Field solar degradation of pesticides and emerging water contaminants mediated by polymer films containing titanium and iron oxide with synergistic heterogeneous photocatalytic activity at neutral pH

Photocatalytic degradation of phenol, nalidixic acid, mixture of pesticides, and another of emerging contaminants in water was mediated by TiO₂ and iron oxide immobilized on functionalized polyvinyl fluoride films (PVF^f-TiO₂-Fe oxide) in a compound parabolic collector (CPC) solar photoreactor. During degradation, little iron leaching (<0.2 mg L⁻¹) was observed. Phenol was efficiently degraded and mineralized at operational pH < 5 and nalidixic acid degradation was complete even at pH 7, but mineralization stopped at 35%. Pesticide mixture was slowly degraded (50%) after 150 min of irradiation. Degradation of the emergent contaminant mixture was successful for eight compounds and less efficient for six other compounds. The significant reactivity differences between tested compounds were assigned to the differences in structure namely that the presence of complexing or chelating groups enhanced the rates.PVF^f-TiO₂-Fe oxide photoactivity gradually increased during 20 days of experiments. X-ray photoelectron spectroscopy (XPS) measurements revealed significant changes on the catalyst surface. These analyses confirm that during photocatalysis mediated by PVF^f-TiO₂-Fe oxide, some iron leaching led to enlargement of the TiO₂ surface exposed to light, increasing its synergy with iron oxides and leading to enhanced pollutant degradation.     

Effect of sunlight irradiation on photocatalytic pyrene degradation in contaminated soils by micro-nano size TiO2

The enhanced catalytic pyrene degradation in quartz sand and alluvial and red soils by micro-nano size TiO₂ in the presence and absence of sunlight was investigated. The results showed that the synergistic effect of sunlight irradiation and TiO₂ was more efficient on pyrene degradation in quartz sand and red and alluvial soils than the corresponding reaction system without sunlight irradiation. In the presence of sunlight irradiation, the photooxidation (without TiO₂) of pyrene was very pronounced in alluvial and red soils and especially in quartz sand. However, in the absence of sunlight irradiation, the catalytic pyrene degradation by TiO₂ and the photooxidation (without TiO₂) of pyrene were almost nil. This implicates that ultra-violet (UV) wavelength range of sunlight plays an important role in TiO₂-enhanced photocatalytic pyrene degradation and in photooxidation (without TiO₂) of pyrene. The percentages of photocatalytic pyrene degradation by TiO₂ in quartz sand, alluvial and red soils under sunlight irradiation were 78.3, 23.4, and 31.8%, respectively, at 5 h reaction period with a 5% (w/w) dose of the amended catalyst. The sequence of TiO₂-enhanced catalytic pyrene degradation in quartz sand and alluvial and red soils was quartz sand > red soil > alluvial soil, due to different texture and total organic carbon (TOC) contents of the quartz sand and other two soils. The differential Fourier transform infrared (FT-IR) spectra of degraded pyrene in alluvial soil corroborate that TiO₂-enhanced photocatalytic degradation rate of degraded pyrene was much greater than photooxidation (without TiO₂) rate of degraded pyrene. Based on the data obtained, the importance for the application of TiO₂-enhanced photocatalytic pyrene degradation and associated organic contaminants in contaminated soils was elucidated.     

Preliminary trial on degradation of waste activated sludge and simultaneous hydrogen production in a newly-developed solar photocatalytic reactor with AgX/TiO2-coated glass tubes

A solar fluidized tubular photocatalytic reactor (SFTPR) with simple and efficient light collector was developed to degrade waste activated sludge (WAS) and simultaneously produce hydrogen. The photocatalyst was a TiO₂ film doped by silver and silver compounds (AgX). The synthesized photocatalyst, AgX/TiO₂, exhibited higher photocatalytic activity than TiO₂ (99.5% and 30.6% of methyl orange removal, respectively). The installation of light collector could increase light intensity by 26%. For WAS treatment using the SFTPR, 69.1% of chemical oxygen demand (COD) removal and 7866.7 μmol H₂/l-sludge of hydrogen production were achieved after solar photocatalysis for 72 h. The SFTPR could be a promising photocatalysis reactor to effectively degrade WAS with simultaneous hydrogen production. The results can also provide a useful base and reference for the application of photocatalysis on WAS degradation in practice.     

