Mitigation of the inhibitory effects of co-existing substances on the Fenton process by UV light irradiation.

Co-existing substances (substances not targeted for degradation) can negatively affect wastewater treatment process performance. Here, we quantitatively evaluated the effects of propanal, a common co-existing substance, on the degradation of the azo-dye Orange II, a common pollutant, by the Fenton process to provide data for the development of measures to reduce the effects of co-existing substances on this wastewater treatment process. Inhibition rate (IR; ratio of the reaction rate constants obtained in the absence and presence of propanal) was calculated to examine the effects of propanal on the degradation of Orange II. The IRs for the Fenton process in the first phase and the second phase were 1.6 and 4.2, respectively. However, addition of ultraviolet irradiation to the Fenton process (i.e., the photo-Fenton process) resulted in a comparable IR for the first phase but a markedly lower IR for the second phase. We attributed this to the improvement of the photo-reduction reaction rate due to complexation of propanal with ferric ions, which compensated for the scavenger effects (the trapping of OH radicals) of propanal. Thus, ultraviolet irradiation reduced the inhibitory effects of propanal on the degradation of Orange II by the Fenton process.

An integrin-targeting glutathione-activated zinc(II) phthalocyanine for dual targeted photodynamic therapy.

A zinc(II) phthalocyanine substituted with three 2,4-dinitrobenzenesulfonate (DNBS) groups and a cyclic arginine-glycine-aspartic acid (cRGDfK) moiety was prepared and characterized. With three strongly electron-withdrawing DNBS groups, this compound was fully quenched in terms of fluorescence emission and singlet oxygen generation in N,N-dimethylformamide and phosphate buffered saline due to the strong photoinduced electron transfer effect. In the presence of glutathione (GSH), which is the most abundant intracellular thiol particularly in tumor cells, the DNBS moieties were cleaved, thereby restoring these photoactivities and making the conjugate as a GSH-activated photosensitizer. Being a well-known integrin antagonist, the cyclic RGD peptide sequence could enhance the localization of the conjugate in integrin-upregulated tumor cells. As shown by confocal laser scanning microscopy and flow cytometry, the intracellular fluorescence intensity of the conjugate was significantly higher in the integrin-positive A549 and MDA-MB-231 cells than in the integrin-negative MCF-7 and HEK293 cells. The photocytotoxicity of the conjugate against MDA-MB-231 cells was also higher than that toward MCF-7 cells. The results suggest that this dual-functional photosensitizer is a promising candidate for targeted photodynamic therapy.

Assessment of the Content of Fluorescent Tracer in Granular Feed Mixture.

Background: This paper describes the use of fluorescence induced by UV radiation to evaluate the share of tracer in feed mixture. Methods: For the purpose of this study, three substances were used. They are as follows: Tinopal, Rhodamine B, and Uranine. Tracer in the form of maize or kardi was added to chicken feed before the mixing process. Grains used in the process were grinded in the mill sieve with a mesh size of 4 and 6 mm. The drawn samples of the mixture were illuminated with UV radiation to make grain tracer light, and then the photo was taken with a digital camera. The acquired images were analyzed with the use of a computer program running on the RGB color model, which was the way to obtain essential information about the percentage share of tracer. Results: It was observed that, in the case of kardi grains, the proposed method gives results significantly deviating from the verification method. Conclusions: Only the tests with the use of maize having an average particle diameter of 2.4 mm and tinted with the solution of Rhodamine B led to acceptable results (consensual with the predetermined verification level).

Ultrasonic Destruction of Acid Orange 7: Effect of Humic Acid, Surfactants and Complex Matrices.

The ultrasonic degradation at 600 kHz of an azo dye, acid orange 7 (AO7), in the presence of various dissolved natural organic matters (humic acid and surfactants) and in environmentally relevant matrices (natural water and seawater) was investigated. Additionally, the dependence of AO7 degradation on several operating parameters was clarified. The obtained results showed that ultrasound completely destroyed AO7 in 90 min of treatment but only 10% of TOC was removed after a long irradiation time. Investigations using the radical scavengers tert-butyl alcohol and KI revealed that AO7 degradation proceeds through radical reactions occurring at the bubble-liquid interface. AO7 conversion was strongly affected by the operating conditions. While the degradation of the dye was not affected by the presence of humic acid, it was impacted negatively by the presence of surfactants. Replacing deionized water by natural water and seawater as real environmental matrices did not affect the degradation of the dye.

