Graphene oxide/titania photocatalytic ozonation of primidone in a visible LED photoreactor.

A graphene oxide-titania (GO/TiO2) composite was synthesized via sol-gel method, and studied in aqueous Primidone mineralization with ozone and LED visible light. The photocatalyst was characterized by different techniques (XRD, TEM, SBET, TGA, UV-vis diffuse reflectance spectroscopy). The band gap value decrease from 3.14 eV for bare TiO2 samples to 2.5 eV in GO/TiO2 composites clearly shows the interaction of GO with TiO2 structure. Approximately 20 mg L-1 of Primidone was removed in less than 20 min if ozone was applied, regardless of the presence or absence of light and catalyst. However, reactivity tests show a synergism effect between photocatalysis and ozonation for mineralization purposes. The combination of ozone and GO improved the activation of TiO2 under visible light. Process optimization led us to select a catalyst dosage of 0.25 g L-1, a light radiance of 359 W m-2 and a GO loading in the catalyst around 0.75%. At these conditions, with photocatalytic ozonation, the presence of GO in the catalyst improved mineralization up to 82% in 2 h compared to 70% reached with bare TiO2. Catalyst reusability shows no decrease of photocatalytic activity. Scavenger tests point to hydroxyl radicals as the main species responsible for Primidone removal.

Atomic force acoustic microscopy: Influence of the lateral contact stiffness on the elastic measurements.

Atomic force acoustic microscopy is a dynamic technique where the resonances of a cantilever, that has its tip in contact with the sample, are used to quantify local elastic properties of surfaces. Since the contact resonance frequencies (CRFs) monotonically increase with the tip-sample contact stiffness, they are used to evaluate the local elastic properties of the surfaces through a suitable contact mechanical model. The CRFs depends on both, normal and lateral contact stiffness, kN and kS respectively, where the last one is taken either as constant (kS<1), or as zero, leading to uncertainty in the estimation of the elastic properties of composite materials. In this work, resonance spectra for free and contact vibration were used in a finite element analysis of cantilevers to show the influence of kS in the resonance curves due to changes in the kS/kN ratio. These curves have regions for the different vibrational modes that are both, strongly and weakly dependent on kS, and they can be used in a selective manner to obtain a precise mapping of elastic properties.

Fast frequency sweeping in resonance-tracking SPM for high-resolution AFAM and PFM imaging.

A new resonance-tracking (RT) method using fast frequency sweeping excitation was developed for quantitative scanning probe microscopy (SPM) imaging. This method allows quantitative imaging of elastic properties and ferroelectrical domains with nanoscale resolution at high data acquisition rates. It consists of a commercial AFM system combined with a high-frequency lock-in amplifier, a programmed function generator and a fast data acquisition card. The resonance-tracking method was applied to the atomic force acoustic microscopy (AFAM) and to the piezoresponse force microscopy (PFM) modes. Plots of amplitude versus time and phase versus time for resonant spectra working with different sweeping frequencies were obtained to evaluate the response speed of the lock-in amplifier. It was proved that this resonance-tracking method allows suitable spectral acquisition at a rate of about 5 ms/pixel, which is useful for SPM imaging in a practical scanning time. In order to demonstrate the system performance, images of RT-AFAM for TiN films and RT-PFM for GeTe are shown.

Degradation of bisphenol A in water by Fe(III)/UVA and Fe(III)/polycarboxylate/UVA photocatalysis.

The photodegradation of the endocrine disrupting chemical Bisphenol A (BPA) under UVA irradiation in the presence of Fe(III) or Fe(III)-polycarboxylate systems was studied. The effect of Fe(III) concentration, aqueous pH and the presence of four carboxylic acids (oxalic, malic, tartaric and citric) were investigated. The Fe(III)/UVA system was able to effectively degrade BPA at pH 3 but failed at pH > 4. At any rate, no mineralization of BPA was achieved with the Fe(III)/UVA system. The presence of carboxylic acids greatly enhanced the BPA degradation rate because of the formation of photoactive Fe(III)-polycarboxylate complexes. Aqueous pH in the 3-7 range exerted a negative effect on the BPA degradation rate and TOC conversion in the presence of oxalic, malic and tartaric acids. Only slight effect of pH was observed in the presence of citric acid, being the BPA degradation rate significant even at pH 7.

