Comparison of various advanced oxidation processes for the degradation of phenylurea herbicides.

Various types of advanced oxidation processes (AOPs), such as UV photolysis, ozonation, heterogeneous photocatalysis and their combinations were comparatively examined at the same energy input in a home-made reactor. The oxidative transformations of the phenylurea herbicides fenuron, monuron and diuron were investigated. The initial rates of transformation demonstrated that UV photolysis was highly efficient in the cases of diuron and monuron. Ozonation proved to be much more effective in the transformation of fenuron than in those of the chlorine containing monuron and diuron. In heterogeneous photocatalysis, the rate of decomposition decreased with increase of the number of chlorine atoms in the target molecule. Addition of ozone to UV-irradiated solutions and/or TiO2-containing suspensions markedly increased the initial rates of degradation. Dehalogenation of monuron and diuron showed that each of these procedures is suitable for the simultaneous removal of chlorinated pesticides and their chlorinated intermediates. Heterogeneous photocatalysis was found to be effective in the mineralization.

"Crystallographic" holes: new insights for a beneficial structural feature for photocatalytic applications.

One of the most fundamental aspects of the heterogeneous catalysis field is the manipulation of the catalysts' activity. In photocatalysis this is carried out by maximizing the right crystal plane of a semiconductor oxide. Until now, most of the papers have achieved this by a combination of different oxides, with noble metals and sometimes with carbon nanomaterials. In this work MWCNTs (multiwalled carbon nanotubes) were applied as "crystallization promoters" in a very simple, safe, one-step hydrothermal method. By this method TiO2 nano/micro crystals with exposed {001} facets were obtained in the first step. The next episode in the crystal manipulation "saga" was the modification of the (001) crystallographic plane's structure by creating ordered/own faceted "crystallographic holes". These elements are capable of further enhancing the obtained activity of titania microcrystals to a higher extent, as shown by the UV driven photocatalytic phenol degradation experiments. The appearance of the holes was "provoked" by simple calcination and their presence and influence were demonstrated by XPS and HRTEM.

Ketoprofen removal by O3 and O3/UV processes: kinetics, transformation products and ecotoxicity.

Ozonation (O3) and its combination with ultraviolet radiation (O3/UV) were used to decompose ketoprofen (KET). Depending on the initial KET concentration, fourteen to fifty time's faster KET degradation was achieved using combined O3/UV method compared to simple ozonation. Using both methods, formation of four major aromatic transformation products were observed: 3-(1-hydroxyethyl)benzophenone, 3-(1-hydroperoxyethyl) benzophenone, 1-(3-benzoylphenyl) ethanone and 3-ethylbenzophenone. In the combined treatment the degradation was mainly due to the direct effect of UV light, however, towards the end of the treatment, O3 highly contributed to the mineralization of small carboxylic acids. High (~90%) mineralization degree was achieved using the O3/UV method. Toxicity tests performed using representatives of three trophic levels of the aquatic ecosystems (producers, consumers and decomposers) Pseudokirchneriella subcapitata green algae, Daphnia magna zooplanktons and Vibrio fischeri bacteria showed that under the used experimental conditions the transformation products have significantly higher toxicity towards all the test organisms, than KET itself. The bacteria and the zooplanktons showed higher tolerance to the formed products than algae. The measured toxicity correlates well with the concentration of the aromatic transformation products, therefore longer treatments than needed for complete degradation of KET are strongly suggested, in order to avoid possible impact of aromatic transformation products on the aquatic ecosystem.

Vacuum ultraviolet photolysis of diclofenac and the effects of its treated aqueous solutions on the proliferation and migratory responses of Tetrahymena pyriformis.

The effects of dissolved O2, phosphate buffer and the initial concentration of diclofenac on the vacuum ultraviolet photolysis of this contaminant molecule were studied. Besides kinetic measurements, the irradiated, multicomponent samples were characterized via the proliferation and migratory responses (in sublethal concentrations) of the bioindicator eukaryotic ciliate Tetrahymena pyriformis. The results suggest that hydroxyl radicals, hydrogen atoms and hydroperoxyl radicals may all contribute to the degradation of diclofenac. The aromatic by-products of diclofenac were presumed to include a hydroxylated derivative, 1-(8-chlorocarbazolyl)acetic acid and 1-(8-hydroxycarbazolyl)acetic acid. The biological activity of photoexposed samples reflected the chemical transformation of diclofenac and was also dependent on the level of dissolved O2. The increase in toxicity of samples taken after different irradiation times did not exceed a factor of two. Our results suggest that the combination of vacuum ultraviolet photolysis with toxicity and chemotactic measurements can be a valuable method for the investigation of the elimination of micropollutants.