Photolytic and photocatalytic decomposition of aqueous ciprofloxacin: Transformation products and residual antibacterial activity

Previous work demonstrates that widely used fluoroquinolone antibacterial agents, including ciprofloxacin, are degraded by means of aqueous ultraviolet photolytic and titanium dioxide (TiO₂) photocatalytic (using both ultraviolet-A (UVA) and visible light (Vis) irradiation) treatment processes. In this study, we investigate the effects of photolytic and photocatalytic treatment processes on the antibacterial activity of ciprofloxacin solutions under controlled laboratory conditions. In agreement with earlier work, rates of ciprofloxacin degradation under comparable solution conditions (100 μM ciprofloxacin, 0 or 0.5 g/L TiO₂, pH 6, 25 °C) follow the trend UVA-TiO₂ > Vis-TiO₂ > UVA. Release of ammonia and fluoride ions is observed and a range of organic products have been identified with liquid chromatography-tandem mass spectrometry. However, the identified organic products all appear to retain the core quinolone structure, raising concerns about residual antibacterial potency of the treated solutions. Quantitative microbiological assays with a reference Escherichia coli strain indicate that the antimicrobial potency of ciprofloxacin solutions track closely with the undegraded ciprofloxacin concentration during photolytic or photocatalytic reactions. Quantitative analysis shows that for each mole of ciprofloxacin degraded, the antibacterial potency of irradiated solutions decreases by approximately one “mole” of activity relative to that of the untreated ciprofloxacin solution. This in turn indicates that the ciprofloxacin photo(cata)lytic transformation products retain negligible antibacterial activity relative to the parent compound. The energy demands for achieving one order of magnitude reduction in antibacterial activity within the experimental system are estimated to be 175 J/cm² (UVA-only), 29 J/cm² (Vis-TiO₂), and 20 J/cm² (UVA-TiO₂), which indicates that the UVA-TiO₂ photocatalysis is the most energy efficient process for achieving ciprofloxacin inactivation under laboratory conditions.     

Heterogeneous photocatalytic removal of toluene from air on building materials enriched with TiO2

This paper reports the potential of heterogeneous photocatalysis as an advanced oxidation technology for removal of toluene from air using TiO₂ as a photocatalyst in building materials. First, the photocatalytic activity of two types of TiO₂ containing building materials, i.e. roofing tiles and corrugated sheets, has been investigated at ambient conditions (T=25.0 °C; relative humidity RH=47%; toluene inlet concentration [TOL]_in=17–35 ppbv). Toluene removal efficiencies up to 63% were observed at a gas residence time (τ) of 17 s. Second, the effect of RH (1–77%), [TOL]_in (23–465 ppmv) and τ (17–115 s) on toluene removal has been systematically investigated using TiO₂ containing roofing tiles as photocatalytic building materials. Results revealed lower toluene removal efficiencies at higher RH and [TOL]_in, whereas a positive effect was observed with increased τ. Under optimal conditions, toluene removal efficiencies up to 78±2% and elimination rates higher than 100 mg h⁻¹ m⁻² roofing tile were obtained. A decline in photocatalytic activity by a factor of 2 was observed after operation at gas residence times shorter than 69 s and [TOL]_in higher than 76 ppmv. Washing the building materials with deionized water, simulating rainfall, could partially (i.e. by a factor 1.3) regenerate the catalyst activity.     

Antifungal capability of TiO2 coated film on moist wood

Photocatalytic oxidation by TiO₂ has been shown to deactivate biological pollutants. Most previous studies evaluated TiO₂'s antimicrobial performance using bacteria, with Escherichia coli most commonly applied as the test microbe. There have not been concentrated studies focusing on the photocatalytic disinfection of fungi which widely exist in buildings and cause health problems. In this study, the antifungal activity of TiO₂ photocatalytic reaction against Aspergillus niger was investigated for moist wood boards during periods of several weeks. TiO₂ coated film in the presence of UVA (365 nm) irradiation exhibited antifungal capability. No visible growth was observed on specimens during the photo-process. Re-growth appeared in subsequent dark, indicating that the photocatalytic reaction was not sufficient for total disinfection against mold fungi but did suppress fungi growth. The study sheds light on conditions and potential applications of photocatalytic deactivation of fungi.     

