Synthesis and characterisation of Pd-modified N-doped TiO2 for photocatalytic degradation of natural organic matter (NOM) fractions

Introduction

The removal of natural organic matter (NOM) from water is becoming increasingly important in order to prevent the formation of carcinogenic disinfection by-products. The inadequate removal of NOM has a bearing on the capacity of the other treatment processes to remove organic micro-pollutants or inorganic species that may be present in the water. New methods are therefore currently being sought to effectively characterise NOM and also to ensure that it is sufficiently removed from drinking water sources.

Methodology

Nitrogen- and palladium-co-doped TiO₂ was synthesised by a modified sol?Cgel method and evaluated for its photocatalytic degradation activity on NOM fractions under simulated solar radiation. The photocatalyst was characterised by FT-IR, Raman, XRD, DRUV?Cvis, SEM, TEM, EDS, XPS and TGA. FT-IR confirmed the presence of OH groups on thermally stable, nearly spherical anatase nanoparticles with an average diameter of 20?nm. PdO species appeared on the surface of the TiO₂ as small uniformly dispersed particles (2 to 3?nm). A red shift in the absorption edge compared to commercial anatase TiO₂ was confirmed by DRUV?Cvis. In order to gain a better insight into the response of NOM to photodegradation, the NOM was divided into three different fractions based on its chemical nature.

Results and discussion

Photodegradation efficiencies of 96, 38 and 15?% were realised for the hydrophobic, hydrophilic and transphilic NOM fractions, respectively. A reasonable mechanism was proposed to explain the photocatalytic degradation of the NOM fractions. The high photocatalytic activity could be attributed to the larger surface area, smaller crystalline size and synergistic effects of the co-dopants N and Pd in the TiO₂ crystal.     

Photocatalytic degradation of gaseous toluene by using immobilized titania/silica on aluminum sheets

Purpose

The aim of this study was to prepare a highly active immobilized titania/silica photocatalyst and to test its performance in situ toward degradation of toluene as one of the major toxic indoor contaminants.

Methods

In this work, two different titania layers immobilized on Al sheets were synthesized via low temperature sol?Cgel method employing presynthesized highly active titania powders (Degussa P25 and Millennium PC500, mass ratio 1:1): (a) with a silica/titania binder and a protective layer and (b) without the binder. The photocatalysts were characterized by X-ray diffraction, nitrogen sorption measurements, scanning electron microscopy (SEM), infrared spectroscopy, and UV?Cvis diffuse reflectance spectroscopy (DRS). The in situ photocatalytic degradation of gaseous toluene was selected as a probe reaction to test photocatalytic activity and to verify the potential application of these materials for air remediation.

Results

Results show that nontransparent highly photocatalytically active coatings based on the silica/titania binder and homogeneously dispersed TiO₂ powders were obtained on the Al sheets. The crystalline structure of titania was not altered upon addition of the binder, which also prevented inhomogeneous agglomeration of particles on the photocatalyst surface. The photoactivity results indicate that the adsorption properties and photocatalytic activity of immobilized photocatalysts with the silica/titania binder and an underlying protective layer were very effective and additionally, they exhibited considerably improved adhesion and uniformity.

Conclusion

We present a new highly photocatalytically active immobilized catalyst on a convenient metallic support, which has a potential application in an air cleaning device.     

Study of TiO2 anatase nano and microstructures with dominant {001} facets for NO oxidation

Introduction

TiO₂ anatase nanoplates and hollow microspheres were fabricated by a solvothermal?Chydrothermal method using titanium isopropoxide as a titanium precursor and hydrofluoric acid as a capping agent in order to enhance the formation of the {001} crystal facets of the anatase nanocrystals.

Methods

These different morphological structures of TiO₂ anatase can be achieved by only changing the solvent, keeping the amount of the precursor and of the capping agent identical during the solvothermal?Chydrothermal process.

Results and discussion

After calcination of the samples, the adsorbed fluoride atoms on the {001} crystal facets of the TiO₂ anatase nanocrystals were completely removed from their surface according to XPS analysis. The calcined TiO₂ anatase structures were higher crystallized and the specific surface area of the catalysts increased, enhancing their photocatalytic activity in comparison to the non-calcined TiO₂ anatase structures. All TiO₂ anatase samples with adsorbed as well as non-adsorbed fluoride atoms on their {001} crystal facets, exhibited a higher photonic efficiency than Degussa P25, which was used as a reference.