Photocatalysis of fluorene adsorbed onto TiO2.

The adsorption of fluorene onto TiO2 has been investigated by conducting equilibrium and kinetic experiments. Adsorption isotherms have been evaluated at two different pHs in the range of temperatures 296-325 K. The type III isotherm shapes obtained were modelled by considering several expressions taken from the literature. Temperature exerted a positive influence in fluorene uptake. Addition of phosphates involved a negative effect when computing the final equilibrium fluorene removal. The kinetic experiments carried out at 296 K corroborated the competitiveness of phosphates to occupy the active sites on the titania surface. Nevertheless, equilibrium conditions are faster achieved at pH 2 than at pH 5. The photocatalysis of fluorene at different initial concentrations of the parent compound revealed a slight improvement of the process at pH 5 if compared to the results obtained at pH 2. A Langmuir-Hinselwood representation of the data confirms the previous statement. Catalyst load shows an optimum, concentration values of the photocatalyst above the optimum provoke a decrease in the fluorene abatement rate. Reutilisation of the catalyst indicates that fluorene is completely eliminated from the solid, i.e. it is suggested that fluorene and intermediates are surface oxidised.

Adsorption of landfill leachates onto activated carbon. Equilibrium and kinetics.

The adsorption of stabilized leachates generated in a municipal landfill onto three commercial activated carbons has been investigated. Norit 0.8, Chemviron AQ40 and Picacarb 1240 have been used as adsorbents. Equilibrium experiments have been conducted to obtain the experimental isotherm profiles. Isotherms have been plotted based on the adsorption of general parameters, for instance chemical oxygen demand, total carbon, absorption at 410 nm and absorption at 254 nm. Different literature models and error functions have been used to adequately fit the experimental data. As a rule of thumb, three-parameter models do adjust experimental results better than two-parameter models. Norit 0.8 shows better adsorption characteristics than the rest of activated carbons, both in terms of contaminant level reduction of per unit mass of absorbent and in terms of the process kinetics.

Ozonation of activated carbons: Effect on the adsorption of selected phenolic compounds from aqueous solutions.

The impact of ozonation on textural and chemical surface characteristics of two granular activated carbons (GAC), namely F400 and AQ40, and their ability to adsorb phenol (P), p-nitrophenol (PNP), and p-chlorophenol (PCP) from aqueous solutions have been studied. The porous structure of the ozone-treated carbons remained practically unchanged with regard to the virgin GAC. However, important modifications of the chemical surface and hydrophobicity were observed from FTIR spectroscopy, pH titrations, and determination of pH(PZC). As a rule, the ozone treatment at either room temperature (i.e., about 25 degrees C) or 100 degrees C gave rise to acidic surface oxygen groups (SOG). At 25 degrees C primarily carboxylic acids were formed while a more homogeneous distribution of carboxylic, lactonic, hydroxyl, and carbonyl groups was obtained at 100 degrees C. The experimental isotherms for phenolic compounds on both GAC were analyzed using the Langmuir model. Dispersive interactions between pi electrons of the ring of the aromatics and those of the carbon basal planes were thought to be the primary forces responsible for the physical adsorption whereas oxidative coupling of phenolic compounds catalyzed by basic SOG was a major cause of irreversible adsorption. The exposure of both GAC to ozone at room temperature decreased their ability to adsorb P, PNP, and PCP. However, when ozone was applied at 100 degrees C adsorption was not prevented but in some cases (P and PNP on F400) the adsorption process was even enhanced.

Comparison between thermal and ozone regenerations of spent activated carbon exhausted with phenol.

