Ozonation of a mixture of estrogens and progestins in aqueous solution: interpretation of experimental results by computational methods.

The degradation of the mixture of steroid hormones including seven estrogens (17α-estradiol, 17ß-estradiol, 17α-dihydroequilin, 17α-ethinyl estradiol, estriol, estrone and equilin) and five progestins (levonorgestrel, gestodene, trimegestrone, medrogestone and progesterone) by ozonation in aqueous solution is investigated. The ozonation process provides high removal (up to 100%) of hormones and estrogenicity in the treated water. Computational methods such as quantum chemistry calculations (QCCs) are applied to interpret the observed results. Quantum chemistry descriptors computed for steroid hormones explain the nature of the reactions and differences in reactivities between estrogen and progestin hormones within the framework of the Density Functional Theory (DFT). Computed molecular descriptors were combined with physical properties to develop qualitative structure activity relationship (QSAR) models (using multiple linear regression algorithm). The developed models have correlation coefficients (R(2)) of 0.994 for estrogens and 0.997 for progestins, and could be used to predict the removal efficiencies for similar compounds. The frontier molecular orbitals (the HOMO and the LUMO) have a major impact on the reactivity of steroid hormones. The susceptibility of certain functional groups to ozone and possible reactive sites for all steroids was discussed by Frontier Molecular Orbital approach.

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.

Application of density functional theory (DFT) to study the properties and degradation of natural estrogen hormones with chemical oxidizers.

Estrone (E1), 17ß-estradiol (E2), estriol (E3), equilin (EQ) and 17α-estradiol (17α) estrogen hormones are released by humans and animals and have been detected in the environment and municipal wastewater treatment plants. The structural and electronic properties of natural hormone molecules are investigated by performing density functional theory calculations and used to predict their properties and chemical behavior. Quantitative structure property relationship (QSPR) approach is applied to correlate the estrogenicity associated with the natural estrogen hormones according to their molecular properties. The obtained relationship reveals the importance of the frontier molecular orbital energy in the interpretation of estrogenic activity of hormones, which is consistent with the previous research. Moreover, the obtained molecular descriptors also aid determination of the degradability of hormones, and to rationalize degradation pathways, with chemical oxidizers such as ozone and hydroxyl radical. Both types of interactions belong to the orbital-controlled reactions. The active sites determined by Fukui functions for the estrogen hormone molecules confirm the reaction pattern that initiates the attack of the aromatic ring for both ozone and hydroxyl radical. The reactive sites of the molecules are mapped with subsequent reaction intermediates and compared with experimental data obtained from the literature.

Evaluation of relative importance of ultrasound reactor parameters for the removal of estrogen hormones in water.

The growing interest in sonochemistry as a tool for environmental remediation leads to the need for process optimization. Sonochemistry is a complex process, which depends on physical parameters and also on the process conditions. Physical parameters are interrelated and therefore a systematic approach has to be taken to optimize the process. The effect of physical parameters on the destruction of seven estrogen hormones (17α-estradiol, 17ß-estradiol, estriol, 17α-ethinylestradiol, 17α-dihydroequilin, estrone and equilin) is reported in this study. Artificial neural networks (ANN) was used as a tool to identify the correlations between these process parameters. ANN enabled the establishment of relationship between sonication parameters such as power density, power intensity, ultrasound amplitude, as well as the reactor design parameters. The major significance was attributed to the area-specific power density and the volume-specific power intensity. The results of this work provide a sound basis to design pilot and full-scale ultrasound treatment systems. Process optimization lead to a 5-fold decrease in energy consumption as compared to the commercially available reactors, thereby making the process attractive for field applications.

Combination of neural networks and DFT calculations for the comprehensive analysis of FDMPO radical adducts from fast isotropic electron spin resonance spectra.

The 4-hydroxy-5,5-dimethyl-2-trifluoromethylpyrroline-1-oxide (FDMPO) spin trap is very attractive for spin trapping studies due to its high stability and high reaction rates with various free radicals. However, the identification of FDMPO radical adducts is a challenging task since they have very comparable Electron Spin Resonance (ESR) spectra. Here we propose a new method for the analysis and interpretation of the ESR spectra of FDMPO radical adducts. Thus, overlapping ESR spectra were analyzed using computer simulations. As a result, the N- and F-hyperfine splitting constants were obtained. Furthermore, an artificial neural network (ANN) was adopted to identify radical adducts formed during various processes (e.g., Fenton reaction, cleavage of peracetic acid over MnO(2), etc.). The ANN was effective on both "known" FDMPO radical adducts measured in slightly different solvents and not a priori "known" FDMPO radical adducts. Finally, the N- and F-hyperfine splitting constants of ·OH, ·CH(3), ·CH(2)OH, and CH(3)(C═O)O(·) radical adducts of FDMPO were calculated using density functional theory (DFT) at the B3LYP/6-31G(d,p)//B3LYP/6-31G++//B3LYP/EPR-II level of theory to confirm the experimental data.

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.

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.

Comparative kinetic analysis of silent and ultrasound-assisted catalytic wet peroxide oxidation of phenol.

The kinetic study of silent and ultrasound-assisted catalytic wet peroxide oxidation of phenol in water was performed to qualitatively assess the effect of ultrasound on the process kinetics. Various kinetic parameters such as the apparent kinetic rate constants, the surface utilization coefficient and activation energy of phenol oxidation over RuI(3) catalyst were investigated. Comparative analysis revealed that the use of ultrasound irradiation reduced the energy barrier of the reaction but had no impact on the reaction pathway. The activation energy for the oxidation of phenol over RuI(3) catalyst in the presence of ultrasound was found to be 13kJmol(-1), which was four times smaller in comparison to the silent oxidation process (57kJmol(-1)). Finally, 'figures-of-merit' was utilized to assess different experimental strategies such as sonolysis alone, H(2)O(2)-enhanced sonolysis and sono-catalytic oxidation of phenol in order to estimate the electric energy consumption based on the kinetic rate constants of the oxidation process.

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 Fenton's 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 Fenton's 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.

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.

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.

Optimization of pulp mill effluent treatment with catalytic adsorbent using orthogonal second-order (Box-Behnken) experimental design.

Novel catalytic adsorbent (ruthenium on carbon) was employed for the treatment of pulp mill effluent in the presence of hydrogen peroxide. Mathematical model and optimization of the process regarding the most favorable COD (%), TOC (%) and color (%) removal rates was developed and performed with experimental design taking into account catalytic adsorption process kinetics. As the initial experimental design, 3(3-1) half-fractional factorial design (H-FFD) was accomplished at two levels to study the significance of the main effects, such as catalytic adsorbent (g l(-1)) and hydrogen peroxide (ppm) concentrations using the response surface methodology (RSM). Finally, a four factor-three coded level central composite design (CCD) with 28 runs was performed in order to fit a second-order polynomial model. Validation of the model was accomplished by different criteria including coefficient of determination and the corresponding analysis of variance. The achieved removal rates for TOC (up to 75%), COD (up to 73%) and color (up to 68%) were observed for the defined optimal conditions: 1g l(-1) of ruthenium on carbon, 7 ppm of hydrogen peroxide, pH = 4 and ambient temperature. The proposed method benefited significantly improved TOC, COD and color removal efficiency, regenerability and reusability of the catalytic adsorbent and unaltered initial pH of an effluent in comparison to traditional adsorption or oxidation processes.