Conclusion

The fluoride free TiO₂ anatase nanoplates exhibited the best photocatalytic activity in oxidizing the NO gas to NO₂ and NO₃ ^?.     

Photocatalytic behavior of nanosized TiO2 immobilized on layered double hydroxides by delamination/restacking process

Introduction

Efficient immobilization of TiO₂ nanoparticles on the surface of Mg₂Al-LDH nanosheets was performed by delamination/restacking process.

Experimental part

The structural and textural properties of as-prepared nanocomposite were deeply analyzed using different solid-state characterization techniques such as: X-ray powder diffraction, Fourier transform infrared spectroscopy, and Raman spectroscopies, chemical analysis, X-ray photoelecton spectroscopy, N₂ adsorption?Cdesorption, and electronic microscopy.

Results and discussion

The photocatalytic properties of immobilized TiO₂ nanoparticles on Mg₂Al were investigated using the photodegradation of two model pollutants: Orange II and 4-chlorophenol, and compared with pure colloidal TiO₂ solution.

Conclusion

It appears that Orange II photodegradation was systematically faster and more efficient than 4-chlorophenol photodegradation regardless of the medium pH. Moreover under slightly basic conditions, even if the TiO₂ photocatalytic efficiency decreases, photodegradation performed in presence of easily recovered TiO₂/Mg₂Al_1.5 nanocomposite gives rise to comparable or better results than pure TiO₂.     

In situ photoelectrochemical/photocatalytic study of a dye discoloration in a microreactor system using TiO2 thin films

Introduction

In this work, we report in situ studies of UV photoelectrocatalytic discoloration of a dye (indigo carmine) by a TiO₂ thin film in a microreactor to demonstrate the driving force of the applied electrode potential and the dye flow rate toward dye discoloration kinetics.

Methods

TiO₂ 65-nm-thick thin films were deposited by PVD magnetron sputtering technique on a conducting glass substrate of fluorinated tin oxide. A microreactor to measure the discoloration rate, the electrode potential, and the photocurrent in situ, was developed. The dye solutions, before and after measurements in the microreactor, were analyzed by Raman spectroscopy.

Results

The annealed TiO₂ thin films had anatase structure with preferential orientation (101). The discoloration rate of the dye increased with the applied potential to TiO₂ electrode. Further, acceleration of the photocatalytic reaction was achieved by utilizing dye flow recirculation to the microreactor. In both cases the photoelectrochemical/photocatalytic discoloration kinetics of the dye follows the Langmuir?CHinshelwood model, with first-order kinetics.

Conclusions

The feasibility of dye discoloration on TiO₂ thin film electrodes, prepared by magnetron sputtering using a flow microreactor system, has been clearly demonstrated. The discoloration rate is enhanced by applying a positive potential (E _AP) and/or increasing the flow rate. The fastest discoloration and shortest irradiation time (50?min) produced 80% discoloration with an external anodic potential of 0.931?V and a flow rate of 12.2?mL?min^?1.     

Superior photodecomposition of pyrene by metal ion-loaded TiO2 catalyst under UV light irradiation

Background

The photocatalytic degradation of pyrene under UV (125?W Hg-Arc, 10.4?mW/cm²) irradiation of TiO₂ aqueous suspension has been found to be highly improved with the dissolved transition metal ions like Cu²⁺, Fe³⁺, Ag⁺, and Au³⁺, etc. As the reduction potential of these metals lies below the conduction band (CB) position (?0.1?eV) of TiO₂, the photoexcited electron transfer occurs more readily and reduces electron?Chole recombination rate. Therefore, it has a beneficial influence on the photocatalytic ability of TiO₂ because of rapid Fermi energy equilibrium between the CB of TiO₂ and its surface adsorbed metal ions.

Results and discussion

The Fermi level is referred to as the electrochemical potential and plays an important role in the band theory of solids. When metal and semiconductor are in contact, electron migration from photoirradiated semiconductor to the deposited metal occurs at the interface until two Fermi levels equilibrate and enhanced the photocatalytic activity of semiconductor photocatalyst. Ni²⁺ having more negative reduction potential (?0.25?eV) than the CB of TiO₂ imparts negligible co-catalytic activity to TiO₂ photoreaction. It also revealed that loading of Au³⁺ ions displayed higher degradation rate of pyrene than Au photodeposition. Furthermore, when the amount of dissolved Fe⁺³ and Au³⁺ ions gradually increases from 0.1 to 2?wt.%, the pyrene photodecomposition rate also become faster.     

