Effect of substituents in hydroxyl radical-mediated degradation of azo pyridone dyes: Theoretical approaches on the reaction mechanism

Understanding the degradation behavior of azo dyes in photocatalytic wastewater treatment is of fundamental and practical importance for their application in textile-processing and other coloration industries. In this study, quantum chemistry, as density functional theory, was used to elucidate different degradation pathways of azo pyridone dyes in a hydroxyl radical (HO^?)-initiated photocatalytic system. A series of substituted azo pyridone dyes were synthesized by changing the substituent group in the para position of the benzene moiety, ranging from strong electron-donating to strong electron-withdrawing groups. The effect of dye molecular structure on the photocatalytic degradation reaction mechanism was analyzed and quantification of substituent effects on the thermodynamic and kinetics parameters was performed. Potential energy surface analysis revealed the most susceptible reaction site for the HO^? attack. The calculated reaction barriers are found to be strongly affected by the nature of substituent group with a good correlation using Hammett σ_p constants and experimentally determined reaction rates. The stability of pre-reaction complexes and transition state complexes were analyzed applying the distortion-interaction model. The increased stability of the transition state complexes with the distancing from the substituent group has been established.     

贵州喀斯特地区旅游资源的变异与可持续利用

喀斯特景观与民族文化是不可再生的旅游资源,其开发在促进喀斯特地区经济、文化发展的同时,也加剧了环境的损耗和地方特色的消失,旅游资源变异现象普遍发生。文中分析了资源变异的几种情况,并指出控制资源变异,实现可持续利用的途径     

Degradation of azo dyes in water by Electro-Fenton process

The degradation of the azo dyes azobenzene, p-methyl red and methyl orange in aqueous solution at room temperature has been studied by an advanced electrochemical oxidation process (AEOPs) under potential-controlled electrolysis conditions, using a Pt anode and a carbon felt cathode. The electrochemical production of Fenton's reagent (H₂O₂, Fe²⁺) allows a controlled in situ generation of hydroxyl radicals (^·OH) by simultaneous reduction of dioxygen and ferrous ions on the carbon felt electrode. In turn, hydroxyl radicals react with azo dyes, thus leading to their mineralization into CO₂ and H₂O. The chemical composition of the azo dyes and their degradation products during electrolysis were monitored by high performance liquid chromatography (HPLC). The following degradation products were identified: hydroquinone, 1,4-benzoquinone, pyrocatechol, 4-nitrocatechol, 1,3,5-trihydroxynitrobenzene and p-nitrophenol. Degradation of the initial azo dyes was assessed by the measurement of the chemical oxygen demand (COD). Kinetic analysis of these data showed a pseudo-first order degradation reaction for all azo dyes. A pathway of degradation of azo dyes is proposed. Specifically, the degradation of dyes and intermediates proceeds by oxidation of azo bonds and aromatic ring by hydroxyl radicals. The results display the efficiency of the Electro-Fenton process to degrade organic matter. Electronic Publication     

Treatment of azo dye Orange II in a sequential anaerobic and aerobic-sequencing batch ractor system

We studied the biodegradation of Orange II in a sequential anaerobic and aerobic-sequencing batch reactor system. Granular activated carbon was used either packed into a column or added directly into the anaerobic reactor to investigate the treatment performance between the two operation conditions. We found that the circulation of mixed liquor between the anaerobic reactor and the carbon-packed column enhanced the chemical oxygen demand from 28 to 52% and Orange II removal efficiencies from 88 to 96%, under simultaneous adsorption and biodegradation process. The morphology of microbes was observed under an electron-scanning microscope.     

Efficient treatment of azo dye containing wastewater in a hybrid acidogenic bioreactor stimulated by biocatalyzed electrolysis

In this study, a novel scaled-up hybrid acidogenic bioreactor(HAB) was designed and adopted to evaluate the performance of azo dye(acid red G, ARG) containing wastewater treatment. Principally, HAB is an acidogenic bioreactor coupled with a biocatalyzed electrolysis module. The effects of hydraulic retention time(HRT) and ARG loading rate on the performance of HAB were investigated. In addition, the influent was switched from synthetic wastewater to domestic wastewater to examine the key parameters for the application of HAB. The results showed that the introduction of the biocatalyzed electrolysis module could enhance anoxic decolorization and COD(chemical oxygen demand) removal. The combined process of HAB-CASS presented superior performance compared to a control system without biocatalyzed electrolysis(AB-CASS). When the influent was switched to domestic wastewater, with an environment having more balanced nutrients and diverse organic matters, the ARG, COD and nitrogen removal efficiencies of HAB-CASS were further improved, reaching 73.3% ± 2.5%, 86.2% ± 3.8% and 93.5% ± 1.6% at HRT of 6 hr, respectively, which were much higher than those of AB-CASS(61.1% ± 4.7%,75.4% ± 5.0% and 82.1% ± 2.1%, respectively). Moreover, larger TCV/TV(total cathode volume/total volume) for HAB led to higher current and ARG removal. The ARG removal efficiency and current at TCV/TV of 0.15 were 39.2% ± 3.7% and 28.30 ± 1.48 m A,respectively. They were significantly increased to 62.1% ± 2.0% and 34.55 ± 0.83 m A at TCV/TV of 0.25. These results show that HAB system could be used to effectively treat real wastewater.     