Development of a TiO2 modified optical fiber electrode and its incorporation into a photoelectrochemical reactor for wastewater treatment

Electrochemical advanced oxidation processes (EAOPs) are used to chemically burn non biodegradable complex organic compounds that are present in polluted effluents. A common approach involves the use of TiO₂ semiconductor substrates as either photocatalytic or photoelectrocatalytic materials in reactors that produce a powerful oxidant (hydroxyl radical) that reacts with pollutant species. In this context, the purpose of this work is to develop a new TiO₂ based photoanode using an optic fiber support. The novel arrangement of a TiO₂ layer positioned on top of a surface modified optical fiber substrate, allowed the construction of a photoelectrochemical reactor that works on the basis of an internally illuminated approach. In this way, a semi-conductive optical fiber modified surface was prepared using 30 μm thickness SnO₂:Sb films on which the photoactive TiO₂ layer was electrophoretically deposited. UV light transmission experiments were conducted to evaluate the transmittance along the optical fiber covered with SnO₂:Sb and TiO₂ showing that 43% of UV light reached the optical fiber tip. With different illumination configurations (external or internal), it was possible to get an increase in the amount of photo-generated H₂O₂ close to 50% as compared to different types of TiO₂ films. Finally, the electro-Fenton photoelectrocatalytic Oxidation process studied in this work was able to achieve total color removal of Azo orange II dye (15 mg L⁻¹) and a 57% removal of total organic carbon (TOC) within 60 min of degradation time.     

Development of solar-driven electrochemical and photocatalytic water treatment system using a boron-doped diamond electrode and TiO2 photocatalyst

A high-performance, environmentally friendly water treatment system was developed. The system consists mainly of an electrochemical and a photocatalytic oxidation unit, with a boron-doped diamond (BDD) electrode and TiO₂ photocatalyst, respectively. All electric power for the mechanical systems and the electrolysis was able to be provided by photovoltaic cells. Thus, this system is totally driven by solar energy. The treatment ability of the electrolysis and photocatalysis units was investigated by phenol degradation kinetics. An observed rate constant of 5.1 × 10⁻³ dm³ cm⁻² h⁻¹ was calculated by pseudo-first-order kinetic analysis for the electrolysis, and a Langmuir-Hinshelwood rate constant of 5.6 μM⁻¹ min⁻¹ was calculated by kinetic analysis of the photocatalysis. According to previous reports, these values are sufficient for the mineralization of phenol. In a treatment test of river water samples, large amounts of chemical and biological contaminants were totally wet-incinerated by the system. This system could provide 12 L/day of drinking water from the Tama River using only solar energy. Therefore, this system may be useful for supplying drinking water during a disaster.     

Photoassisted reduction of metal ions and organic dye by titanium dioxide nanoparticles in aqueous solution under anoxic conditions

The photoassisted reduction of metal ions and organic dye by metal-deposited Degussa P25 TiO₂ nanoparticles was investigated. Copper and silver ions were selected as the target metal ions to modify the surface properties of TiO₂ and to enhance the photocatalytic activity of TiO₂ towards methylene blue (MB) degradation. X-ray powder diffraction (XRPD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) were used to characterize the crystallinity, chemical species and morphology of metal-deposited TiO₂, respectively. Results showed that the particle size of metal-deposited TiO₂ was larger than that of Degussa P25 TiO₂. Based on XRPD patterns and XPS spectra, it was observed that the addition of formate promoted the photoreduction of metal ion by lowering its oxidation number, and subsequently enhancing the photodegradation efficiency and rate of MB. The pseudo-first-order rate constant (k_obs) for MB photodegradation by Degussa P25 TiO₂ was 3.94 × 10^− 2 min^− 1 and increased by 1.4-1.7 times in k_obs with metal-deposited TiO₂ for MB photodegradation compared to simple Degussa P25 TiO₂. The increase in mass loading of metal ions significantly enhanced the photodegradation efficiency of MB; the k_obs for MB degradation increased from 3.94 × 10^− 2 min^− 1 in the absence of metal ion to 4.64-7.28 × 10^− 2 min^− 1 for Ag/TiO₂ and to 5.14-7.61 × 10^− 2 min^− 1 for Cu/TiO₂. In addition, the electrons generated from TiO₂ can effectively reduce metal ions and MB simultaneously under anoxic conditions. However, metal ions and organic dye would compete for electrons from the illuminated TiO₂.     