Advanced Oxidation of Tartrazine and Brilliant Blue with Pulsed Ultraviolet Light Emitting Diodes.

This study investigated the effect of ultraviolet light-emitting diodes (UVLEDs) coupled with hydrogen peroxide as an advanced oxidation process (AOP) for the degradation of two test chemicals. Brilliant Blue FCF consistently exhibited greater degradation than tartrazine, with 83% degradation after 300 minutes at the 100% duty cycle compared with only 17% degradation of tartrazine under the same conditions. These differences are attributable to the structural properties of the compounds. Duty cycle was positively correlated with the first-order rate constants (k) for both chemicals but, interestingly, negatively correlated with the normalized first-order rate constants (k/duty cycle). Synergistic effects of both hydraulic mixing and LED duty cycle were manifested as novel oscillations in the effluent contaminant concentration. Further, LED output and efficiency were dependent upon duty cycle and less efficient over time perhaps due to heating effects on semiconductor performance.

Accelerating biodegradation of a monoazo dye Acid Orange 7 by using its endogenous electron donors.

Biodegradation of a monoazo dye - Acid Orange 7 (AO7) was investigated by using an internal circulation baffled biofilm reactor. For accelerating AO7 biodegradation, endogenous electron donors produced from AO7 by UV photolysis were added into the reactor. The result shows that AO7 removal rate can be accelerated by using its endogenous electron donors, such as sulfanilic and aniline. When initial AO7 concentration was 13.6mg/L, electron donors generated by 8h UV photolysis were added into the same system. The biodegradation rate 0.4mg0.05h-1 was enhanced 60% than that without adding electron donor. Furthermore, sulfanilic and aniline were found to be the main endogenous electron carriers, which could accelerate the steps of the azo dye biodegradation.

pH-degradable PVA-based nanogels via photo-crosslinking of thermo-preinduced nanoaggregates for controlled drug delivery.

pH-Degradable PVA nanogels, which are prepared by photo-crosslinking thermo-preinduced PVA nanoaggregates in water without any surfactants or toxic organic solvents, are used for intracellular PTX release and anticancer treatment. These nanogels fast degraded at mildly acidic conditions with a pH-triggered PTX release, and the degradation products are only native PVA and poly(hydroxyethyl acrylate) (PHEA) as well as acetaldehyde without any toxic byproducts. The nanogel sizes could be tailored by different temperatures during the crosslinking process. The results of confocal microscopy and flow cytometry revealed that smaller nanogels exhibited enhanced internalization with MCF-7 cells than the ones treated with larger nanogels, by which the smaller PTX-loaded nanogels induced a more significant cytotoxicity against MCF-7 cells. GRAPHIC ABSTRACT: pH-Degradable PVA nanogels can be prepared by photo-crosslinking of thermo-preinduced nanoaggregates with tailored nanogel sizes given their pH-triggered PTX release and fast acid-degradation into native PVA and cell-compatible poly(hydroxyethyl acrylate) (PHEA) as well as acetaldehyde.

Efficiency of a Photoreactor Packed with Immobilized Titanium Dioxide Nanoparticles in the Removal of Acid Orange 7.

In this paper, the removal efficiency of Color Index Acid Orange 7 (AO7) as a model contaminant was investigated in a batch-recirculated photoreactor packed with immobilized titanium dioxide type P25 nanoparticles on glass beads. The effects of different operational parameters such as the initial concentration of AO7, the volume of solution, the volumetric flowrate, and the light source power in the photoreactor were investigated. The results indicate that the removal percent increased with the rise in volumetric flowrate and power of the light source, but decreased with the rise of the initial concentration of AO7 and the volume of solution. The AO7 degradation was followed through total organic carbon, gas chromatography/mass spectroscopy (GC/MS), and mineralization products analysis. The ammonium and sulfate ions were analyzed as mineralization products of nitrogen and sulfur heteroatoms, respectively. The results of GC/MS revealed the production of 1-indanone, 1-phthalanone, and 2-naphthalenol as intermediate products for the removal of AO7 in this process.