Thermal and ozone regenerations of granular activated carbons (GAC) used in the removal of phenol from aqueous solution have been studied. The phenol isotherms for virgin GAC could be well represented by the Langmuir equation. Direct ozonation of GAC introduced large amounts of acidic surface oxygen groups, which caused a decrease in the phenol uptake. Thermogravimetric methods were used to investigate the mechanism of phenol adsorption onto virgin and ozonated carbons. Thermal regeneration was carried out at 1123K using nitrogen (pyrolysis alone) or nitrogen and carbon dioxide (pyrolysis plus oxidation). Results showed that spent carbons do not recover their adsorption characteristics when heated under inert conditions whereas carbon dioxide regeneration was effective at about 15% wt burn-off. Regeneration of GAC was also carried out with ozone as oxidizing gas at room temperature. Ozone dose and the nature of GAC have much influence on the regeneration performance. For an individual GAC there exits an optimum ozone dose for which phenol is eliminated together with most of its oxidation by-products without incurring in carbon surface chemical alterations. However, if excessive ozone is applied some acidic surface groups are formed on the GAC, thereby decreasing the adsorption capacity for phenol. Results showed that spent carbons can recover most of their adsorption characteristics and specific surface areas when regenerated through a number of adsorption-ozone regeneration cycles.

Treatment of high strength distillery wastewater (cherry stillage) by integrated aerobic biological oxidation and ozonation.

The performance of integrated aerobic digestion and ozonation for the treatment of high strength distillery wastewater (i.e., cherry stillage) is reported. Experiments were conducted in laboratory batch systems operating in draw and fill mode. For the biological step, activated sludge from a municipal wastewater treatment facility was used as inoculum, showing a high degree of activity to distillery wastewater. Thus, BOD and COD overall conversions of 95% and 82% were achieved, respectively. However, polyphenol content and absorbance at 254 nm (A(254)) could not be reduced more than 35% and 15%, respectively, by means of single biological oxidation. By considering COD as substrate, the aerobic digestion process followed a Contois' model kinetics, from which the maximum specific growth rate of microorganisms (mu(max)) and the inhibition factor, beta, were then evaluated at different conditions of temperature and pH. In the combined process, the effect of a post-ozonation stage was studied. The main goals achieved by the ozonation step were the removal of polyphenols and A(254). Therefore, ozonation was shown to be an appropriate technology to aid aerobic biological oxidation in the treatment of cherry stillage.

Homogenous catalyzed ozonation of simazine. Effect of Mn(II) and Fe(II).

Simazine, [2-chloro, 4,6-bis(ethylamino)-1,3,5-s-triazine], a common herbicide typically found in surface and ground water was ozonised by using catalytic amounts of Mn(II) and Fe(II). An optimum value for metal concentration was found in the process. Some inhibition of the simazine degradation rate was observed when these metals were added above the optimum concentration. The pH of the reaction media played a significant role in the simazine oxidation rate. Thus, an increase in simazine conversion was observed when the pH was raised from 5 to 9. However, the catalytic effect of added manganese was negligible at the highest pH used in this study (pH 9). The beneficial influence of Fe(II) was also observed when utilising the combination of ozone and hydrogen peroxide. Contrarily, Mn(II) presented a negative influence on simazine conversion when using this oxidation technology.

Treatment of olive oil mill wastewater by Fenton's reagent.

Wastewater from olive oil mills has been treated by means of the Fe(II)/H(2)O(2) system (Fenton's reagent). Typical operating variables such as reagent concentration (C(H(2)O(2)) = 1.0--0.2 M; C(Fe(II)) = 0.01--0.1 M) and temperature (T = 293--323 K) exerted a positive influence on the chemical oxygen demand and total carbon removal. The optimum working pH was found to be in the range 2.5--3.0. The exothermic nature of the process involved a significant increase of the temperature of the reaction media. The process was well simulated by a semiempirical reaction mechanism based on the classic Fenton chemistry. From the model, the reaction between ferric iron and hydrogen peroxide [k = 1.8 x 10(15) exp((-12,577 +/- 1248)/T)] was suggested to be the controlling step of the system. Also, the simultaneous inefficient decomposition of hydrogen peroxide [k = 6.3 x 10(12) exp((-11,987 +/- 2414)/T)] into water and oxygen was believed to play an important role in the process. On the basis of stoichiometric calculations for hydrogen peroxide consumption, an estimation of the process economy has been completed.