Alginate fibers as photocatalyst immobilizing agents applied in hybrid photocatalytic/ultrafiltration water treatment processes

Ca alginate polymer fibers were developed to effectively disperse and stabilize an efficient photocatalyst such as AEROXIDE^® TiO₂ P25 in their matrix. The biopolymer/TiO₂ fibers were prepared and tested either in the hydrogel non-porous form or in the highly porous aerogel form prepared by sc-CO₂ drying. Batch photocatalytic experiments showed that the porous, Ca alginate/TiO₂ fibers, exhibited high efficiency for the removal of methyl orange (MO) from polluted water. In addition, their high porosity and surface area led to high MO degradation rate which was faster than that observed not only for their non-porous analogs but also of the bulk P25 TiO₂ powder. Specifically, 90% removal for 20 μM MO was achieved within 220 min for the porous sc-CO₂ dried fibers while for their non-porous analogs at 325 min. The corresponding value (at 60 μM MO) for the porous sc-CO₂ dried fibers was 140 min over 240 min for the AEROXIDE^® TiO₂ P25 as documented in the literature. Furthermore the composite alginate/photocatalyst porous fibers were combined with TiO₂ membranes in a continuous flow, hybrid photocatalytic/ultrafiltration water treatment process that led to a three fold enhancement of the MO removal efficiency at 400 ml of 20 μM MO total treated volume and to dilution rather than condensation in the membrane retentate as commonly observed in filtration processes. Furthermore the permeability of the photocatalytic membrane was enhanced in the presence of the fibers by almost 20%. This performance is achieved with 26 cm² and 31 cm² of membrane and stabilized photocatalyst surfaces respectively and in this context there is plenty of room for the up-scaling of both membranes and fibers and the achievement of much higher water yields since the methods applied for the development of the involved materials (CVD and dry-wet phase inversion in a spinning set-up) are easily up-scalable and are not expected to add significant cost to the proposed water treatment process.     

Visible-light-induced photocatalysis of low-level methyl-tertiary butyl ether (MTBE) and trichloroethylene (TCE) using element-doped titanium dioxide

While the photocatalytic degradation of various volatile organic compounds in conjunction with UV light has been widely reported, visible-light-induced photocatalytic degradation of low-levels of the pollutants MTBE and TCE, which have been linked to potential adverse health effects, is rarely reported. The present study examined whether visible-light-activated S- or N-doped TiO₂ photocatalytic technology can be used to control indoor concentrations of MTBE and TCE. This study consists of the characterization of the doped TiO₂ powders, as well as an investigation of their photocatalytic activities. In regards to both powders, a shift of the absorbance spectrum towards the visible light region was observed. An activity test suggested that these photocatalysts exhibited reasonably high degradation efficiencies towards MTBE and TCE under visible light irradiation. The degradation efficiencies of MTBE and TCE by S- and N-doped photocatalysts exceeded 75 and 80%, respectively, at input concentrations (IC) of 0.1 ppm. Degradation efficiency was dependent on both IC and relative humidity. TCE could enhance the degradation efficiency of MTBE even under visible-light irradiation. The estimated mineralization efficiencies (MEs) were comparable to those of previous studies conducted with UV/TiO₂ systems. Similar to the relative degradation efficiencies, the ME of TCE was higher in comparison to that of MTBE. The CO production measured during the photocatalytic processes represented a negligible addition to indoor CO levels. These results suggest that visible-light-activated S- and N-doped TiO₂ photocatalysts may prove a useful tool in the effort to improve indoor air quality.     