Iron in non-hydroxyl radical mediated photochemical processes for dye degradation: Catalyst or inhibitor?

The acetylacetone (AA) mediated photochemical process has been proven as an efficient approach for decoloration. For azo dyes, the UV/AA process was several to more than ten times more efficient than the UV/H2O2 process. Iron is one of the most common elements on the earth. It is well known that iron can improve the UV/H2O2 process through thermal Fenton and photo-Fenton reactions. What will be the role of iron in the UV/AA process? Could iron-AA complexes act as photocatalysts in environmental remediation? To answer these questions, the photo-degradation of an azo dye, Acid Orange 7 (AO7), was conducted under the variant combinations of AA with iron species in both ionic (Fe2+, Fe3+) and complex (Fe(AA)3) forms. The pseudo-first-order decoloration rate constants of AO7 in these photochemical processes followed such an order: UV/Fe(II)/AA

Heterogeneous photo-Fenton decolorization of Orange II over Al-pillared Fe-smectite: response surface approach, degradation pathway, and toxicity evaluation.

A ferric smectite clay material was synthesized and further intercalated with Al2O3 pillars for the first time with the aim of evaluating its ability to be used as heterogeneous catalyst for the photo-Fenton decolorization of azo dye Orange II. UV irradiation was found to enhance the activity of the catalyst in the heterogeneous photo-Fenton process. Catalyst loading of 0.5g/L and hydrogen peroxide concentration of 13.5mM yielded a remarkable color removal, accompanied by excellent catalyst stability. The decolorization of Orange II followed the pseudo-first-order kinetics for initial dye concentrations from 20 to 160mg/L. The central composite design (CCD) based on the response surface methodology (RSM) was applied to evaluate the effects of several operating parameters, namely initial pH, catalyst loading and hydrogen peroxide concentration, on the decolorization efficiency. The RSM model was derived and the response surface plots were developed based on the results. Moreover, the main intermediate products were separated and identified using gas chromatography-mass spectrometry (GC-MS) and a possible degradation pathway was proposed accordingly. The acute toxicity experiments illustrated that the Daphniamagna immobilization rate continuously decreased during 150min reaction, indicating that the effluent was suitable for sequential biological treatment.

Mechanism of enhanced removal of quinonic intermediates during electrochemical oxidation of Orange II under ultraviolet irradiation.

The effect of ultraviolet irradiation on generation of radicals and formation of intermediates was investigated in electrochemical oxidation of the azo-dye Orange II using a TiO2-modified ß-PbO2 electrode. It was found that a characteristic absorbance of quinonic compounds at 255 nm, which is responsible for the rate-determining step during aromatics degradation, was formed only in electrocatalytic oxidation. The dye can be oxidized by either HO radicals or direct electron transfer. Quinonic compounds were produced concurrently. The removal of TOC by photo-assisted electrocatalytic oxidation was 1.56 times that of the sum of the other two processes, indicating a significant synergetic effect. In addition, once the ultraviolet irradiation was introduced into the process of electrocatalytic oxidation, the degradation rate of quinonic compounds was enhanced by as much as a factor of two. The more efficient generation of HO radicals resulted from the introduction of ultraviolet irradiation in electrocatalytic oxidation led to the significant synergetic effect as well as the inhibiting effect on the accumulation of quinonic compounds.

Ultrasound enhanced heterogeneous activation of peroxydisulfate by bimetallic Fe-Co/GAC catalyst for the degradation of Acid Orange 7 in water.

Bimetallic Fe-Co/GAC (granular activated carbon) was prepared and used as heterogeneous catalyst in the ultrasound enhanced heterogeneous activation of peroxydisulfate (PS, S2O(2-)8) process. The effect of initial pH, PS concentration, catalyst addition and stirring rate on the decolorization of Acid Orange 7 (AO7) was investigated. The results showed that the decolorization efficiency increased with an increase in PS concentration from 0.3 to 0.5 g/L and an increase in catalyst amount from 0.5 to 0.8 g/L. But further increase in PS concentration and catalyst addition would result in an unpronounced increase in decolorization efficiency. In the range of 300 to 900 r/min, stirring rate had little effect on AO7 decolorization. The catalyst stability was evaluated by measuring decolorization efficiency for four successive cycles.