Photocatalytic H2 Production Using Pt-TiO2 in the Presence of Oxalic Acid: Influence of the Noble Metal Size and the Carrier Gas Flow Rate.

The primary objective of the experiments was to investigate the differences in the photocatalytic performance when commercially available Aeroxide P25 TiO2 photocatalyst was deposited with differently sized Pt nanoparticles with identical platinum content (1 wt%). The noble metal deposition onto the TiO2 surface was achieved by in situ chemical reduction (CRIS) or by mixing chemically reduced Pt nanoparticle containing sols to the aqueous suspensions of the photocatalysts (sol-impregnated samples, CRSIM). Fine and low-scale control of the size of resulting Pt nanoparticles was obtained through variation of the trisodium citrate concentration during the syntheses. The reducing reagent was NaBH4. Photocatalytic activity of the samples and the reaction mechanism were examined during UV irradiation (λmax = 365 nm) in the presence of oxalic acid (50 mM) as a sacrificial hole scavenger component. The H2 evolution rates proved to be strongly dependent on the Pt particle size, as well as the irradiation time. A significant change of H2 formation rate during the oxalic acid transformation was observed which is unusual. It is probably regulated both by the decomposition rate of accumulated oxalic acid and the H⁺/H2 redox potential on the surface of the catalyst. The later potential is influenced by the concentration of the dissolved H2 gas in the reaction mixture.

Photocatalytic H2 Evolution Using Different Commercial TiO2 Catalysts Deposited with Finely Size-Tailored Au Nanoparticles: Critical Dependence on Au Particle Size.

One weight percent of differently sized Au nanoparticles were deposited on two commercially available TiO2 photocatalysts: Aeroxide P25 and Kronos Vlp7000. The primary objective was to investigate the influence of the noble metal particle size and the deposition method on the photocatalytic activity. The developed synthesis method involves a simple approach for the preparation of finely-tuned Au particles through variation of the concentration of the stabilizing agent. Au was deposited on the TiO2 surface by photo- or chemical reduction, using trisodium citrate as a size-tailoring agent. The Au-TiO2 composites were synthetized by in situ reduction or by mixing the titania suspension with a previously prepared gold sol. The H2 production activities of the samples were studied in aqueous TiO2 suspensions irradiated with near-UV light in the absence of dissolved O2, with oxalic acid or methanol as the sacrificial agent. The H2 evolution rates proved to be strongly dependent on Au particle size: the highest H2 production rate was achieved when the Au particles measured ~6 nm.

Degradation of naproxen by UV, VUV photolysis and their combination.

Naproxen is a widely used nonsteroidal anti-inflammatory drug. Recently, this medicine was detected both in natural waters (up to 1.5 µg L(-1)) and in sewage treatment plant effluents (up to 5.2 µg L(-1)). Moreover, naproxen is only partly eliminated by classical processes used in sewage treatment plants. Therefore, its degradation is of utmost interest. Advanced oxidation processes proved to be the most suitable methods for the elimination of persistent organic contaminants. In this work ultraviolet (UV, 254 nm), vacuum ultraviolet photolysis (VUV, 172 nm) and their combination (UV/VUV, 254/185 nm) were investigated. The efficiency of the methods increased in the following order: UV < VUV < UV/VUV photolysis. However, VUV irradiation was found to mineralize the contaminant molecule most effectively. The chemical structures of three out of four aromatic by-products and of some aliphatic carboxylic acids were presumed. The effects of dissolved O2 and the initial concentration of naproxen on the degradation were also investigated.

Hydroxyl radical induced degradation of ibuprofen.