Heterogenous photocatalytic degradation kinetics and detoxification of an urban wastewater treatment plant effluent contaminated with pharmaceuticals

Degradation kinetics and mineralization of an urban wastewater treatment plant effluent contaminated with a mixture of pharmaceutical compounds composed of amoxicillin (10 mg L⁻¹), carbamazepine (5 mg L⁻¹) and diclofenac (2.5 mg L⁻¹) by TiO₂ photocatalysis were investigated. The photocatalytic effect was investigated using both spiked distilled water and actual wastewater solutions. The process efficiency was evaluated through UV absorbance and TOC measurements. A set of bioassays (Daphnia magna, Pseudokirchneriella subcapitata and Lepidium sativum) was performed to evaluate the potential toxicity of the oxidation intermediates. A pseudo-first order kinetic model was found to fit well the experimental data. The mineralization rate (TOC) of the wastewater contaminated with the pharmaceuticals was found to be really slow (t_1/2 = 86.6 min) compared to that of the same pharmaceuticals spiked in distilled water (t_1/2 = 46.5 min). The results from the toxicity tests of single pharmaceuticals, their mixture and the wastewater matrix spiked with the pharmaceuticals displayed a general accordance between the responses of the freshwater aquatic species (P. subscapitata > D. magna). In general the photocatalytic treatment did not completely reduce the toxicity under the investigated conditions (maximum catalyst loading and irradiation time 0.8 g TiO₂ L⁻¹ and 120 min respectively).     

Mineralization enhancement of a recalcitrant pharmaceutical pollutant in water by advanced oxidation hybrid processes

Degradation of the biorecalcitrant pharmaceutical micropollutant ibuprofen (IBP) was carried out by means of several advanced oxidation hybrid configurations. TiO₂ photocatalysis, photo-Fenton and sonolysis - all of them under solar simulated illumination - were tested in the hybrid systems: sonophoto-Fenton (FS), sonophotocatalysis (TS) and TiO₂/Fe²⁺/sonolysis (TFS). In the case of the sonophoto-Fenton process, the IBP degradation (95%) and mineralization (60%) were attained with photo-Fenton (FH). The presence of ultrasonic irradiation slightly improves the iron catalytic activity. On the other hand, total removal of IBP and elimination of more than 50% of dissolved organic carbon (DOC) were observed by photocatalysis with TiO₂ in the presence of ultrasound irradiation (TS). In contrast only 26% of mineralization was observed by photocatalysis with H₂O₂ (TH) in the absence of ultrasound irradiation. Additional results showed that, in the TFS system, 92% of DOC removal and complete degradation of IBP were obtained within 240 min of treatment. The advanced oxidation hybrid systems seems to be a promising alternative for full elimination/mineralization for the recalcitrant micro-contaminant IBP.     

Evaluation of a photocatalytic reactor membrane pilot system for the removal of pharmaceuticals and endocrine disrupting compounds from water

A photocatalytic reactor membrane pilot system, employing UV/TiO₂ photocatalysis, was evaluated for its ability to remove thirty-two pharmaceuticals, endocrine disrupting compounds, and estrogenic activity from water. Concentrations of all compounds decreased following treatment, and removal followed pseudo-first-order kinetics as a function of the amount of treatment. Twenty-nine of the targeted compounds in addition to total estrogenic activity were greater than 70% removed while only three compounds were less than 50% removed following the highest level of treatment (4.24 kW h/m³). No estrogenically active transformation products were formed during treatment. Additionally, the unit was operated in photolytic mode (UV only) and photolytic plus H₂O₂ mode (UV/H₂O₂) to determine the relative amount of energy required. Based on the electrical energy per order (EEO), the unit achieved the greatest efficiency when operated in photolytic plus H₂O₂ mode for the conditions tested.     