Oxidation of p-hydroxybenzoic acid by Fenton's reagent.

Fenton's reagent has been shown to be a feasible technique to treat phenolic-type compounds present in a variety of food processing industry wastewaters. A model compound, p-hydroxybenzoic acid was oxidised by continuously pumping two solutions of ferrous iron and hydrogen peroxide. Typical operating variables like reagent feeding concentrations and flowrate, temperature and pH were studied. A mechanism of reactions based on the classical Fenton's chemistry was assumed, and computed concentration profiles of the parent compound, ferrous ion and dihydroxybenzene were compared to experimental results. The model qualitatively predicted the influence of several operating variables, however, calculated results suggested the presence of parallel routes of substrate elimination and/or a initiating rate constant with a higher value. The low efficiency of a well-known hydroxyl radical scavenger (tert-butyl alcohol) also supports the contribution of oxidising species different from the hydroxyl radical to substrate removal. Further evidence of the presence of reactions different from the hydroxyl radical oxidation was observed from comparison of the simultaneous Fenton's or UV/H2O2 oxidations of p-hydroxybenzoic acid, tyrosol and p-coumaric acid.

pH sequential ozonation of domestic and wine-distillery wastewaters.

Domestic and wine-distillery wastewaters were treated by semi-batch and continuous pH sequential ozonations. The process involves a succession of acidic and alkaline wastewater pH conditions. The alkaline periods allow oxidation of organic matter by hydroxyl radical and produce carbonates that eventually would inhibit the oxidation. On the other hand, the acidic periods favour the development of direct ozone reactions and strip off carbonates as carbon dioxide from the wastewater. Experimental results of pH sequential ozonation showed degradation and removal rates of wastewater pollutants higher than those achieved at constant either acidic or basic pH. The most significant improvement of ozone efficiency and pollutants removal were obtained by controlling the number of cycles, pH and time of acidic and alkaline phases. Also, ozonated wastewaters showed high biodegradability as deduced from their BOD/COD ratios. The feasibility of treating domestic and wine-distillery wastewater by an integrated activated sludge (ASP)-pH sequential ozonation system was evaluated. Integrated ASP-ozonation at constant pH processes were also carried out for comparative purposes. In these combined experiments, pH sequential ozonation showed advantages compared to ozonation at constant pH in reducing global parameters such as COD, TOC and TKN, but ozonation at constant pH led to higher removal of polyphenols and UV254 absorbing compounds.

Simazine removal from water in a continuous bubble column by O3 and O3/H2O2.

Simazine, [2-chloro, 4,6-bis(ethylamino)-1,3,5-s-triazine], a common herbicide found in surface and ground water has been ozonized in continuous flow mode. Typical operating variables in ozonation processes have been investigated. Thus, the ozone dose fed to the system exerted a positive effect, while the gas flow rate did not influence the efficiency of the process provided ozone mass flow rate was kept constant. Increasing the pH led to a higher extension of the free radical degradation of simazine and, therefore, to a higher efficiency of the process. Also, addition of free radical promoters, i.e. hydrogen peroxide, did result in a significant improvement of the simazine removal rate. A first approach to process economy showed the system ozone/hydrogen peroxide as the most advantageous in terms of electrical energy requirements.

Estimation of biological kinetic parameters from a continuous integrated ozonation-activated sludge system treating domestic wastewater.

The feasibility of treating municipal wastewater by a combined ozone-activated sludge continuous flow system was studied. Lab-scale experiments of both single activated sludge and combined ozone-activated sludge processes were carried out to determine the kinetic coefficients of the biological stage. The results obtained indicated a clear improvement in the kinetic parameters of the aerobic oxidation when a pre-ozonation stage was applied. Particularly, COD removal and nitrification rates were highly increased. The biokinetic parameters were also used to simulate and optimize the continuous reaction system. From the model prediction it was concluded that the integrated process (i.e., ozone-ASP) may significantly increase the waste reduction capacity. The results presented here provide a useful basis for further scaling up and efficient operation of ozone-ASP units in wastewater treatment processes.