Effects of glucose on the decolorization of Reactive Black 5 by yeast isolates

The cometabolic roles of glucose were investigated in decolorization of an azo dye, Reactive Black 5, by yeast isolates, Debaryomyces polymorphus and Candida tropicalis. The results indicated that the dye degradation by the two yeasts was highly associated with the yeast growth process and glucose presence in the medium. Color removal of 200 mg dye/L was increased from 76.4% to 92.7% within 60 h to 100% within 18-24 h with the increase of glucose from 5 to 10 g/L, although the activity of manganese dependent peroxidase （MnP） decreased by 2-8 times in this case. Hydrogen peroxide of 233.3 μg/L was detected in 6 h in D. polymorphus culture. The cometabolic functions of glucose and hydrogen peroxide could be also confirmed by the further color removals of 95.8% or 78,9% in the second cycle of decolorization tests in which 7 g glucose/L or 250 μg H202/L was superadded respectively together with 200 mg dye/L.     

Acid Orange 7 degradation using methane as the sole carbon source and electron donor

• AO7 degradation was coupled with anaerobic methane oxidation. • Higher concentration of AO7 inhibited the degradation. • The maximum removal rate of AO7 reached 280 mg/(L·d) in HfMBR. • ANME-2d dominated the microbial community in both batch reactor and HfMBR. • ANME-2d alone or synergistic with the partner bacteria played a significant role. Azo dyes are widely applied in the textile industry but are not entirely consumed during the dyeing process and can thus be discharged to the environment in wastewater. However, azo dyes can be degraded using various electron donors, and in this paper, Acid Orange 7 (AO7) degradation performance is investigated using methane (CH₄) as the sole electron donor. Methane has multiple sources and is readily available and inexpensive. Experiments using ¹³C-labeled isotopes showed that AO7 degradation was coupled with anaerobic oxidation of methane (AOM) and, subsequently, affected by the initial concentrations of AO7. Higher concentrations of AO7 could inhibit the activity of microorganisms, which was confirmed by the long-term performance of AO7 degradation, with maximum removal rates of 8.94 mg/(L·d) in a batch reactor and 280 mg/(L·d) in a hollow fiber membrane bioreactor (HfMBR). High-throughput sequencing using 16S rRNA genes showed that Candidatus Methanoperedens, affiliated to ANME-2d, dominated the microbial community in the batch reactor and HfMBR. Additionally, the relative abundance of Proteobacteria bacteria (Phenylobacterium, Pseudomonas, and Geothermobacter) improved after AO7 degradation. This outcome suggested that ANME-2d alone, or acting synergistically with partner bacteria, played a key role in the process of AO7 degradation coupled with AOM.     

Kinetic mechanism and effects of molecular structure on thermal hazards of azo compounds

In this paper, the kinetic mechanism of AIBN, AMBN, and ABVN was proposed, and the effect of molecular structure on their thermal hazards based on the kinetic mechanism was investigated. Calculated by non-isothermal DSC datum, the kinetic mechanism of AIBN, AMBN, and ABVN is revealed by the linear relationship between the integrated form of mechanical function and reaction time. The results indicate that the thermal decomposition process is controlled by the Johnson-Mehl-Avrami equation. Based on the determination of kinetic mechanism function, the reaction rate constants at various heating rates are directly calculated, and the intercept of the best fitting straight line of reaction rate constants with heating rate is approximately equal to the reaction rate constant under isothermal conditions. Besides, theoretical values obtained by multiplying kinetic mechanism function by reaction rate are well consistent with the experimental values, suggesting that the kinetic mechanism obtained is credible. Bond Dissociation Energies (BDE) calculated by quantum chemical equations are employed to evaluate the thermodynamics stability of AIBN, AMBN, and ABVN. Depending on similar molecular structures, the influence of differentiated group structure on the thermodynamic stability represented by BDE and heat release and the kinetic stability characterized by reaction rate constant were revealed. Finally, the results demonstrate that the thermal hazard increases as the volume of substituent group and molecular weight.     

Investigating the sources of the mutagenic activity found in a river using the Salmonella assay and different water extraction procedures

In the routine São Paulo state (Brazil) surface water quality-monitoring program, which includes the Salmonella microsome mutagenicity assay as one of its parameters, a river where water is taken and treated for drinking water purposes has repeatedly shown mutagenic activity. A textile dyeing facility employing azo-type dyes was the only identifiable source of mutagenic compounds. We extracted the river and drinking water samples with XAD4 at neutral and acidic pH and with blue rayon, which selectively adsorbs polycyclic compounds. We tested the industrial effluent, raw, and treated water and sediment samples with YG1041 and YG1042 and compared the results with the TA98 and TA100 strains. The elevated mutagenicity detected with YG-strains suggested that nitroaromatics and/or aromatic amines were causing the mutagenicity detected in the samples analyzed. Positive responses for the blue rayon extracts indicated that mutagenic polycyclic compounds were present in the water samples analyzed. The mutagen or mixture of mutagens present in the effluent and water samples cause mainly frameshift mutations and are positive with and without metabolic activation. The Salmonella assay combined with different extraction procedures proved to be very useful in the identification of the origin of the pollution and in the identification of the classes of chemical compounds causing the mutagenic activity in the river analyzed.