Degradation of the antibiotic oxolinic acid by photocatalysis with TiO2 in suspension

In the work presented here, a photocatalytic system using titanium Degussa P-25 in suspension was used to evaluate the degradation of 20 mg L⁻¹ of antibiotic oxolinic acid (OA). The effects of catalyst load (0.2-1.5 g L⁻¹) and pH (7.5-11) were evaluated and optimized using the surface response methodology and the Pareto diagram. In the range of variables studied, low pH values and 1.0 g L⁻¹ of TiO₂ favoured the efficiency of the process. Under optimal conditions the evolution of the substrate, chemical oxygen demand, dissolved organic carbon, toxicity and antimicrobial activity on Escherichia coli cultures were evaluated. The results indicate that, under optimal conditions, after 30 min, the TiO₂ photocatalytic system is able to eliminate both the substrate and the antimicrobial activity, and to reduce the toxicity of the solution by 60%. However, at the same time, ∼53% of both initial DOC and COD remain in solution. Thus, the photocatalytical system is able to transform the target compound into more oxidized by-products without antimicrobial activity and with a low toxicity. The study of OA by-products using liquid chromatography coupled with mass spectrometry, as well as the evaluation of OA degradation in acetonitrile media as solvent or in the presence of isopropanol and iodide suggest that the reaction is initiated by the photo-Kolbe reaction. Adsorption isotherm experiments in the dark indicated that under pH 7.5, adsorption corresponded to the Langmuir adsorption model, indicating the dependence of the reaction on an initial adsorption step.     

Mechanism of phenol photodegradation in the presence of pure and modified-TiO(2): A review

In recent years, the application of heterogeneous photocatalytic water purification processes has gained wide attention due to its effectiveness in degrading and mineralizing the recalcitrant organic compounds as well as the possibility of utilizing the solar UV and visible-light spectrum. By far, titania has played a much larger role in this scenario compared to other semiconductor photocatalysts due to its costly effectiveness, inert nature and photostability. A substantial amount of research has focused on the enhancement of TiO₂ photocatalysis by modification with metal, non-metal and ion doping.This paper aims to review and summarize the recent works on the titanium dioxide (TiO₂) photocatalytic oxidation of phenol and discusses various mechanisms of phenol photodegradation (indicating the intermediates products) and formation of OH radicals. Phenol degradation pathway in both systems, TiO₂/UV and doped-TiO₂/Vis, are described.     

Drugs degrading photocatalytically: Kinetics and mechanisms of ofloxacin and atenolol removal on titania suspensions

The conversion of the antibiotic ofloxacin and the β-blocker atenolol by means of TiO₂ photocatalysis was investigated. Irradiation was provided by a UVA lamp at 3.37 × 10⁻⁶ einstein/s photon flux, while emphasis was given on the effect of catalyst type and loading (50-1500 mg/L), initial substrate concentration (5-20 mg/L), initial pH (3-10) and the effect of H₂O₂ (0.07-1.4 mM) as an additional oxidant on substrate conversion and mineralization in various matrices (i.e. pure water, groundwater and treated municipal effluent). Conversion was assessed measuring sample absorbance at 288 and 224 nm for ofloxacin and atenolol, respectively, while mineralization measuring the dissolved organic carbon. Degussa P25 TiO₂ was found to be more active than other TiO₂ samples for either substrate degradation, with ofloxacin being more reactive than atenolol. Conversion generally increased with increasing catalyst loading, decreasing initial substrate concentration and adding H₂O₂, while the effect of solution pH was substrate-specific. Reaction rates, following a Langmuir-Hinshelwood kinetic expression, were maximized at a catalyst to substrate concentration ratio (w/w) of 50 and 15 for ofloxacin and atenolol, respectively, while higher ratios led to reduced efficiency. Likewise, high concentrations of H₂O₂ had an adverse effect on reaction, presumably due to excessive oxidant scavenging radicals and other reactive species. The ecotoxicity of ofloxacin and atenolol to freshwater species Daphnia magna was found to increase with increasing substrate concentration (1-10 mg/L) and exposure time (24-48 h), with atenolol being more toxic than ofloxacin. Photocatalytic treatment eliminated nearly completely toxicity and this was more pronounced for atenolol.     