Comparison of methods for evaluation of activity of photocatalytic films

Objective

This work aims to investigate the correlation between the photocatalytic activity determined by methylene blue bleaching (DIN 52980), stearic acid degradation, and degradation of acetone in gas phase.

Method

The photocatalytic TiO₂ coatings included in this investigation ranged from thin commercially available coatings (Activ^TM and BioClean^TM) and ready to use suspensions (Nano-X PK1245) to lab-produced PVD and sol?Cgel coatings. XRD analysis of the photocatalytic coatings showed that all the coatings consisted of nanocrystalline anatase, although the thickness and porosity varied considerably.

Results

The study showed that the reproducibility of the activity measurements was good. However, more importantly, the investigation showed that there is a good correlation between the activities determined by the different methods even though the characteristics of the photocatalytic coatings and the organic probe molecules varied considerably.

Conclusion

The overall findings of this work suggest that there is a good correlation between the investigated methods. These results are promising for the future work concerning standardization of methods for determination of the activity of photocatalytic films.     

Heterogeneous photocatalytic degradation of methyl orange in schwertmannite/oxalate suspension under UV irradiation

Introduction

Schwertmannite was synthesized through an oxidation of FeSO₄ by Acidithiobacillus ferrooxidans LX5 cell suspension at an initial pH?2.5 and 28°C for 3?days and characterized using X-ray diffraction spectroscopy and scanning electron microscope. The schwertmannite photocatalytic degradation of methyl orange (MO) by oxalate was investigated at different initial pH values, concentrations of schwertmannite, oxalate, and MO.

Results

The results demonstrated that photodegradation of MO in the presence of schwertmannite or oxalate alone was very weak. However, the removal of MO was significantly enhanced when schwertmannite and oxalate coexisted in the reaction system. Low pH (4 or less) was beneficial to the degradation of MO. The optimal doses of schwertmannite and oxalate were 0.2?g?L^?1 and 2?mM, respectively. Hydroxyl radicals (·OH) and Fe(II), the intermediate products, were also examined during the reaction to explore their correlation with the degradation of MO.

Conclusion

A possible mechanism for the photocatalytic decomposition of MO in the study was proposed. The formation of Fe(III)-oxalate complexes on the surface of schwertmannite was a precursor of H₂O₂ and Fe(II) production, further leading to the yield of ·OH responsible for the decomposition of MO.     

Biodegradation of benzene, toluene, and xylene (BTX) in liquid culture and in soil by Bacillus subtilis and Pseudomonas aeruginosa strains and a formulated bacterial consortium

Purpose

The major aromatic constituents of petroleum products viz. benzene, toluene, and mixture of xylenes (BTX) are responsible for environmental pollution and inflict serious public concern. Therefore, BTX biodegradation potential of individual as well as formulated bacterial consortium was evaluated. This study highlighted the role of hydrogen peroxide (H₂O₂), nitrate, and phosphate in stimulating the biodegradation of BTX compounds under hypoxic condition.

Materials and methods

The individual bacterium viz. Bacillus subtilis DM-04 and Pseudomonas aeruginosa M and NM strains and a consortium comprising of the above bacteria were inoculated to BTX-containing liquid medium and in soil. The bioremediation experiment was carried out for 120?h in BTX-containing liquid culture and for 90?days in BTX-contaminated soil. The kinetics of BTX degradation either in presence or absence of H₂O₂, nitrate, and phosphate was analyzed using biochemical and gas chromatographic (GC) technique.

Results

Bacterial consortium was found to be superior in degrading BTX either in soil or in liquid medium as compared to degradation of same compounds by individual strains of the consortium. The rate of BTX biodegradation was further enhanced when the liquid medium/soil was exogenously supplemented with 0.01?% (v/v) H₂O₂, phosphate, and nitrate_. The GC analysis of BTX biodegradation (90?days post-inoculation) in soil by bacterial consortium confirmed the preferential degradation of benzene compared to m-xylene and toluene.

Conclusions

It may be concluded that the bacterial consortium in the present study can degrade BTX compounds at a significantly higher rate as compared to the degradation of the same compounds by individual members of the consortium. Further, addition of H₂O₂ in the culture medium as an additional source of oxygen, and nitrate and phosphate as an alternative electron acceptor and macronutrient, respectively, significantly enhanced the rate of BTX biodegradation under oxygen-limited condition.     

