the reactor in one stroke and in the continuous mode it was fed with a constant flow rate during a definite time interval. Cerium(IV) concentration was kept at high and constant level by selecting correct relation between cerium(IV) production in the electrochemical cell and the EDTA added. During the organic mineralization process cerium(IV) is reduced to cerium(III). The process was carried out at different temperatures, concentrations of nitric acid and cerium(IV). To obtain the limiting factors in the batch mode reaction, the dependence of CO2 evolution with time and carrier gas blowing rate was studied. Application of the model previously developed by us to the continuous process gave us the possibility to calculate pseudo first order kinetic constant on the basis of CO2 evolution data of both EDTA destruction regimes during feeding mode and after stopping organic addition. The efficiency of organic destruction estimated on the basis of CO2 evolved was in the range 75–95% and on the basis of liquid phase residual organic carbon analysis 95–99%.

Determination of overall kinetic constants for mediated electrochemical oxidation of phenol from CO2 measurements

Mediated electrochemical oxidation is the latest achievement in environmental electrochemistry for the complete oxidation of organic pollutants. Transition or inner transition elements in an acid medium are usually employed as the mediator-electrolyte combination. The organic pollutants upon oxidation are completely converted to carbon dioxide and water. Since the oxidizing ability of the medium is so vigorous, the changes in the reactant concentrations or intermediates formed are usually difficult to analyze, but the product formed (CO2) can be measured and quantified in most of the cases. Therefore, in MEO reactions the kinetics can be followed either by monitoring the oxidant concentration changes or by measuring the product concentrations. In real applications the oxidant is regenerated continuously in situ and, hence, the oxidant concentration is maintained throughout the system. Therefore, in continuous organic feeding reactions, the product CO2 could be monitored and kinetics could be followed. We report in this paper a simple procedure for the calculation of the overall kinetic constants for the destruction of phenol from CO2 measurements. The procedure is based on the summation of the difference between the total amounts of organic added to the system and reacted to obtain CO2 evolution patterns. The CO2 patterns were then fitted with the experimental results to obtain the overall kinetic constants. Thermodynamic parameters have been obtained for phenol destruction from the overall kinetic constants.

BIOCOMPUTATIONAL ANALYSIS AND CHARACTERIZATION OF SOME ANTIFREEZE PROTEINS

Novel bioinformatic procedures and computational methods have been used to analyze, characterize and provide more detailed description of some selected fish antifreeze proteins (AFPs) retrieved from Swiss–Prot database. Analysis shows that AFPs are rich in non-polar residues and that the AFPs Q01758 and P05140 contain SS bonds. The aliphatic index computed by ExPasys ProtParam infers that AFPs may be stable for a wide range of temperatures and the AFP P80961 is classified as an unstable protein. The very low GRAVY index of AFP P80961 infers its higher hydrosolubility. Secondary structure analysis shows that the flounder and sculpin fish AFPs are found to be of predominant ∝–helical structures and the rest of them are with mixed secondary structures. The average molecular weight of AFPs computed is 9584 Da. SOSUI server predicts one transmembrane region in P04002 (winter flounder fish) and two regions in P09031 (yellowtail flounder fish). The predicted transmembrane regions were visualized and analyzed us...