Ekaterina V. Rokhina

Low-frequency ultrasound in biotechnology: state of the art

The use of low-frequency (10-60 kHz) ultrasound for enhancement of various biotechnological processes has received increased attention over the last decade as a rapid and reagentless method. Recent breakthroughs in sonochemistry have made the ultrasound irradiation procedure more feasible for a broader range of applications. By varying the sonication parameters, various physical, chemical and biological effects can be achieved that can enhance the target processes in accordance with the applied conditions. However, the conditions that have provided beneficial effects of ultrasound on bioprocesses are case-specific and are therefore not widely available in the literature. This review summarizes the current state of the art in areas where sonochemistry could be successfully combined with biotechnology with the aim of enhancing the efficiency of bioprocesses, including biofuel production, bioprocess monitoring, enzyme biocatalysts, biosensors and biosludge treatment.

Optimisation of Electro-Fenton denitrification of a model wastewater using a response surface methodology.

Electro-Fenton denitrification of a model wastewater was studied using platinized titanium electrodes in a batch electrochemical reactor. The model wastewater was prepared from components based on the real aquaculture effluent with nitrate concentrations varying from 200 to 800 mg L(-1). The technical as well as scientific feasibility of the method was assessed by the relationship between the most significant process variables such as various Fentons reagent to hydrogen peroxide ratios (1:5; 1:20 and 1:50) and current densities (0.17 mA cm(-2), 0.34 mA cm(-2) and 0.69 mA cm(-2)) and their response on denitrification efficiency in terms of nitrate degradation using central composite Box-Behnken experimental design was determined. The goodness of the model was checked by the coefficient of determination R(2) (0.9775), the corresponding analysis of variance P>F and a parity plot. The ANOVA results indicated that the proposed model was significant and therefore can be used to optimize denitrification of a model wastewater. The optimum reaction conditions were found to be 1:20 Fentons reagent/hydrogen peroxide ratio, 400 mg L(-1) initial nitrate concentration and 0.34 mA cm(-2) current density. Treatment costs in terms of electricity expenditure at 0.17, 0.34 and 0.69 mA cm(-2) was 7.6, 16 and 41.8 euro, respectively, per kilogram of nitrates and 1, 2 and 4 euro, respectively, per cubic meter of wastewater.

Environmental Application of Catalytic Processes: Heterogeneous Liquid Phase Oxidation of Phenol With Hydrogen Peroxide

The authors review the status of heterogeneous catalytic oxidation processes with hydrogen peroxide as an oxidant in a liquid phase. They focus on the priority organic pollutant–phenol as one of the most common persistent organic water contaminants, toxic even at low concentrations. A wide range of heterogeneous catalysts is covered, with a special emphasis on rapidly developing new catalytic systems. Generally accepted mechanisms of the catalytic oxidation via the formation of the most abundant reaction intermediates and terminal products followed by the conceptual kinetic models developed especially for the oxidation of phenol with hydrogen peroxide are also discussed. Theoretical methods, widely used to gain a profound process understanding, such as factorial design and life-cycle assessment, are summarized with popularization of their main principles, based on the most recent studies. The main idea is to identify and resume the main points of interest and problems encountered, estimate the attribution of operation parameters for catalyst selectivity and activity, elucidate the role of reactive oxidizing species in the process, and evaluate process potential for the future applications.

Free Radical Reaction Pathway, Thermochemistry of Peracetic Acid Homolysis, and Its Application for Phenol Degradation: Spectroscopic Study and Quantum Chemistry Calculations

The homolysis of peracetic acid (PAA) as a relevant source of free radicals (e.g., *OH) was studied in detail. Radicals formed as a result of chain radical reactions were detected with electron spin resonance and nuclear magnetic resonance spin trapping techniques and subsequently identified by means of the simulation-based fitting approach. The reaction mechanism, where a hydroxyl radical was a primary product of O-O bond rupture of PAA, was established with a complete assessment of relevant reaction thermochemistry. Total energy analysis of the reaction pathway was performed by electronic structure calculations (ab initio and semiempirical methods) at different levels and basis sets [e.g., HF/6-311G(d), B3LYP/6-31G(d)]. Furthermore, the heterogeneous MnO2/PAA system was tested for the elimination of a model aromatic compound, phenol from aqueous solution. An artificial neural network (ANN) was designed to associate the removal efficiency of phenol with relevant process parameters such as concentrations of both the catalyst and PAA and the reaction time. Results were used to train and test ANN to identify an optimized network structure, which represented the correlations between the operational parameters and removal efficiency of phenol.