Remediation of 4-nonylphenol in aqueous solution by using free radicals generated by the oxidative reactions

Introduction

This study relates to use of zerovalent iron to generate hydroxyl free radicals and undergo subsequent oxidation to destroy 4-nonylphenol (NP) by mild process in aqueous solution and activation of oxygen gas (O₂) at room temperature. This technology is based on a novel oxidative mechanism mediated by zerovalent iron rather than commonly used reduction mechanism.

Materials and methods

A laboratory scale device consisting of a 250?ml pyrex serum vials fixed to a Vortex agitator was used. Different amounts of zerovalent iron powder (ZVI; 1, 10, and 30?g/l) at pH?4 and room temperature with bubbling of oxygen gas were investigated.

Results and conclusion

Experiments showed an observed degradation rate k _(obs) directly proportional to the amount of iron. 4-Nonylphenol degradation reactions demonstrated first-order kinetics with a half-life of about 10.5?±?0.5 and 3.5?±?0.2?min when experiments were conducted at [ZVI]?=?1 and 30?g/l respectively. Three analytical techniques were employed to monitor 4-nonylphenol degradation and mineralization: (1) spectrofluorimetry; (2) high-performance liquid chromatography; (3) total organic carbon meter (TOC meter). Results showed a complete disappearance of 4-nonylphenol after 20?min of contact with ZVI. The intermediate by-products of the reaction were not identified but the disappearance of NP was monitored by the three above-mentioned techniques.     

Performance evaluation of a continuous flow photocatalytic reactor for wastewater treatment

A novel photocatalytic reactor for wastewater treatment was designed and constructed. The main part of the reactor was an aluminum tube in which 12 stainless steel circular baffles and four quartz tube were placed inside of the reactor like shell and tube heat exchangers. Four UV–C lamps were housed within the space of the quartz tubes. Surface of the baffles was coated with TiO₂. A simple method was employed for TiO₂ immobilization, while the characterization of the supported photocatalyst was based on the results obtained through performing some common analytical methods such as X-ray diffraction (XRD), scanning electron microscope (SEM), and BET. Phenol was selected as a model pollutant. A solution of a known initial concentration (20, 60, and 100 ppmv) was introduced to the reactor. The reactor also has a recycle flow to make turbulent flow inside of the reactor. The selected recycle flow rate was 7?×?10^?5 m³.s^?1, while the flow rate of feed was 2.53?×?10^?7, 7.56?×?10^?7, and 1.26?×?10^?6 m³.s^?1, respectively. To evaluate performance of the reactor, response surface methodology was employed. A four-factor three-level Box–Behnken design was developed to evaluate the reactor performance for degradation of phenol. Effects of phenol inlet concentration (20–100 ppmv), pH (3–9), liquid flow rate (2.53?×?10^?7?1.26?×?10^?6 m³.s^?1), and TiO₂ loading (8.8–17.6 g.m^?2) were analyzed with this method. The adjusted R ² value (0.9936) was in close agreement with that of corresponding R ² value (0.9961). The maximum predicted degradation of phenol was 75.50 % at the optimum processing conditions (initial phenol concentration of 20 ppmv, pH?～?6.41, and flow rate of 2.53?×?10^?7 m³.s^?1 and catalyst loading of 17.6 g.m^?2). Experimental degradation of phenol determined at the optimum conditions was 73.7 %. XRD patterns and SEM images at the optimum conditions revealed that crystal size is approximately 25 nm and TiO₂ nanoparticles with visible agglomerates distribute densely and uniformly over the surface of stainless steel substrate. BET specific surface area of immobilized TiO₂ was 47.2 and 45.8 m² g^?1 before and after the experiments, respectively. Reduction in TOC content, after steady state condition, showed that maximum phenol decomposition occurred at neutral condition (pH?～?6). Figure

The schematic view of the experimental set-up     

An integrated approach to identify the origin of PM10 exceedances

Purpose

This study was aimed to the development of an integrated approach for the characterization of particulate matter (PM) pollution events in the South of Italy.

Methods

PM₁₀ and PM_2.5 daily samples were collected from June to November 2008 at an urban background site located in Bari (Puglia Region, South of Italy). Meteorological data, particle size distributions and atmospheric dispersion conditions were also monitored in order to provide information concerning the different features of PM sources.