Pulse radiolysis experiments were used to characterize the intermediates formed from ibuprofen during electron beam irradiation in a solution of 0.1mmoldm(-3). For end product characterization (60)Co γ-irradiation was used and the samples were evaluated either by taking their UV-vis spectra or by HPLC with UV or MS detection. The reactions of OH resulted in hydroxycyclohexadienyl type radical intermediates. The intermediates produced in further reactions hydroxylated the derivatives of ibuprofen as final products. The hydrated electron attacked the carboxyl group. Ibuprofen degradation is more efficient under oxidative conditions than under reductive conditions. The ecotoxicity of the solution was monitored by Daphnia magna standard microbiotest and Vibrio fischeri luminescent bacteria test. The toxic effect of the aerated ibuprofen solution first increased upon irradiation indicating a higher toxicity of the first degradation products, then decreased with increasing absorbed dose.

Removal of organic pollutants in model water and thermal wastewater using clay minerals.

Water treatment method was developed for the removal of different anionic dyes such as methyl orange and indigo carmine, and also for thymol applying sodium bentonite and cationic surfactant - hexadecyltrimethylammonium bromide (HTAB) - or polyelectrolytes (polydiallyldimethylammonium chloride, poly-DADMAC and poly-amines). The removal efficiency of these model substrates was examined in model water using UV-Vis spectrophotometry, HPLC and TOC analysis. The clay mineral and HTAB were added in one step to the polluted model water in Jar-test experiments. The influence of the cation exchange capacity (CEC) of the applied clay mineral and the presence of polyaluminium chloride coagulant (BOPAC) were also tested for the water treatment process. The structures of the in situ produced and pre-prepared organoclay composites were compared by XRD analysis. The rapid formation of organoclay adsorbents provided very efficient removal of the dyes (65-90 % in 3-10 mg/L TOC(0) range) with 200 mg/L sodium bentonite dose, however thymol was less efficiently separated. Adsorption efficiencies of the composites were compared at different levels of ion exchange such as at 40, 60 and 100 %. In the case of thymol, the elimination of inorganic carbon from the model water before the TOC analysis resulted in some loss of the analysed volatile compound therefore the HPLC analysis was found to be the most suitable tool for the evaluation of the process. This one-step adsorption method using in situ formed organoclay was better performing than the conventional process in which the montmorillonite-surfactant composite is pre-preapared and subsequently added to the polluted water. The purification performance of this method was also evaluated on raw and artificially polluted thermal wastewater samples containing added thymol.

TiO2-based photocatalytic degradation of 2-chlorophenol adsorbed on hydrophobic clay.

The combination of adsorption and heterogeneous photocatalysis has been investigated as a promising technology for the removal of organic water pollutants. A laboratory study of the removal and decomposition of 2-chlorophenol (2-CP) as a toxic organic pollutant was carried out under various conditions with an organophilized clay mineral (hexadecylpyridinium chloride-modified montmorillonite; HDPM) as adsorbent and Degussa P25 TiO2 as photocatalyst. Three different oxidation processes leading to the degradation of 2-CP were compared: direct photolysis, heterogeneous photocatalysis in a TiO2 suspension, and the decomposition of substrate adsorbed on HDPM in the presence of TiO2. Both the degradation of 2-CP and the formation of intermediates were analyzed by HPLC, the total organic carbon content and the total organic and inorganic chloride contents were measured to monitor the mineralization process, and X-ray diffraction and thermoanalytical measurements were made to characterize the hydrophobic clay adsorbent. The heterogeneous photocatalytic degradation of dissolved (2-CP/UV/TiO2) and desorbed 2-CP (2-CP/HDPM/UV/TiO2) appeared to be equally efficient, whereas direct photolysis of 2-CP was far less efficient in the oxidative destruction. HDPM proved to be a suitable adsorbent, capable of adsorbing toxic organics from water. It was demonstrated that the adsorbent (at relatively high concentration) did not decrease the rate of mineralization of 2-CP. The results confirmed that the adsorbent retains its structure and composition during the mineralization process, and thus it can be reused without regeneration. The combination of adsorption and heterogeneous photocatalysis studied may be an efficient and economical means of accumulating, removing, and oxidizing organic water contaminants, and its application is in accordance with the growing environmental demands.