ESR ST study of hydroxyl radical generation in wet peroxide system catalyzed by heterogeneous ruthenium.

Ru-based catalysts gained popularity because of their applicability for a variety of processes, including carbon monoxide oxidation, wet air catalytic oxidation and wastewater treatment. The focus of a current study was generation of hydroxyl radicals in the wet peroxide system catalyzed by heterogeneous ruthenium, spin-trapped by DEPMPO and DIPPMPO by means of electron spin resonance spin-trapping technique (ESR ST). The mechanism of free radicals formation was proposed via direct cleavage of hydrogen peroxide over ruthenium active sites. The chemical reactions occurring in the system were introduced according to the experimental results. Also, radical production rate was assessed based on concentration changes of species involved in the bulk liquid phase oxidation.

Evaluation of UV LEDs Performance in Photochemical Oxidation of Phenol in the Presence of H2O2

A novel application of ultraviolet (UV) light emitting diodes (LEDs) as a light source for the degradation of organic contaminant has been investigated. Photocleaving of hydrogen peroxide ( H2 O2 ) via UV LEDs photolysis resulted in the generation of hydroxyl radicals. It was found that phenol removal was insignificant in the absence of hydrogen peroxide, therefore oxidation of phenol was attributed to the formed radicals. Two criteria were selected to provide detailed information on the performance of UV LEDs in phenol oxidation: (1) the reaction quantum efficiency and (2) the energy consumption. Statistical tools such as the response surface methodology and the ANOVA were applied to estimate the influence of various process parameters such as the wavelength (255, 269, and 276 nm) and H2 O2 to phenol molar ratio (5, 50, and 100) on phenol degradation reaction quantum efficiency. The decay of phenol (initial concentration of 1.06 mM) was the most pronounced at 255 nm and H2 O2 to phenol molar ratio of 50....

Theoretical and practical aspects of chemical functionalization of carbon nanofibers (CNFs): DFT calculations and adsorption study

The nitric acid-functionalized commercial carbon nanofibers (CNFs) were comprehensively studied by instrumental (XRD, BET, SEM, TGA) and theoretical (DFT calculations) methods. The detailed surface study revealed the variation in the characteristics of functionalized CNFs, such as a decreased (up to 34%) surface area and impacted structural, electronic and chemical properties. The effects of functional groups were studied by comparison with pristine nanofibers. The results showed that the C-C bond lengths of the modified CNFs varied significantly. Chemical functionalization altered the frontier orbitals of the pristine material, and therefore altered the nature of their interactions with other substances. Moreover, the pristine and modified CNFs were tested for the removal of phenol from aqueous solutions. It was observed that surface modification tuned the adsorption capacity of carbon nanofibers (up to 0.35 mmol g(-1)), whereas original fibers did not demonstrate any adsorption capacity of phenol.

The effect of electrodialytic treatment and Na2H2EDTA addition on methanogenic activity of copper-amended anaerobic granular sludge: Treatment costs and energy consumption

The effect of electrodialytic treatment in terms of a current density, pH and Na(2)H(2)EDTA addition on the methanogenic activity of copper-amended anaerobic granular sludge taken from the UASB reactor from paper mill was evaluated. Moreover, the specific energy consumption and simplified operational and treatment costs were calculated. Addition of Na(2)H(2)EDTA (at pH7.7) to copper-amended sludge resulted in the highest microbial activity (62 mg CH(4)-COD g VSS(-1)day(-1)) suggesting that Na(2)H(2)EDTA decreased the toxic effects of copper on the methanogenic activity of the anaerobic granular sludge. The highest methane production (159 %) was also observed upon Na(2)H(2)EDTA addition and simultaneous electricity application (pH7.7). The energy consumption during the treatment was 560, 840, 1400 and 1680 kW h m(-3) at current densities of 0.23, 0.34, 0.57 and 0.69 mA cm(-2), respectively. This corresponded to a treatment costs in terms of electricity expenditure from 39.2 to 117.6 € per cubic meter of sludge.