Solar Fenton and solar TiO2 catalytic treatment of ofloxacin in secondary treated effluents: Evaluation of operational and kinetic parameters

Two different technical approaches based on advanced oxidation processes (AOPs), solar Fenton homogeneous photocatalysis (hv/Fe²⁺/H₂O₂) and heterogeneous photocatalysis with titanium dioxide (TiO₂) suspensions were studied for the chemical degradation of the fluoroquinolone ofloxacin in secondary treated effluents. A bench-scale solar simulator in combination with an appropriate photochemical batch reactor was used to evaluate and select the optimal oxidation conditions of ofloxacin spiked in secondary treated domestic effluents. The concentration profile of the examined substrate during degradation was determined by UV/Vis spectrophotometry. Mineralization was monitored by measuring the dissolved organic carbon (DOC). The concentrations of Fe²⁺ and H₂O₂ were the key factors for the solar Fenton process, while the most important parameter of the heterogeneous photocatalysis was proved to be the catalyst loading. Kinetic analyses indicated that the photodegradation of ofloxacin can be described by a pseudo-first-order reaction. The rate constant (k) for the solar Fenton process was determined at different Fe²⁺ and H₂O₂ concentrations whereas the Langmuir-Hinshelwood (LH) kinetic expression was used to assess the kinetics of the heterogeneous photocatalytic process. The conversion of ofloxacin depends on several parameters based on the various experimental conditions, which were investigated. A Daphnia magna bioassay was used to evaluate the potential toxicity of the parent compound and its photo-oxidation by-products in different stages of oxidation. In the present study solar Fenton has been demonstrated to be more effective than the solar TiO₂ process, yielding complete degradation of the examined substrate and DOC reduction of about 50% in 30 min of the photocatalytic treatment.     

Photocatalytic transformation and mineralization of 2,4,6-trinitrotoluene (TNT) in TiO2 slurries

An analysis of the photodegradation of TNT in a TiO₂ slurry reactor is presented. The rates and extent of TNT transformation and mineralization are compared for photocatalytic and direct photolytic reactions under conditions of varying light energies and in the presence and absence of oxygen. Certain initial organic transformation products are identified for both photocatalytic and photolytic reactions. Nitrate, nitrite, and ammonium ions are analyzed and the possibility of semiconductor sensitization by colored compounds is considered. TNT was transformed rapidly under each set of photochemical conditions but destruction was faster and more complete with TiO₂ photocatalysis. Transformation by-products were destroyed readily under oxygenated photocatalytic conditions and were observed to be more refractory under direct photolytic conditions. Mass balances performed on carbon and nitrogen revealed that when the TiO₂ photocatalyst was utilized in the presence of oxygen and near u.v. radiation (λ > 340 nm) approx. 90% of the TNT was mineralized and 35% of the total nitrogen was recovered as ammonium ion after 120 min. Among the large number of organic transformation products produced photocatalytically, trinitrobenzoic acid, trinitrobenzene and trinitrophenol have been identified as oxidative intermediate species and dinitroaniline as a reduction product. The photocatalytic transformation of TNT appears to involve both oxidative and reductive steps and sensitization by colored compounds plays no detectable role in degradation.     

Preparation of DNA-adsorbed TiO2 particles — Augmentation of performance for environmental purification by increasing DNA adsorption by external pH regulation

We have previously developed a novel photocatalyst, DNA-attached titanium dioxide (DNA-TiO₂), useful for the recovery and decomposition of chemicals [Suzuki et al. Environ. Sci. Technol. 42, 8076, 2008]. Chemicals accumulated in DNA near the surface of TiO₂ and were degraded under UV light. The efficiency of their removal was dependent on the amount of DNA adsorbed on TiO₂, indicating the attachment of larger amounts of DNA to result in higher efficiency. In this study, we succeeded in improving the performance of DNA-TiO₂ by increasing the amount of DNA adsorbed by regulating the external pH. The adsorption of DNA by TiO₂ dramatically increased at pH2, to about fourfold that at other pH values (pH4-10). Repeating the process of DNA addition increased the adsorption further. The attached DNA was stable on the surface of TiO₂ at pH2-10 and 4-56 °C, the same as DNA-TiO₂ prepared at pH7. As the DNA-TiO₂ prepared at pH2 retained much DNA on its surface, chemicals (methylene blue, ethidium bromide, etc.) which could intercalate or react with DNA were effectively removed from solutions. The photocatalytic degradation was slow at first, but the final degradation rate was higher than for non-adsorbed TiO₂ and DNA-TiO₂ prepared at pH7. These results indicated that preparation of DNA-TiO₂ at pH2 has advantages in that much DNA can be attached and large amounts of chemicals can be concentrated in the DNA, resulting in extensive decomposition under UV light.