Results

The collected data allowed suggesting four indicators to characterize different PM₁₀ exceedances. PM_2.5/PM₁₀ ratio, natural radioactivity, aerosol maps and back-trajectory analysis and particle distributions were considered in order to evaluate the contribution of local anthropogenic sources and to determine the different origins of intrusive air mass coming from long-range transport, such as African dust outbreaks and aerosol particles from Central and Eastern Europe. The obtained results were confirmed by applying principal component analysis to the number particle concentration dataset and by the chemical characterization of the samples (PM₁₀ and PM_2.5).

Conclusions

The integrated approach for PM study suggested in this paper can be useful to support the air quality managers for the development of cost-effective control strategies and the application of more suitable risk management approaches.     

Improvement of biodegradability of PVA-containing wastewater by ionizing radiation pretreatment

Background

Polyvinyl alcohol (PVA) has been widely used as sizing agents in textile and manufacturing industry, and it is a refractory compound with low biodegradability.

Objective

The objective of this paper was to treat the PVA-containing wastewater using gamma irradiation as a pretreatment strategy to improve its biodegradability and to determine the roles of different kinds of radical species played during pretreatment.

Methods

Gamma radiation was carried out in a ⁶⁰Cobalt source station, PVA concentration was analyzed by using a visible spectrophotometer and specific oxygen uptake rate (SOUR, milligram of O₂ per gram of mixed liquor volatile suspended solids (MLVSS) per hour) was measured by a microrespirometer.

Results

The results showed that the biodegradability of PVA-containing wastewater with low initial concentration (e.g., 327.8?mg/l) could be improved greatly with increasing irradiation dose. However, PVA gel formation was observed at higher initial PVA concentration (e.g., 3,341.6?mg/l) and higher irradiation dose, which inhibited PVA degradation by aerobic microorganisms. However, the formed gel could be separated by microfiltration, which led to more than 90% total organic carbon (TOC) removal.

Conclusion

Ionizing radiation could be used as a pretreatment technology for PVA-containing wastewater, and its combination with biological process is feasible.     

Enhanced degradation of azo dye alizarin yellow R in a combined process of iron–carbon microelectrolysis and aerobic bio-contact oxidation

Purpose

With the aim of enhanced degradation of azo dye alizarin yellow R (AY) and further removal of the low-strength recalcitrant matter (LsRM) of the secondary effluent as much as possible, our research focused on the combination of aerobic bio-contact oxidation (ABO) with iron/carbon microelectrolysis (ICME) process.

Materials and methods

The combined ABO (with effective volume of 2.4?l) and ICME (with effectively volume of 0.4?l) process were studied with relatively short hydraulic retention time (HRT) of 4 or 6?h.

Results

At the HRT of 6?h with the reflux ratio of 1 and 2, the AY degradation efficiency in the final effluent was >96.5%, and the total organic carbon (TOC) removal efficiency were 69.86% and 79.44%, respectively. At the HRT of 4?h and the reflux ratio of 2, TOC removal efficiency and AY degradation efficiency were 73.94% and 94.89%, respectively. The ICME process obviously enhanced the total AY removal and the generated micromolecule acids and aldehydes then that wastewater backflow to the ABO where they were further biodegraded.

Conclusion

The present research might provide the potential options for the advanced treatment azo dyes wastewater with short HRT and acceptable running costs.     

Heterocatalytic Fenton oxidation process for the treatment of tannery effluent: kinetic and thermodynamic studies

Background, aim, scope

Treatment of wastewater has become significant with the declining water resources. The presence of recalcitrant organics is the major issue in meeting the pollution control board norms in India. The theme of the present investigation was on partial or complete removal of pollutants or their transformation into less toxic and more biodegradable products by heterogeneous Fenton oxidation process using mesoporous activated carbon (MAC) as the catalyst.

Materials and methods

Ferrous sulfate (FeSO₄·7H₂O), sulfuric acid (36?N, specific gravity 1.81, 98% purity), hydrogen peroxide (50% v/v) and all other chemicals used in this study were of analytical grade (Merck). Two reactors, each of height 50?cm and diameter 6?cm, were fabricated with PVC while one reactor was packed with MAC of mass 150?g and other without MAC served as control.