A novel photochemical system of ferrous sulfite complex: kinetics and mechanisms of rapid decolorization of Acid Orange 7 in aqueous solutions.

We previously reported the decolorization of the azo dye Acid Orange 7 (AO7) by sulfate radical (SO4(-)) in the presence of iron(II) sulfite complex and oxygen under UV-vis irradiation (photo-iron(II) sulfite system). This system, however, achieves very limited mineralization of AO7 (in terms of total organic carbon (TOC) removal), which is not in accordance with literature reports on the oxidation of organic contaminants by SO4(-). In the present work, kinetics and products under irradiation of xenon lamp (350 W) were analyzed to reveal the reaction pathway of decolorization of AO7. Steady-state approximation (SSA) of SO4(-) radicals and apparent kinetics of AO7 were examined. The reaction between AO7 and SO4(-) was found to proceed in two steps, namely, electron transfer and SO4(-) addition. The second-order rate constant for the reaction between AO7 and SO4(-) was found to be 8.07 ± 1.07 × 10(9) M(-1) s(-1) by SSA and 6.80 ± 0.68 × 10(9) M(-1) s(-1) by competition kinetics method. The apparent kinetics of the decolorization of AO7 under irradiation closely fits the mechanism of radical chain reactions of various reactive sulfur species. By liquid chromatography coupled with mass spectrometry, we identified the sulfate adduct AO7-SO4 and confirmed the two-step reaction between AO7 and SO4(-). This stable sulfate adduct provides a good explanation of the poor TOC removal during decolorization of AO7 by the photo-iron(II) sulfite system.

Degrading a mixture of three textile dyes using photo-assisted electrochemical process with BDD anode and O2-diffusion cathode.

In this paper, degradation of a mixture of three azo dyes was studied by the photo-assisted electrochemical process using an O2-diffusion cathode containing carbon nanotubes and boron-doped diamond (BDD) anode. The concentration of three textile dyes (C.I. Acid Orange 8 (AO8), C.I. Acid Orange 10 (AO10), and C.I. Acid Orange 12 (AO12)) was determined simultaneously despite the severe overlap of their spectra. For this purpose, partial least square (PLS), as a multivariate calibration method, was utilized based on recording UV-Vis spectra during the decolorization process. Moreover, the central composite design was used for the modeling of photo-assisted electrochemical decolorization of the aqueous solutions containing three dyes. The investigated parameters were the initial concentration of three dyes, applied current and reaction time. Analysis of variance (ANOVA) revealed that the obtained regression models match the experimental results well with R (Khataee et al. 2010, Clean-Soil Air Water 38 (1):96-103, 2010) of 0.972, 0.971, and 0.957 for AO8, AO10, and AO12, respectively. Three-dimensional surface and contour plots were applied to describe the relation between experimental conditions and the observed response. The results of TOC analysis confirmed good ability of proposed photo-assisted electrochemical process for degradation and mineralization of textile industry wastewater.

Characterization and photocatalytic activity of Ag-Cu/TiO2 nanoparticles prepared by sol-gel method.

In this study, monometallic and bimetallic silver and copper doped TiO2 nanoparticles were prepared by sol-gel method. Structural and morphological characterizations of prepared nanoparticles were performed by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and N2 physisorption techniques. Co-doped TiO2 nanoparticles displayed pure anatase phase with 20-30 nm particle size and a humdrum distribution. The stability of anatase phase was increased with co-doping of silver and copper to TiO2 lattice. In addition, the co-doped TiO2 nanoparticles had a mesoporous structure with slit-shaped pores. The photocatalytic activity of all samples was evaluated in the photocatalytic removal of C.I. Acid Orange 7. Co-doped TiO2 nanoparticles by Ag and Cu were shown to have highest activity as compared with the Ag/TiO2, Cu/TiO2 and pure TiO2 nanoparticles. The best performance of co-doped TiO2 nanoparticles was observed for a sample calcined under 550 degrees C, containing optimum molar contents of silver (0.08 mol%) and copper (0.01 mol%) dopant ions.