Kinetic modelling of aqueous atrazine ozonation processes in a continuous flow bubble contactor.

The ozonation of atrazine in different waters (ultrapure and surface waters) has been studied in continuous bubble contactors with kinetic modelling purposes. Three ozonation processes have been considered: ozonation alone and combined with hydrogen peroxide or UV radiation. The kinetic models are based on a molecular and free radical mechanism of reactions, reaction rate and mass transfer data and non-ideal flow analysis models for gas and water phases through the contactors (the tanks in series model and the dispersion model). The models predict well the experimental concentrations of atrazine, dissolved ozone and hydrogen peroxide both at non-steady state and steady state regimes. From both experimental and calculated results, atrazine conversions are observed to be highly dependent on the nature of water where ozonation is carried out. As far as removal of atrazine and oxidation intermediates are concerned, ozone combined with UV radiation resulted in the most effective ozonation process among the three studied.

Chemical and photochemical degradation of acenaphthylene. Intermediate identification.

Removal of acenaphthylene from water has been carried out by means of different treatments combining UV radiation, ozone and hydrogen peroxide. Ozonation alone or in conjunction with hydrogen peroxide (10(-3) M) resulted in the highest elimination rates. Thus, conversions as high as 95-100% were obtained in less than 3 min with an ozone dose of 4.1x10(-3) mol O(3) h(-1) (flow rate 2x10(-2) m(3) h(-1)). Slightly lower efficiencies were experienced when using systems containing UV radiation. By considering the kinetics of the direct photolysis of acenaphthylene and the UV/H(2)O(2) system the photochemical reaction quantum yield φ(A) (4.0+/-0.1x10(-3) mol/photon) and the rate constant of the reaction of acenaphthylene with the hydroxyl radical k(OH,A) (8.0+/-0.5x10(9) M(-1) s(-1)) were calculated. Intermediates identified by GC/MS were in many cases similar regardless of the oxidation treatment used. Most of these by-products constituted oxygenated species of the parent compound (mainly ketones, aldehydes and carboxylic acids) that further degraded to low molecular, harmless end products.

Kinetics of simazine advanced oxidation in water.

Comparison of the effects and kinetics of UV photolysis and four advanced oxidation systems (ozone, ozone/hydrogen peroxide, ozone/UV radiation and UV radiation/hydrogen peroxide) for the removal of simazine from water has been investigated. At the conditions applied, the order of reactivity was ozone < ozone/hydrogen peroxide < UV radiation < ozone/UV radiation and UV radiation/hydrogen peroxide. Rate constants of the reactions between ozone and simazine and hydroxyl radical and simazine were found to be 8.7 M-1s-1 and 2.1 x 10(9) M-1s-1, respectively. Also, a quantum yield of 0.06 mol.photon-1 was found for simazine at 254 nm UV radiation. The high value of the quantum yield corroborated the importance of the direct photolysis process. Percentage contributions of direct reaction with ozone, reaction with hydroxyl radicals and direct photolysis were also quantified.

Wine distillery wastewater degradation. 1. Oxidative treatment using ozone and its effect on the wastewater biodegradability.

Laboratory-scale experiments were conducted to investigate the impact of ozonation on the degradability of wine distillery wastewaters, usually called vinasses, with the goal of developing combined chemical-biological methods for their treatment. Chemical oxygen demand (COD), biological oxygen demand (BOD), total organic carbon (TOC), and ultraviolet absorbance at 254 nm (UV(254)) were taken as reference parameters to follow the pollution level. The vinasses were treated both directly and after being mixed with domestic sewage. Ozonation of pure vinasses required high ozone doses to achieve a significant efficiency for removing the organic matter. Mixing vinasses with domestic sewage allowed higher degradation rates with ozone. Ozone was also demonstrated to be an appropriate oxidizing agent to improve vinasses's biodegradability and organic matter removal. A mathematical model of the ozonation kinetics based on the film theory concept is also presented.