Results and discussion

The oxidation process was presented with kinetic and thermodynamic constants for the removal of COD, BOD, and TOC from the wastewater. The activation energy (Ea) for homogeneous and heterogeneous Fenton oxidation processes were 44.79 and 25.89?kJ/mol, respectively. The thermodynamic parameters ??G, ??H, and ??S were calculated for the oxidation processes using Van??t Hoff equation. Furthermore, the degradation of organics was confirmed through FTIR and UV?Cvisible spectroscopy, and cyclic voltammetry.

Conclusions

The heterocatalytic Fenton oxidation process efficiently increased the biodegradability index (BOD/COD) of the tannery effluent. The optimized conditions for the heterocatalytic Fenton oxidation of organics in tannery effluent were pH 3.5, reaction time?C4?h, and H₂O₂/FeSO₄·7H₂O in the molar ratio of 2:1.     

Characterization of PM10 atmospheric aerosol at urban and urban background sites in Fuzhou city, China

Background

PM₁₀ aerosol samples were simultaneously collected at two urban and one urban background sites in Fuzhou city during two sampling campaigns in summer and winter. PM₁₀ mass concentrations and chemical compositions were determined.

Methods

Water-soluble inorganic ions (Cl^?, NO ₃ ^? , SO ₄ ^2? , NH ₄ ⁺ , K⁺, Na⁺, Ca²⁺, and Mg²⁺), carbonaceous species (elemental carbon and organic carbon), and elements (Al, Si, Mg, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Br, and Pb) were detected using ion chromatography, thermal/optical reflectance, and proton-induced X-ray emission methods, respectively.

Results

PM₁₀ mass concentrations, as well as most of the chemical components, were significantly increased from urban background to urban sites, which were due to enhanced anthropogenic activities in urban areas. Elements, carbonaceous species, and most of the ions were more uniformly distributed at different types of sites in winter, whereas secondary ion SO ₄ ^2? , NO ₃ ^? , and NH ₄ ⁺ showed more evident urban-background contrast in this season. The chemical mass closure indicated that mineral dust, organic matters, and sulfate were the most abundant components in PM₁₀. The sum of individually measured components accounted for 86.9?C97.7% of the total measured PM₁₀ concentration, and the discrepancy was larger in urban area than in urban background area.

Conclusion

According to the principal component analysis?Cmultivariate linear regression model, mineral dust, secondary inorganic ions, sea salt, and motor vehicle were mainly responsible for the PM₁₀ particles in Fuzhou atmosphere, and contributed 19.9%, 53.3%, 21.3%, and 5.5% of PM₁₀, respectively.     

Source apportionment of ultrafine and fine particle concentrations in Brisbane, Australia

Purpose

To investigate the significance of sources around measurement sites, assist the development of control strategies for the important sources and mitigate the adverse effects of air pollution due to particle size.

Methods

In this study, sampling was conducted at two sites located in urban/industrial and residential areas situated at roadsides along the Brisbane Urban Corridor. Ultrafine and fine particle measurements obtained at the two sites in June?CJuly 2002 were analysed by positive matrix factorization.

Results

Six sources were present, including local traffic, two traffic sources, biomass burning and two currently unidentified sources. Secondary particles had a significant impact at site 1, while nitrates, peak traffic hours and main roads located close to the source also affected the results for both sites.

Conclusions

This significant traffic corridor exemplifies the type of sources present in heavily trafficked locations and future attempts to control pollution in this type of environment could focus on the sources that were identified.     

Degradation and mineralization of sulcotrione and mesotrione in aqueous medium by the electro-Fenton process: a kinetic study

Introduction

The degradation and mineralization of two triketone (TRK) herbicides, including sulcotrione and mesotrione, by the electro-Fenton process (electro-Fenton using Pt anode (EF-Pt), electro-Fenton with BDD anode (EF-BDD) and anodic oxidation with BDD anode) were investigated in acidic aqueous medium.

Methods

The reactivity of both herbicides toward hydroxyl radicals was found to depend on the electron-withdrawing effect of the aromatic chlorine or nitro substituents. The degradation of sulcotrione and mesotrione obeyed apparent first-order reaction kinetics, and their absolute rate constants with hydroxyl radicals at pH?3.0 were determined by the competitive kinetics method.