CeO2 mediated photocatalytic degradation studies of C.I. acid orange 7.

CeO2 nanoparticles were prepared by a simple precipitation method, followed by calcination treatment. By selecting photocatalytic degradation of acid orange 7 (AO7) as a probe reaction, the influences of calcination temperature of catalyst, the concentration of AO7, initial pH value of AO7 solution and catalyst dosage on the photocatalytic activity of CeO2 were studied. It was found that CeO2 calcined at 550 degrees C shows the highest photocatalytic activity under visible light irradiation. It was revealed that under visible light irradiation the degradation of AO7 over CeO2 nanoparticles follows a dye self-sensitization mechanism. The degradation rate of AO7 increases with decrease in the initial pH value of the reaction solution, and degradation efficiency decreases with increase in the initial dye concentration. The optimal dosage of CeO2 in solution for AO7 degradation is 1 g/L.

Optimization of photocatalytic degradation of methyl blue using silver ion doped titanium dioxide by combination of experimental design and response surface approach.

Photocatalytic degradation of methyl blue (MYB) was studied using Ag(+) doped TiO(2) under UV irradiation in a batch reactor. Catalytic dose, initial concentration of dye and pH of the reaction mixture were found to influence the degradation process most. The degradation was found to be effective in the range catalytic dose (0.5-1.5g/L), initial dye concentration (25-100ppm) and pH of reaction mixture (5-9). Using the three factors three levels Box-Behnken design of experiment technique 15 sets of experiments were designed considering the effective ranges of the influential parameters. The results of the experiments were fitted to two quadratic polynomial models developed using response surface methodology (RSM), representing functional relationship between the decolorization and mineralization of MYB and the experimental parameters. Design Expert software version 8.0.6.1 was used to optimize the effects of the experimental parameters on the responses. The optimum values of the parameters were dose of Ag(+) doped TiO(2) 0.99g/L, initial concentration of MYB 57.68ppm and pH of reaction mixture 7.76. Under the optimal condition the predicted decolorization and mineralization rate of MYB were 95.97% and 80.33%, respectively. Regression analysis with R(2) values >0.99 showed goodness of fit of the experimental results with predicted values.

Adsorption and photocatalytic and photosensitised bleaching of acid orange 7 on multilayer mesoporous films of TiO2.

A series of mesoporous films of titania of different thicknesses are prepared and their surface areas and porosities determined by physical adsorption using Kr as the adsorbate. The amounts of acid orange 7 (AO7) adsorbed by these films are found to be proportional to their measured surface areas and so the possibility of using this as a method of determining the surface area of thin titania films is discussed. The initial rates of UV-driven photocatalytic- and visible-driven photosensitised-bleaching of AO7 in solution, upon UVA and visible light irradiation, respectively, are also directly dependent upon the measured surface areas of the titania films. The quantum efficiencies for the UV photocatalytic- and visible photosensitised-bleaching of AO7 by the thickest of the AO7 films were estimated to be 0.08 and 0.01%, respectively.

A study of parameter setting and characterization of visible-light driven nitrogen-modified commercial TiO2 photocatalysts.

An optimal condition applied to the Taguchi method with an L(9) orthogonal array for preparing a visible-light driven nitrogen-modified TiO(2) (N-TiO(2)) photocatalyst by a simple hydrolysis method has been examined for material characteristics and a photodecolorization test of methyl blue (MB) under various visible light source (fluorescent and blue LED lamps) irradiations. Results of the material characterization showed that the absorption of prepared N-TiO(2) powder exhibited a significant extension into visible light regimes with an optical bandgap (Eg) of around 2.96 eV, which subsequently improved the visible-light photocatalytic activity of N-TiO(2) samples. The superior photocatalytic properties, the pseudo first-order reaction rate constants (k) and photodecolorization efficiency (η%) of a N-TiO(2) photocatalyst during the photodecolorization test of methyl blue (MB) under two different visible light irradiations were very evident compared to those for pure TiO(2). For photodecolorization of practical dyeing from the waste water from the dyeing and finishing industry, a higher photodecolorization efficiency of N-TiO(2) powder toward Direct blue-86 (DB-86) (Direct Fast Turquoise Blue GL) dye was also achieved.