Results and discussion

The hydroxylation absolute rate constant (k _abs) values of both TRK herbicides ranged from 8.20?×?10⁸ (sulcotrione) to 1.01?×?10⁹ (mesotrione) L?mol^?1?s^?1, whereas those of the TRK main cyclic or aromatic by-products, namely cyclohexane 1,3-dione , (2-chloro-4-methylsulphonyl) benzoic acid and 4-(methylsulphonyl)-2-nitrobenzoic acid, comprised between 5.90?×?10⁸ and 3.29?×?10⁹?L?mol^?1?s^?1. The efficiency of mineralization of aqueous solutions of both TRK herbicides was evaluated in terms of total organic carbon removal. Mineralization yields of about 97?C98% were reached in optimal conditions for a 6-h electro-Fenton treatment time.

Conclusions

The mineralization process steps involved the oxidative opening of the aromatic or cyclic TRK by-products, leading to the formation of short-chain carboxylic acids, and, then, of carbon dioxide and inorganic ions.     

Removal of faecal indicator pathogens from waters and wastewaters by photoelectrocatalytic oxidation on TiO2/Ti films under simulated solar radiation

Purpose

The disinfection efficiency of water and secondary treated wastewater by means of photoelectrocatalytic oxidation (PEC) using reference strains of Enterococcus faecalis and Escherichia coli as faecal indicators was evaluated. Operating parameters such as applied potential (2?C10?V), initial bacterial concentration (10³?C10⁷?CFU/mL), treatment time (up to 90?min) and aqueous matrix (pure water and treated effluent) were assessed concerning their impact on disinfection.

Methods

PEC experiments were carried out using a TiO₂/Ti film anode and a zirconium cathode in the presence of simulated solar radiation. Bacterial inactivation was monitored by the culture method and real-time SYBR green PCR.

Results

A 6.2 log reduction in E. faecalis population was achieved after 15?min of PEC treatment in water at 10?V of applied potential and an initial concentration of 10⁷?CFU/mL; pure photocatalysis (PC) led to only about 4.3 log reduction, whilst negligible inactivation was recorded when the respective electrochemical oxidation process was applied (i.e. without radiation). PEC efficiency was generally improved increasing the applied potential and decreasing initial bacterial concentration. Regarding real wastewater, E. coli was more susceptible than E. faecalis during treatment at a potential of 5?V. Wastewater disinfection was affected by its complex composition and the contained mixed bacterial populations, yielding lower inactivation rates compared to water treatment. Screening the results obtained from both applied techniques (culture method and real-time PCR), there was a discrepancy regarding the recorded time periods of total bacterial inactivation, with qPCR revealing longer periods for complete bacterial reduction.

Conclusions

PEC is superior to PC in terms of E. faecalis inactivation presumably due to a more efficient separation and utilization of the photogenerated charge carriers, and it is mainly affected by the applied potential, initial bacterial concentration and the aqueous matrix.     

An investigation of anthraquinone dye biodegradation by immobilized Aspergillus flavus in fluidized bed bioreactor

Purpose

Biodegradation and biodecolorization of Drimarene blue K₂RL (anthraquinone) dye by a fungal isolate Aspergillus flavus SA2 was studied in lab-scale immobilized fluidized bed bioreactor (FBR) system.

Method

Fungus was immobilized on 0.2-mm sand particles. The reactor operation was carried out at room temperature and pH?5.0 in continuous flow mode with increasing concentrations (50, 100, 150, 200, 300, 500?mg?l^?1) of dye in simulated textile effluent on the 1st, 2nd, 5th, 8th, 11th, and 14th days. The reactors were run on fill, react, settle, and draw mode, with hydraulic retention time (HRT) of 24?C72?h. Total run time for reactor operation was 17?days.

Results

The average overall biological oxygen demand (BOD), chemical oxygen demand (COD), and color removal in the FBR system were up to 85.57%, 84.70%, and 71.3%, respectively, with 50-mg?l^?1 initial dye concentration and HRT of 24?h. Reductions in BOD and COD levels along with color removal proved that the mechanism of biodecolorization and biodegradation occurred simultaneously. HPLC and LC?CMS analysis identified phthalic acid, benzoic acid, 1, 4-dihydroxyanthraquinone, 2,3-dihydro-9,10-dihydroxy-1,4-anthracenedione, and catechol as degradation products of Drimarene blue K₂RL dye. Phytotoxicity analysis of bioreactor treatments provided evidence for the production of less toxic metabolites in comparison to the parent dye.

Conclusion

The present fluidized bed bioreactor setup with indigenously isolated fungal strain in its immobilized form is efficiently able to convert the parent toxic dye into less toxic by-products.